CN107487778A - High-pure anhydrous rare earth halide and preparation method thereof - Google Patents

High-pure anhydrous rare earth halide and preparation method thereof Download PDF

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CN107487778A
CN107487778A CN201610410901.7A CN201610410901A CN107487778A CN 107487778 A CN107487778 A CN 107487778A CN 201610410901 A CN201610410901 A CN 201610410901A CN 107487778 A CN107487778 A CN 107487778A
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rare earth
earth halide
crude product
anhydrous
anhydrous rare
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CN107487778B (en
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余金秋
张辉
刁成鹏
吴浩
刘荣辉
何华强
胡运生
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China Youyan Technology Group Co ltd
Grirem Advanced Materials Co Ltd
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Grirem Advanced Materials Co Ltd
Beijing General Research Institute for Non Ferrous Metals
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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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention discloses a kind of method for preparing high-pure anhydrous rare earth halide, using the hydrolysis of rare earth halide crude product to produce HX gases, and then carries out deoxygenation purifying to rare earth halide crude product using HX gases are dried, acquisition formula is REX3High-pure anhydrous rare earth halide, wherein RE be selected from rare earth element La and Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y any one, X is halogens Cl or Br.In addition, the invention also discloses the high-pure anhydrous rare earth halide obtained by this method and the scintillation crystal, ceramics or the thin-film material that are prepared by the high-pure anhydrous rare earth halide.The anhydrous rare earth halide prepared using this method is free of the crystallization water and oxide impurity, has very high purity and good uniformity, and cost is cheap, can meet the application demand of the materials such as scintillation crystal, scintillating ceramic.

Description

High-pure anhydrous rare earth halide and preparation method thereof
Technical field
The invention belongs to field of light emitting materials, and in particular to inorganic scintillation material, more particularly, to a kind of high-pure anhydrous Rare earth halide and preparation method thereof.
Background technology
Scintillation material is that one kind can send ultraviolet or optical photon material after the energy of high-energy ray or particle is absorbed Material.It can be used for the detection of the high energy particles such as high-energy ray and neutron such as alpha ray, gamma-rays, X ray, in nuclear medicine, high energy Physics, safety inspection, industrial non-destructive flaw detection, space physics and core mine locating etc. extensive application.They are generally with monocrystalline The form of body is applied, and can also be glass, ceramics or other forms in some circumstances.
Because of the excellent scintillation properties such as its High Light Output, high energy resolution, fast decay, rare earth halide scintillation material (such as LaCl3:Ce、LaBr3:Ce、CeBr3、Cs2LiYCl6:Ce etc.) get more and more people's extensive concerning, in high-energy physics, safety inspection Look into, there is good application prospect in the field such as oil well logging, medical imaging.These scintillation materials are generally with high-pure anhydrous rare earth oxyhalide Compound is that raw material carries out crystal growth or preparation.However, due to rare earth halide easily deliquescence and oxidation, preparation is very difficult, Cost is very expensive, and existing market price is up to first per kilograms up to ten thousand, so as to seriously hinder the further development of scintillation material And application.Therefore, if a kind of simple, efficient and cheap cost method can be found, it is possible to achieve high-pure anhydrous rare earth halide Prepared by the low-coat scaleization of thing, great impetus is played in development and application that will be to rare earth halide scintillation material.
The content of the invention
An object of the present invention is to provide a kind of simple and effective and the cheap high-pure anhydrous rare earth halide of cost Preparation method.The second object of the present invention is to provide the high-pure anhydrous rare earth halide that above-mentioned preparation method obtains, the height It is inclined that pure anhydrous rare earth halide effectively overcomes impurity present in prior art (especially water and oxide impurity) content The defects of high, it can fully meet the preparation demand of scintillation crystal, ceramics or thin-film material.The third object of the present invention is to provide A kind of scintillation crystal, ceramics or thin-film material being prepared by above-mentioned high-pure anhydrous rare earth halide.
In order to achieve the above object, the present invention intends using following technical scheme：One kind prepares high-pure anhydrous rare earth halide Method, produce HX gases using the hydrolysis of rare earth halide crude product, and then using drying HX gases to rare earth halide Thing crude product carries out deoxygenation purifying, and acquisition formula is REX3High-pure anhydrous rare earth halide, wherein RE be selected from rare-earth elements La, Any one in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y, X is halogens Cl or Br.
More specifically, preparation in accordance with the present invention comprises the following steps：
(1) anhydrous rare earth halide crude product is obtained, is divided into three parts R1, R2 and R3；
(2) HX gases are produced by anhydrous rare earth halide crude product R1 hydrolysis；
(3) HX gases are dried using anhydrous rare earth halide crude product R2 as drier；
(4) using HX gases are dried to anhydrous rare earth halide crude product R3 progress deoxygenation purifying, acquisition formula is REX3It is high-purity Anhydrous rare earth halide.
Further, the step (1) is：The rare earth oxide of purity >=99.9% or carbonate or hydroxide is molten In halogen acids, the settled solution of rare earth halide is obtained, the aqueous salt of rare earth halide, subsequent vacuum are obtained after evaporation and concentration Dehydration obtains anhydrous rare earth halide crude product.Wherein, vacuum dehydration can take technology well known to those skilled in the art.One In individual embodiment, the aqueous salt of rare earth halide can be placed in quartz container, connection vacuum plant and heating fill Put and vacuum dehydration is carried out to it.Anhydrous rare earth halide crude product R1, R2 and the R3 of step (1) three parts mass ratio is 10- 30：10-20：50-80, preferable mass ratio are 15-30：15-20：50-70, most preferred mass ratio are 15-25：15-20： 55-70。
Further, the step (2) is：Under inert gas shielding, by the anhydrous rare earth halide crude product of step (1) R1 is heated to 350~700 DEG C, more preferably 450~650 DEG C, most preferably 500~600 DEG C, is subsequently passed aatomized water vapor, passes through Hydrolysis obtains the HX gases containing part inert gas and vapor.Wherein, the example of inert gas includes, but unlimited In nitrogen or argon gas.
Further, the step (3) is：After the anhydrous rare earth halide crude product R2 of step (1) is pulverized as Drier, by HX gases obtained by step (2) by the drying tube filled with the drier, the moisture in gas is removed, is obtained only Drying HX gases containing part inert gas.
Further, the step (4) is：The anhydrous dilute of step (1) is continually fed into by HX gases are dried obtained by step (3) In native halide crude product R3 high-temperature fusant, 1~12h, most preferably more preferably 2~10h, 4~8h are reacted, to remove oxygen therein Compound impurity, cooling, acquisition formula is REX3High-pure anhydrous rare earth halide.Typically, high-pure anhydrous rare earth halide with The form of polycrystalline block is present.
Further, the preparation method also includes producing the anhydrous rare earth halide crude product R1 of the step (2) hydrolysis Thing is re-converted into the step of anhydrous rare earth halide crude product.Typically, the anhydrous rare earth halide crude product R1 water of the step (2) Product after solution is REOX, can be re-converted into anhydrous rare earth halide crude product REX3.In a specific embodiment, institute Step of converting is stated as sour molten, concentration and vacuum dehydration step.
Further, the preparation method also includes producing drying for the anhydrous rare earth halide crude product R2 of the step (3) Thing is re-converted into the step of anhydrous rare earth halide crude product.Typically, the anhydrous rare earth halide crude product R2 of step (3) is done Product after dry (moisture absorption) is REX3Crystallization hydrate, anhydrous rare earth halide crude product REX can be re-converted into3.At one In specific embodiment, the step of converting is vacuum dehydration step.
On the other hand, the present invention relates to a kind of high-pure anhydrous rare earth halide, obtained by foregoing preparation method. Wherein, REX3It is any one in following rare earth halide：LaCl3、CeCl3、GdCl3、YCl3、LaBr3、CeBr3、GdBr3、 YBr3.Preferably, purity >=99.9% of high-pure anhydrous rare earth halide, water content≤20ppm, preferably≤15ppm, more preferably ≤ 12ppm, most preferably≤10ppm；Oxygen content≤100ppm, preferably≤80ppm, more preferably≤60ppm, most preferably≤40ppm.
Another aspect, the present invention relates to a kind of scintillation crystal being prepared by foregoing high-pure anhydrous rare earth halide, Ceramics or thin-film material.
Below will be with LaBr3Preparation exemplified by, technical scheme is illustrated.
In the prior art, high-pure anhydrous LaBr3Preparation generally use ammonium bromide evaporation, concrete operations are as follows：First will La2O3And NH4Br is codissolved in HBr acid, obtains mixed solution.Concentration is then evaporated to it, obtains blocks of solid, afterwards Vacuum dehydration and the processing of de- ammonium are carried out again, obtain anhydrous LaBr3Product.In this method, NH4Br, which can be played, suppresses LaBr3Hydrolysis Effect, therefore using anhydrous LaBr made from the method3Product is compared directly to LaBr3Aquo-compound be dehydrated obtained by Product there is higher purity.Nevertheless, the anhydrous LaBr obtained by the method3Product still suffers from that oxygen content is higher to ask Topic, oxygen content is generally in more than 200ppm, it is difficult to control below 100ppm.If the anhydrous LaBr prepared using this method3 Crystal growth is carried out as raw material, is easy to form foggy inclusion group because of the enrichment of micro amount of oxygen compound impurity in crystal, sternly Ghost image rings the transparency and scintillation properties of crystal.In addition, ammonium bromide evaporation needs to use substantial amounts of NH4Br, and NH4Br is easily waved Hair, the characteristic easily condensed, it is easy to cause pipeline obstruction during vacuum dehydration and de- ammonium, cause equipment fault.Therefore, bromination There is also larger difficulty for the production amplification of ammonium evaporation.
In view of the above-mentioned problems, it has been recognised by the inventors that a kind of simple efficient deoxygenation means of purification is found, effectively to reduce rare earth Oxygen content in halide, it is to solve LaBr3The key of the higher problem of product oxygen content.Therefore, inventor has carried out a large amount of realities Test, find using high-purity dry HBr gases to LaBr3Melt carries out high temperature bromination, is a kind of effective way for reducing oxygen content, It can simply and efficiently obtain the high-pure anhydrous LaBr with low oxygen content, high homogeneity3Product.But commercially available high-purity drying HBr gases are prohibitively expensive, are worth the actual use of this method and are restricted.For this reason, it is necessary to further develop high-purity Dry the low-cost high-efficiency technology of preparing of HBr gases.
The present invention is ingenious to utilize LaBr3Characteristic susceptible to hydrolysis, passes through LaBr3Hydrolysis produce HBr gases, then Utilize LaBr3Superpower hygroscopicity, with LaBr3Powder is that HBr gases are dried drier, obtains drying HBr gases, most Afterwards using dry HBr gases to LaBr3Deoxygenation purifying is carried out, so as to obtain high-pure anhydrous LaBr3Product.It is first sharp during practical operation Anhydrous LaBr is obtained with simple vacuum dehydration method3Crude product, is then divided into three parts, and Part I is used for hydrolyzing system HBr gases, Part II are used as drier after being ground into powder, and Part III is used for obtaining finally as the raw material that deoxygenation purifies High-pure anhydrous LaBr3Product.Part I LaBr3Product after hydrolysis is LaOBr, is reused for producing after theobromine is molten anhydrous LaBr3Crude product, Part II LaBr3Product after moisture absorption is LaBr3Crystallization hydrate, can also be reused for producing nothing Water LaBr3Crude product.Therefore, this method can realize that the efficient circulation of rare earths material utilizes, and totle drilling cost is relatively low.This method is expanded To the preparation of other similar anhydrous rare earth chlorine, bromide, discovery also all has good effect.
Compared with prior art, preparation method of the invention is simple to operate, and cost is cheap, is easy to produce in enormous quantities, gained Product purity is very high, and particularly oxide impurity content is extremely low, can fully meet the needs of materials such as scintillation crystal, ceramics.
Embodiment
Further details of the present invention, its target and advantage will carry out more detailed here with reference to following non-limiting examples Carefully explain.It will be apparent to one skilled in the art that many such embodiments are feasible, and implementation given below Example is used only for illustrative purpose.These should not be interpreted as limiting the scope of the present invention in any way.
Embodiment 1：Accurately weigh 5kg La2O3(99.99%), it is dissolved in hydrobromic acid and obtains LaBr3Settled solution, heating are dense Blocks of solid is obtained after contracting.Connection vacuum and heater progress vacuum in quartz container is contained in after blocks of solid is crushed to take off Water, obtain the anhydrous LaBr of about 11.5kg3Crude product, detect its averaged Oxygen content about 650ppm.Take the anhydrous LaBr of wherein 2kg3Crude product, 600 DEG C are heated under Ar gas shieldeds and is passed through aatomized water vapor, HBr gases are produced in hydrolysis.Gas it will be imported caused by reaction Equipped with the anhydrous LaBr of 2kg3The quartzy drier of crude powder is dried, and imports 7.5kg again afterwards and is heated to 800 DEG C anhydrous LaBr3In melt, sustained response about 4h.The high-pure anhydrous LaBr of about 7.5kg are obtained after cooling3Block, detect its averaged Oxygen content about 40ppm。
Embodiment 2：Accurately weigh 5kg Ce2(CO3)3(99.95%), it is dissolved in hydrobromic acid and obtains CeBr3Settled solution, add Blocks of solid is obtained after heat concentration.It is contained in after blocks of solid is crushed in quartz container and connects vacuum and heater progress vacuum Dehydration, obtains the anhydrous CeBr of about 11.6kg3Crude product, detect its averaged Oxygen content about 850ppm.Take the anhydrous CeBr of wherein 2kg3Slightly Product, 500 DEG C are heated under Ar gas shieldeds and is passed through aatomized water vapor, HBr gases are produced in hydrolysis.Gas caused by reaction is led Enter the anhydrous CeBr of 2kg are housed3The quartzy drier of crude powder is dried, and imports the nothing that 7.6kg is heated to 820 DEG C again afterwards Water CeBr3In melt, sustained response about 6h.The high-pure anhydrous CeBr of about 7.6kg are obtained after cooling3Block, detect its averaged Oxygen content About 30ppm.
Embodiment 3：Accurately weigh 5kg Ce2(CO3)3(99.95%), it is dissolved in hydrochloric acid and obtains CeCl3Settled solution, heating Blocks of solid is obtained after concentration.Connection vacuum and heater progress vacuum in quartz container is contained in after blocks of solid is crushed to take off Water, obtain the anhydrous CeCl of about 5.4kg3Crude product, detect its averaged Oxygen content about 750ppm.Take the anhydrous CeCl of wherein 1kg3Crude product, N2350 DEG C are heated under gas shielded and is passed through aatomized water vapor, HCl gases are produced in hydrolysis.Dress will be imported caused by reaction by gas There are the anhydrous CeCl of 1kg3The quartzy drier of crude powder is dried, and imports again be heated to 900 DEG C of anhydrous CeCl afterwards3It is molten In body (3.4kg), sustained response about 2h.The high-pure anhydrous CeCl of about 3.4kg are obtained after cooling3Block, detect its averaged Oxygen content About 50ppm.
Embodiment 4：Accurately weigh 5kg Gd2O3(99.99%), it is dissolved in hydrobromic acid and obtains GdBr3Settled solution, heating are dense Blocks of solid is obtained after contracting.Connection vacuum and heater progress vacuum in quartz container is contained in after blocks of solid is crushed to take off Water, obtain the anhydrous GdBr of about 11kg3Crude product, detect its averaged Oxygen content about 1200ppm.Take the anhydrous GdBr of wherein 3kg3Crude product, N2450 DEG C are heated under gas shielded and is passed through aatomized water vapor, HBr gases are produced in hydrolysis.Dress will be imported caused by reaction by gas There are the anhydrous GdBr of 2kg3The quartzy drier of crude powder is dried, and imports again be heated to 920 DEG C of anhydrous GdBr afterwards3It is molten In body (6kg), sustained response about 8h.The high-pure anhydrous GdBr of about 6kg are obtained after cooling3Block, detect its averaged Oxygen content about 90ppm。
Embodiment 5：Accurately weigh 5kg Y2O3(99.99%), it is dissolved in hydrochloric acid and obtains YCl3Settled solution, after heating concentration Obtain blocks of solid.It is contained in after blocks of solid is crushed in quartz container and connects vacuum and heater progress vacuum dehydration, is obtained To the anhydrous YCl of about 8.6kg3Crude product, detect its averaged Oxygen content about 900ppm.Take the anhydrous YCl of wherein 2kg3Crude product, in N2Gas is protected 700 DEG C are heated under shield and is passed through aatomized water vapor, HCl gases are produced in hydrolysis.Gas caused by reaction is imported 1.5kg is housed Anhydrous YCl3The quartzy drier of crude powder is dried, and imports again be heated to 800 DEG C of anhydrous YCl afterwards3Melt In (5.1kg), sustained response about 5h.The high-pure anhydrous YCl of about 5.1kg are obtained after cooling3Block, detect its averaged Oxygen content about 60ppm。
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies Change, equivalent substitution, improvement etc., should be included in the scope of the protection.

Claims (15)

  1. A kind of 1. method for preparing high-pure anhydrous rare earth halide, it is characterised in that the hydrolysis using rare earth halide crude product is anti- Should be to produce HX gases, and then deoxygenation purifying is carried out to rare earth halide crude product using HX gases are dried, acquisition formula is REX3 High-pure anhydrous rare earth halide, wherein RE be selected from rare earth element La and Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Any one in Yb, Lu, Sc, Y, X is halogens Cl or Br.
  2. 2. preparation method according to claim 1, the method includes the steps of：
    (1) anhydrous rare earth halide crude product is obtained, is divided into three parts R1, R2 and R3；
    (2) HX gases are produced by anhydrous rare earth halide crude product R1 hydrolysis；
    (3) HX gases are dried using anhydrous rare earth halide crude product R2 as drier；
    (4) using HX gases are dried to anhydrous rare earth halide crude product R3 progress deoxygenation purifying, acquisition formula is REX3High-purity nothing Water rare earth halide.
  3. 3. preparation method according to claim 2, wherein, the step (1) is：By the rare-earth oxidation of purity >=99.9% Thing or carbonate or hydroxide are dissolved in halogen acids, obtain the settled solution of rare earth halide, rare earth is obtained after evaporation and concentration The aqueous salt of halide, subsequent vacuum dehydration obtain anhydrous rare earth halide crude product.
  4. 4. preparation method according to claim 2, wherein, the anhydrous rare earth halide crude product of three parts of the step (1) R1, R2 and R3 mass ratio are 10-30：10-20：50-80.
  5. 5. preparation method according to claim 2, wherein, the step (2) is：Under inert gas shielding, by step (1) anhydrous rare earth halide crude product R1 is heated to 350~700 DEG C, is subsequently passed aatomized water vapor, is obtained by hydrolysis HX gases containing part inert gas and vapor.
  6. 6. preparation method according to claim 2, wherein, the step (3) is：By the anhydrous rare earth halide of step (1) Thing crude product R2 is used as drier after pulverizing, and by HX gases obtained by step (2) by the drying tube filled with the drier, goes Except the moisture in gas, obtain comprising only the drying HX gases of part inert gas.
  7. 7. preparation method according to claim 2, wherein, the step (4) is：HX gases will be dried obtained by step (3) It is continually fed into the anhydrous rare earth halide crude product R3 high-temperature fusant of step (1), 1~12h is reacted, to remove oxidation therein Thing impurity, cooling, acquisition formula is REX3High-pure anhydrous rare earth halide.
  8. 8. preparation method according to claim 2, in addition to the water by the anhydrous rare earth halide crude product R1 of the step (2) The step of solution product is re-converted into anhydrous rare earth halide crude product.
  9. 9. preparation method according to claim 8, wherein, the step of converting is sour molten, concentration and vacuum dehydration step.
  10. 10. preparation method according to claim 2, in addition to by the anhydrous rare earth halide crude product R2's of the step (3) Desciccate is re-converted into the step of anhydrous rare earth halide crude product.
  11. 11. preparation method according to claim 10, wherein, the step of converting is vacuum dehydration step.
  12. 12. a kind of high-pure anhydrous rare earth halide, it is characterised in that pass through the preparation side described in any one of claim 1~11 Method obtains.
  13. 13. high-pure anhydrous rare earth halide according to claim 12, wherein, REX3It is appointing in following rare earth halide Meaning is a kind of：LaCl3、CeCl3、GdCl3、YCl3、LaBr3、CeBr3、GdBr3、YBr3。
  14. 14. high-pure anhydrous rare earth halide according to claim 12, it is characterised in that purity >=99.9%, water content ≤ 20ppm, oxygen content≤100ppm.
  15. 15. the flicker that a kind of high-pure anhydrous rare earth halide by described in any one of claim 12~14 is prepared is brilliant Body, ceramics or thin-film material.
CN201610410901.7A 2016-06-13 2016-06-13 High-purity anhydrous rare earth halide and preparation method thereof Active CN107487778B (en)

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WO2019128388A1 (en) * 2017-12-27 2019-07-04 有研稀土新材料股份有限公司 Rare earth halide scintillation material and application thereof
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
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
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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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
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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