CN107215887B - The preparation method of anhydrous bromination cerium - Google Patents
The preparation method of anhydrous bromination cerium Download PDFInfo
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- CN107215887B CN107215887B CN201710432970.2A CN201710432970A CN107215887B CN 107215887 B CN107215887 B CN 107215887B CN 201710432970 A CN201710432970 A CN 201710432970A CN 107215887 B CN107215887 B CN 107215887B
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- bromination
- cerium
- anhydrous
- bromination cerium
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Abstract
The present invention provides a kind of preparation method of anhydrous bromination cerium, it is using cerous acetate hydrate as cerium source, in HBr gases or NH4The lower dehydration bromination of Br protections prepares bromination cerium powder, and gained bromination cerium powder melts the anhydrous bromination cerium that postcooling is less than 100ppm up to water content under protective atmosphere or vacuum condition.Compared to cerous carbonate, select cerous acetate hydrate that there is obvious advantage as the cerium source for being used to prepare anhydrous bromination cerium：Dehydration is easier, and can effectively control the content of the objectionable impurities such as water in product, oxygen；Operating procedure is simple, and reaction condition is easily reached, and production cost is low, is very beneficial for realizing the large-scale batch production of anhydrous bromination cerium.
Description
Technical field
The invention belongs to rare earth material field of deep, specifically, is related to a kind of preparation method of anhydrous bromination cerium.
Background technology
The halide of rare-earth element cerium has very extensive purposes, including:1. molten-salt electrolysis is produced metallic cerium, is prepared only
Change catalyst, multicomponent complex etc.；2. the Doped ions as scintillation crystal：Such as Ce：LaCl3、Ce：LaBr3、Ce：LuI3、Ce：
YI3、Ce：K2LaBr5Generally there is the characteristics such as specular removal, fast decay, high energy resolution Deng, these crystal, be particularly suitable for modern doctor
Study the growth requirement of picture, especially Ce：LaBr3, it has very high luminescence yield (about 60000p/MeV), shines faster
Damping time constant (about 16ns) and high energy resolution (about 3%)；3. as scintillation crystal：CeBr3Scintillation crystal has very
High luminescence yield (about 45000p/MeV), high energy resolution (about 4%), compared to Ce：LaBr3Although its performance indicator is omited
Difference, but its intrinsic noise is lower, purposes is also quite varied.
The bromination cerium preparation method reported mainly includes two classes：(1) reacted by metallic cerium and hydrogen bromide or bromine vapor
To prepare bromination cerium.The advantages of this method is the participation that reaction process does not have water, oxygen, at utmost avoids CeOBr and CeO2
Generation, shortcoming is that cerium very active danger coefficient is high, bromine toxicity is big, is difficult to realize large-scale production.(2) using cerous carbonate as
Cerium source, CeBr is generated with HBr reactant aqueous solutions3·7H2O, is then dehydrated under bromination hydrogen stream or ammonium bromide protection.This method
The advantages of be that reaction is simple, easily expand, easily accomplish scale production, shortcoming is water content height, dehydration temperaturre it is high (>220 DEG C), office
Portion's temperature control is bad easily to generate CeOBr and CeO2, it is difficult to ensure the purity and uniformity of product.
2Ce6HBr→2CeBr3+3H2
(1)
2Ce+3Br2→2CeBr3
The content of the invention
The object of the present invention is to provide a kind of method that anhydrous bromination cerium is prepared using cerous acetate hydrate as cerium source.
In order to realize the object of the invention, the preparation method of novel anhydrous bromination cerium provided by the invention, it is with cerous acetate
Hydrate is cerium source, in HBr gases or NH4The lower dehydration bromination of Br protections prepares bromination cerium powder (water content is less than 100ppm),
Gained bromination cerium powder melts the anhydrous bromination that postcooling is less than 100ppm up to water content under protective atmosphere or vacuum condition
Cerium.
The present invention selects cerous acetate hydrate as cerium source, particularly preferred Ce (CH3COO)3·1.5H2O.Other cerous acetates
Hydrate such as Ce (CH3COO)3·2H2O、Ce(CH3COO)3·3H2O etc., can low temperature (<80 DEG C) predrainage is Ce
(CH3COO)3·1.5H2O。
Specific technical solution is as follows：
Circuit 1：The lower dehydration bromination of HBr protections prepares anhydrous bromination cerium
By 0.1-200kg (preferably 1-5kg) Ce (CH3COO)3·1.5H2O is in HBr air-flows, or is containing 1%-10%
Under the high-purity argon gas or high pure nitrogen air-flow of HBr (it is 1-10L/min to control air-flow velocity), 120-150 DEG C keeps 6-12h to slough
The crystallization water, is then progressively warming up to 730-750 DEG C and keeps 1h, is finally cooled to room temperature up to anhydrous bromination cerium (thing block),
Wherein, 1%-10% is percent by volume.
Preferably, with 5 DEG C/min 730-750 DEG C is warming up to from 120-150 DEG C.
Circuit 2：NH4The lower dehydration bromination of Br protections prepares anhydrous bromination cerium
By 0.1-200kg (preferably 1-2kg) Ce (CH3COO)3·1.5H2The NH of O and 6-12 molar equivalents4Br is uniformly mixed
Close, under vacuum condition (0.1Pa-100Pa), 120-150 DEG C keeps 6-12h to slough the crystallization water, is then progressively warming up to 350-
400 DEG C and 3h is kept, be then progressively warming up to 730-750 DEG C and keep 1h, be finally cooled to room temperature up to anhydrous bromination cerium (thing
It is block).
Preferably, with 5 DEG C/min 350-400 DEG C is warming up to from 120-150 DEG C；It is warming up to 5 DEG C/min from 350-400 DEG C
730-750℃。
The present invention has the following advantages：
With it is existing the method for anhydrous bromination cerium is prepared for cerium source with cerous carbonate (cerium carbonate hydrate) compared with, selection cerous acetate water
Compound is as the advantage in cerium source, on the one hand, cerous carbonate usually contains 8 crystallizations water, is not easy to remove whole crystallizations water, and vinegar
Sour cerium is easy to dehydration and obtains the low hydrate with 1.5 crystallizations water of water content；On the other hand, cerous acetate sloughs 1.5
Crystallization water required temperature is 80-150 DEG C lower than cerous carbonate or bromination cerium crystalline hydrate, it is not easy to generates CeOBr and CeO2Impurity.
Method provided by the invention can effectively control the content of the objectionable impurities such as water in product, oxygen, product purity it is high (99.5% with
On)；Operating procedure is simple, product yield height (more than 95%)；Reaction condition is easily reached, and production cost is low, is very beneficial for reality
The large-scale batch production of existing anhydrous bromination cerium.
Embodiment
The present invention is further described below by embodiment.Raw material, reagent used in following embodiments and
Instrument can be obtained by way of buying commercial product.
The lower dehydration bromination of embodiment 1-3 HBr protections prepares anhydrous bromination cerium
By Ce (CH3COO)3·1.5H2O is pushed into tube furnace after being placed in crucible, is passed through protective atmosphere, is protected under temperature T1
Hold time S1 and slough the crystallization water, be then progressively warming up to temperature T2 and retention time S2, be finally cooled to room temperature and obtain anhydrous bromine
Change cerium thing block, cassette acrylonitrile by Coulometry product water content.
Material amounts, preparation condition and product index are shown in Table 1 in embodiment 1-3.
Table 1
Embodiment 4-6 NH4The lower dehydration bromination of Br protections prepares anhydrous bromination cerium
By Ce (CH3COO)3·1.5H2O and NH4Br is uniformly mixed, and is placed in vacuum Muffle furnace, in vacuum condition (vacuum
Spend P1) under, retention time S1 sloughs the crystallization water under temperature T1, is then progressively warming up to temperature T2 and retention time S2, then
Temperature T3 and retention time S3 are progressively warming up to, is cooled to room temperature under last vacuum condition up to anhydrous bromination cerium thing block, cassette
Acrylonitrile by Coulometry product water content.
Material amounts, preparation condition and product index are shown in Table 2 in embodiment 4-6.
Table 2
According to anhydrous bromination cerium product made from above-described embodiment 1-6, with existing method made from anhydrous bromination cerium product
Compare, product purity is high, and impurity content is low, available for the doping of high-performance scintillation crystal containing cerium or the life of bromination cerium scintillator
It is long.
Embodiment described above is only to absolutely prove the preferred embodiment of the invention enumerated, protection scope of the present invention
Not limited to this.The equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, the present invention's
Within protection domain.
Claims (6)
1. the preparation method of anhydrous bromination cerium, it is characterised in that using cerous acetate hydrate as cerium source, in HBr gases or NH4Br is protected
The lower dehydration bromination of shield prepares bromination cerium powder, and gained bromination cerium powder melts postcooling under protective atmosphere or vacuum condition to obtain the final product
Water content is less than the anhydrous bromination cerium of 100ppm；
The cerous acetate hydrate is selected from Ce (CH3COO)3·1.5H2O、Ce(CH3COO)3·2H2O、Ce(CH3COO)3·3H2O
At least one of；If the cerous acetate hydrate is Ce (CH3COO)3·1.5H2O, then directly in HBr gases or NH4Br is protected
The lower dehydration bromination of shield prepares bromination cerium powder, and gained bromination cerium powder melts postcooling under protective atmosphere or vacuum condition to obtain the final product
Water content is less than the anhydrous bromination cerium of 100ppm, otherwise, first by Ce (CH3COO)3·2H2O or Ce (CH3COO)3·3H2O is small
Predrainage is carried out under 80 DEG C of state of temperature, obtains Ce (CH3COO)3·1.5H2O, then in HBr gases or NH4Br is protected
Lower dehydration bromination prepares bromination cerium powder, and gained bromination cerium powder melts postcooling up to water under protective atmosphere or vacuum condition
Content is less than the anhydrous bromination cerium of 100ppm；
Wherein, the bromination that is dehydrated under HBr gas shields prepares bromination cerium powder, gained bromination cerium powder in protective atmosphere or
The anhydrous bromination cerium that postcooling is less than 100ppm up to water content is melted under vacuum condition, including：By 0.1-200kg Ce
(CH3COO)3·1.5H2O is in HBr air-flows, or under the high-purity argon gas containing 1%-10%HBr or high pure nitrogen air-flow,
120-150 DEG C of holding 6-12h, is then progressively warming up to 730-750 DEG C and keeps 1h, be finally cooled to room temperature up to anhydrous bromination
Cerium, wherein, 1%-10% is percent by volume；
It is described in NH4The lower dehydration bromination of Br protections prepares bromination cerium powder, and gained bromination cerium powder is in protective atmosphere or vacuum condition
Lower melting postcooling is less than the anhydrous bromination cerium of 100ppm up to water content, including：By 0.1-200kg Ce (CH3COO)3·
1.5H2The NH of O and 6-12 molar equivalents4Br is uniformly mixed, and under vacuum, 120-150 DEG C of holding 6-12h, then progressively rises
Temperature is to 350-400 DEG C and keeps 3h, is then progressively warming up to 730-750 DEG C and keeps 1h, is finally cooled to room temperature up to anhydrous
Bromination cerium.
2. according to the method described in claim 1, it is characterized in that, it is 1-10L/min to control air-flow velocity.
3. method according to claim 1 or 2, it is characterised in that 730-750 is warming up to from 120-150 DEG C with 5 DEG C/min
℃。
4. according to the method described in claim 1, it is characterized in that, the vacuum condition is 0.1Pa-100Pa.
5. the method according to claim 1 or 4, it is characterised in that 350-400 is warming up to from 120-150 DEG C with 5 DEG C/min
℃。
6. the method according to claim 1 or 4, it is characterised in that 730-750 is warming up to from 350-400 DEG C with 5 DEG C/min
℃。
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| CN109502628A (en) * | 2018-12-29 | 2019-03-22 | 厦门中烁光电科技有限公司 | It is anhydrous to mix cerium lanthanum bromide and preparation method thereof |
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| FR2840926B1 (en) * | 2002-06-12 | 2005-03-04 | Saint Gobain Cristaux Detecteu | USE OF A CRUSH WITH CARBON FOR CRYSTAL GROWTH COMPRISING A RARE EARTH HALIDE |
| FR2847594B1 (en) * | 2002-11-27 | 2004-12-24 | Saint Gobain Cristaux Detecteu | PREPARATION OF RARE EARTH HALIDE BLOCKS |
| CN101891237B (en) * | 2010-07-29 | 2013-11-20 | 中国计量学院 | Method for preparing high-purity anhydrous bromide |
| CN102502755B (en) * | 2011-10-28 | 2013-07-03 | 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 |
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