CN112744854A - Rare earth fluoride and preparation method and application thereof - Google Patents
Rare earth fluoride and preparation method and application thereof Download PDFInfo
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- CN112744854A CN112744854A CN202011562700.1A CN202011562700A CN112744854A CN 112744854 A CN112744854 A CN 112744854A CN 202011562700 A CN202011562700 A CN 202011562700A CN 112744854 A CN112744854 A CN 112744854A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 66
- -1 Rare earth fluoride Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 239000002699 waste material Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 27
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 20
- ANDNPYOOQLLLIU-UHFFFAOYSA-N [Y].[Lu] Chemical compound [Y].[Lu] ANDNPYOOQLLLIU-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- 238000003682 fluorination reaction Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 229910004014 SiF4 Inorganic materials 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 229910052727 yttrium Inorganic materials 0.000 abstract 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910003443 lutetium oxide Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002600 positron emission tomography Methods 0.000 description 3
- APFWLFUGBMRXCS-UHFFFAOYSA-N 4,7-dihydroxy-3-phenylchromen-2-one Chemical compound O=C1OC2=CC(O)=CC=C2C(O)=C1C1=CC=CC=C1 APFWLFUGBMRXCS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YGGJBIMSYKHGAW-UHFFFAOYSA-H [F-].[Lu+3].[Y+3].[F-].[F-].[F-].[F-].[F-] Chemical compound [F-].[Lu+3].[Y+3].[F-].[F-].[F-].[F-].[F-] YGGJBIMSYKHGAW-UHFFFAOYSA-H 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- RCEDACFKCNENSO-UHFFFAOYSA-N cerium lutetium Chemical compound [Ce][Lu] RCEDACFKCNENSO-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C01F17/265—Fluorides
-
- 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
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/1601—Solid materials characterised by an active (lasing) ion
- H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a rare earth fluoride and a preparation method and application thereof, wherein the method comprises the following steps: and carrying out heat treatment on the powder of the scintillation crystal waste in a mixed atmosphere, and then cooling in a protective atmosphere to obtain the rare earth fluoride. The invention crushes and grinds the scintillation crystal waste into fine powder, dries at high temperature in vacuum after washing to remove water and impurities, then carries out high-temperature treatment to convert silicon and oxygen elements in lutetium oxyorthosilicate (yttrium) into gaseous SiF4And H2Discharging O, and absorbing with alkali solution. The high-purity rare earth fluoride in the fluorination reaction furnace is naturally cooled and taken out, can be used for preparing high-purity metals, fluorescent materials, special additives and other high-end materials, and can be used for preparing high-purity metals, fluorescent materials, special additives and other high-end materials due to extremely low impurity and oxygen contentsThe original method is used for preparing high-purity rare earth metal.
Description
Technical Field
The invention relates to the field of solid waste recycling, in particular to a rare earth fluoride and a preparation method and application thereof.
Background
Rare earth is called as industrial gold, has excellent physical properties such as photoelectromagnetism and the like, can form novel materials with various properties and varieties with other materials, is widely applied to more than 40 industries in 13 fields such as metallurgical machinery, petrochemical industry, light industry and agriculture, electronic information, energy environmental protection, national defense and military industry, high and new materials and the like, is a traditional industry for transformation of countries in the world at present, and is indispensable strategic material for developing high and new technologies and national defense advanced technologies.
In recent years, lutetium-based compounds have attracted great interest due to their advantages of high density and rapid decay, and become a research focus in this field, especially lutetium silicate (Lu)2SiO5LSO), lutetium yttrium silicate (Lu)2(1-x)Y2xSiO5LYSO) as representative lutetium-based scintillation crystal, which integrates a plurality of advantages of high density, short afterglow, high light yield and the like into a whole and has become a substituted Bi4Ge3O12The emergence of (BGO) crystals for the most powerful competitors of PET (positron emission tomography) equipment, especially the commercial clinical LSO crystal-based PET devices, has accelerated the consumption of LSO crystals. But at least 20% of cutting scraps are generated in the production process of the LSO crystal, lutetium is one of the most valuable and deficient rare earth elements, the lutetium oxide content in the waste material is up to more than 70%, and the recovery value is very high.
At present, researches on comprehensive recovery of rare earth elements from lutetium (yttrium) silicate scintillation crystal waste are few, and the adopted method mainly comprises the steps of extracting the rare earth elements into acid leaching solution by using a high-concentration strong acid solution, then separating and recovering the rare earth elements by using an organic extractant through regulating the pH value of the acid leaching solution, and preparing rare earth oxides through precipitation and ignition. For example, CN110042245A discloses a method for recovering and purifying lutetium from lutetium yttrium silicate scintillation crystal waste, which comprises using lutetium yttrium silicate waste obtained by laser cutting lutetium yttrium silicate scintillation crystal as raw material, mixing the raw material with alkali fusing agent according to a certain proportion, carrying out thermal decomposition at a certain temperature, cooling, leaching with hydrochloric acid, and converting lutetium yttrium silicate into lutetium yttrium chloride solution. And the lutetium yttrium chloride solution after sodium and silicon removal is synergistically extracted and separated by P507 and C272 to obtain purified LuCl3The liquid is precipitated by oxalic acid, burned and the like to synthesize the high-purity lutetium oxide, and the purity of lutetium reaches 99.999 percent.
CN103436719A discloses lutetium oxide recovered from scintillation crystal waste doped with lutetium cerium aluminate and a recovery method. The method comprises the following steps:
s1, adding sodium hydroxide and/or potassium hydroxide into the scintillation crystal waste, and roasting to obtain a roasted product;
s2, soaking the roasted product in water, filtering, adding nitric acid and an oxidant into the obtained filter residue, and stirring to obtain a mixed solution;
s3, adding the mixed solution into an organic extractant, and extracting to obtain an extract containing cerium and a raffinate containing lutetium;
s4, adding oxalic acid into the lutetium-containing raffinate, stirring, filtering, and burning the obtained precipitate to obtain lutetium oxide. The process obtains the lutetium oxide with the purity of 99 percent and the recovery rate of 99.5 percent, has short process flow, less equipment investment, simple and easy operation, saves resources, reduces pollution, has huge practical value and provides a new way for recovering lutetium from the scintillation crystal waste material doped with cerium lutetium aluminate.
However, the above treatment process is complicated in operation, high in cost, low in added value and large in water consumption.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a rare earth fluoride and a preparation method and application thereof, so that the purposes of efficient comprehensive utilization of rare earth resources and environment-coordinated development are realized, the high-purity rare earth fluoride is prepared by directly fluorinating lutetium yttrium silicate waste, the added value is high, the operation is simple and convenient, the environment is friendly, and the double benefits of economy and environment are achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing rare earth fluoride from scintillation crystal waste, which comprises the following steps: and carrying out heat treatment on the powder of the scintillation crystal waste in a mixed atmosphere, and then cooling in a protective atmosphere to obtain the rare earth fluoride.
The method comprises the steps of crushing and grinding the scintillation crystal waste into fine powder, washing, drying at high temperature in vacuum to remove water and impurities, and then carrying out the treatment in a specific atmosphereHigh temperature treatment, silicon and oxygen in lutetium oxyorthosilicate are converted into SiF in gas state4And H2Discharging O, and absorbing with alkali solution. The high-purity rare earth fluoride in the reaction device is naturally cooled and then taken out, so that the high-purity rare earth fluoride can be used for preparing high-purity metals, fluorescent materials, special additives and other high-end materials, and can be used for preparing the high-purity rare earth metals by a reduction method due to extremely low impurity and oxygen contents. The invention not only recovers the rare earth elements, but also forms new high-added-value high-purity rare earth fluoride, thereby not only meeting the requirements of saving rare earth resources and reasonably utilizing the rare earth resources, but also reducing the environmental pollution and meeting the requirements of environmental protection. The method separates the rare earth from silicon and oxygen, converts the rare earth into rare earth fluoride with high additional value, thereby achieving the purpose of recovering the rare earth, and has the advantages of simple and easy operation, high additional value, environmental protection, resource saving and environmental protection.
As a preferred technical scheme of the invention, the scintillation crystal waste material comprises lutetium silicate waste material and/or yttrium lutetium silicate waste material.
As a preferable technical scheme of the invention, the powder is obtained by sequentially crushing, screening, cleaning and drying the scintillation crystal.
Preferably, the mesh number of the screen in the screening is 60 to 200 mesh, for example, 60 mesh, 80 mesh, 100 mesh, 120 mesh, 140 mesh, 180 mesh or 200 mesh, etc., but is not limited to the enumerated values, and other values not enumerated within the range are also applicable.
Preferably, the cleaning is performed with water.
Preferably, the drying mode is vacuum drying.
In the invention, the vacuum drying equipment comprises a smelting furnace, a resistance furnace, a box-type atmosphere furnace and the like; removing volatile impurities and moisture at high temperature.
Preferably, the drying temperature is 600-1000 deg.C, such as 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C or 1000 deg.C, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the drying time is 5 to 20 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, or 20 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable technical scheme of the invention, the mixed atmosphere comprises hydrogen fluoride gas and inert gas.
In the present invention, the inert gas may be 1 or a combination of at least 2 of helium, neon, or argon, and the like.
The volume ratio of the hydrogen fluoride gas to the inert gas in the mixed atmosphere is preferably 1 (1-10), and examples thereof include, but are not limited to, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, and 1:10, and other values not listed in the range are also applicable.
In a preferred embodiment of the present invention, the heat treatment temperature is 600-1000 deg.C, and may be, for example, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, or 1000 deg.C, but is not limited to the values listed above, and other values not listed above in this range are also applicable.
In a preferred embodiment of the present invention, the heat treatment time is 10 to 40 hours, and may be, for example, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, or 40 hours, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In the present invention, the reaction furnace in the heat treatment is a static or dynamic rotary furnace, and preferably a rotary furnace. The crucible is made of materials such as graphite or platinum which are resistant to hydrogen fluoride corrosion.
As a preferred embodiment of the present invention, the protective atmosphere comprises nitrogen and/or an inert gas.
As a preferred technical solution of the present invention, the method comprises: carrying out heat treatment on the powder of the scintillation crystal waste in a mixed atmosphere, and then cooling in a protective atmosphere to obtain the rare earth fluoride;
the scintillation crystal waste comprises lutetium silicate waste and/or yttrium lutetium silicate waste; the powder is obtained by sequentially crushing, screening, cleaning and drying the scintillation crystal;
the mixed atmosphere comprises hydrogen fluoride gas and inert gas, and the volume ratio of the hydrogen fluoride gas to the inert gas in the mixed atmosphere is 1 (1-10); the temperature of the heat treatment is 600-1000 ℃, and the time of the heat treatment is 10-40 h.
In a second aspect, the present invention provides a rare earth fluoride obtained by the process of the first aspect, said rare earth fluoride having an oxygen content of < 100ppm, such as 95ppm, 90ppm, 85ppm, 80ppm, 75ppm, 70ppm, 65ppm, 60ppm, 55ppm or 50ppm, but not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the purity of the rare earth fluoride is 99.99% or more, and may be, for example, 99.99%, 99.995%, 99.999%, 99.9995%, 99.9999%, 99.99995%, 99.99999%, or the like, but is not limited to the enumerated values, and other values not enumerated within this range are also applicable.
In a third aspect, the present invention provides the use of a rare earth fluoride as described in the second method for the preparation of one of a high purity metal or a laser crystal.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the method provided by the invention is utilized to separate rare earth from silicon and oxygen, and the rare earth is converted into rare earth fluoride with high addition value, so that the purpose of recovering the rare earth is achieved.
(2) The method is simple and easy to operate, has high added value and environmental protection, has double benefits of resource saving and environmental protection, and can be used for preparing high-purity metal or laser crystals, and the purity of the obtained rare earth fluoride is more than or equal to 99.99%.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a method for preparing rare earth fluoride from scintillation crystal waste, which specifically comprises the following steps:
(1) 500g of lutetium silicate scintillation crystal waste is crushed and sieved by a 100-mesh sieve, and then is washed for 3 times by 50L of deionized water and filtered;
(2) then putting the mixture into a vacuum drying smelting furnace, and keeping the temperature of 600 ℃ for vacuum drying for 10 hours;
(3) putting the dried powder into a high-purity graphite crucible of a fluorination reaction furnace, introducing mixed gas of dry HF gas and Ar gas in a volume ratio of 1:3 for reaction at 700 ℃ for 48 hours to generate gaseous SiF4And H2Absorbing tail gas such as O and the like by a sodium hydroxide solution;
(4) naturally cooling the prepared lutetium fluoride to room temperature under the protection of nitrogen;
the prepared rare earth lutetium fluoride has the purity of 99.99 percent, the yield of 98.5 percent and the oxygen content of 85ppm, and can be used for preparing high-purity metal and laser crystals.
Example 2
The embodiment provides a method for preparing rare earth fluoride from scintillation crystal waste, which specifically comprises the following steps:
(1) 500g of yttrium lutetium silicate scintillation crystal waste is crushed and sieved by a 100-mesh sieve, and then is washed for 3 times by 50L of deionized water and filtered;
(2) then putting the mixture into a vacuum drying smelting furnace, and keeping the temperature at 800 ℃ for vacuum drying for 20 hours;
(3) putting the dried powder into a high-purity graphite crucible of a fluorination reaction furnace, introducing mixed gas of dry HF gas and nitrogen gas in a volume ratio of 1:3 for reaction at 900 ℃ for 10 hours, and generating gaseous SiF in the reaction process4And H2Absorbing tail gas such as O and the like by potassium hydroxide solution;
(4) naturally cooling the prepared yttrium lutetium fluoride to room temperature under the protection of argon;
the obtained rare earth lutetium yttrium fluoride has the purity of 99.99 percent and the oxygen content of 92ppm by analysis, and can be used for preparing rare earth alloy.
Example 3
The embodiment provides a method for preparing rare earth fluoride from scintillation crystal waste, which specifically comprises the following steps:
(1) 500g of yttrium lutetium silicate scintillation crystal waste is crushed and sieved by a 100-mesh sieve, and then is washed for 2 times by 50L of deionized water and filtered;
(2) then putting the mixture into a vacuum drying smelting furnace, and keeping the temperature at 800 ℃ for vacuum drying for 20 hours;
(3) putting the dried powder into a high-purity graphite crucible of a fluorination reaction furnace, introducing mixed gas of dry HF gas and nitrogen gas in a volume ratio of 1:7 for reaction at 700 ℃ for 17 hours, and generating gaseous SiF in the reaction process4And H2Absorbing tail gas such as O and the like by potassium hydroxide solution;
(4) naturally cooling the prepared yttrium lutetium fluoride to room temperature under the protection of argon;
the obtained rare earth lutetium yttrium fluoride has the purity of 99.999 percent and the oxygen content of 72ppm by analysis, and can be used for preparing rare earth alloy.
Example 4
The embodiment provides a method for preparing rare earth fluoride from scintillation crystal waste, which specifically comprises the following steps:
(1) 500g of lutetium silicate scintillation crystal waste is crushed and sieved by a 100-mesh sieve, and then is washed for 3 times by 50L of deionized water and filtered;
(2) then putting the mixture into a vacuum drying smelting furnace, and keeping the temperature of 600 ℃ for vacuum drying for 10 hours;
(3) putting the dried powder into a high-purity graphite crucible of a fluorination reaction furnace, introducing mixed gas of dry HF gas and Ar gas in a volume ratio of 1:10 to react for 12 hours at 1000 ℃ to generate gaseous SiF4And H2Absorbing tail gas such as O and the like by a sodium hydroxide solution;
(4) naturally cooling the prepared lutetium fluoride to room temperature under the protection of nitrogen;
the prepared rare earth lutetium fluoride has the purity of 99.99 percent, the yield of 99.2 percent and the oxygen content of 65ppm, and can be used for preparing high-purity metal or laser crystals.
Comparative example 1
The difference from the example 1 is that the mixed gas in the step (3) does not contain nitrogen, and the prepared rare earth lutetium fluoride has the purity of 98.52%, the yield of 97.1% and the oxygen content of 80 ppm.
Comparative example 2
The difference from the example 1 is only that the volume ratio of the hydrogen fluoride gas to the inert gas in the mixed gas in the step (3) is 0.1:3, and the prepared rare earth lutetium fluoride has the purity of 99.91 percent, the yield of 98.3 percent and the oxygen content of 335 ppm.
Comparative example 3
The only difference from example 1 is that the temperature of the treatment was 500 deg.C, and the rare earth lutetium fluoride was prepared with a purity of 99.69%, a yield of 98.8%, and an oxygen content of 266 ppm.
Comparative example 4
The only difference from example 1 is that the temperature of the treatment was 1200 deg.C, and the rare earth lutetium fluoride was prepared with a purity of 98.12%, a yield of 96.5%, and an oxygen content of 90 ppm.
Comparative example 5
The only difference from example 1 is that the treatment time was 5 hours, and the rare earth lutetium fluoride was prepared with a purity of 98.60%, a yield of 97.3% and an oxygen content of 525 ppm.
As can be seen from the results of the above examples and comparative examples, the method provided by the invention realizes the efficient preparation of the rare earth fluoride by controlling the gas composition of the reaction and the reaction conditions, and the purity of the obtained rare earth fluoride is more than or equal to 99.99%, and the rare earth fluoride can be used for preparing high-purity metal or laser crystal. The invention not only recovers the rare earth elements, but also forms new high-added-value high-purity rare earth fluoride, thereby not only meeting the requirements of saving rare earth resources and reasonably utilizing the rare earth resources, but also reducing the environmental pollution and meeting the requirements of environmental protection.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for preparing rare earth fluoride from scintillation crystal waste, characterized in that the method comprises: and carrying out heat treatment on the powder of the scintillation crystal waste in a mixed atmosphere, and then cooling in a protective atmosphere to obtain the rare earth fluoride.
2. The method of claim 1, wherein the scintillation crystal waste comprises lutetium silicate waste and/or yttrium lutetium silicate waste.
3. The method according to claim 1 or 2, wherein the powder is obtained by subjecting the scintillation crystal to pulverization, sieving, washing, and drying in this order;
preferably, the mesh number of the screen in the screening is 60-200 meshes;
preferably, the cleaning is performed by water;
preferably, the drying mode is vacuum drying;
preferably, the temperature of the drying is 600-;
preferably, the drying time is 5-20 h.
4. The method of any one of claims 1-3, wherein the mixed atmosphere comprises hydrogen fluoride gas and an inert gas;
preferably, the volume ratio of the hydrogen fluoride gas to the inert gas in the mixed atmosphere is 1 (1-10).
5. The method according to any one of claims 1 to 4, wherein the temperature of the heat treatment is 600 ℃ and 1000 ℃.
6. The method according to any one of claims 1 to 5, wherein the heat treatment time is 10 to 40 h.
7. The method of any one of claims 1-6, wherein the protective atmosphere comprises nitrogen and/or an inert gas.
8. The method of any one of claims 1-7, wherein the method comprises: carrying out heat treatment on the powder of the scintillation crystal waste in a mixed atmosphere, and then cooling in a protective atmosphere to obtain the rare earth fluoride;
the scintillation crystal waste comprises lutetium silicate waste and/or yttrium lutetium silicate waste; the powder is obtained by sequentially crushing, screening, cleaning and drying the scintillation crystal;
the mixed atmosphere comprises hydrogen fluoride gas and inert gas, and the volume ratio of the hydrogen fluoride gas to the inert gas in the mixed atmosphere is 1 (1-10); the temperature of the heat treatment is 600-1000 ℃, and the time of the heat treatment is 10-40 h.
9. Rare earth fluoride obtainable by the process according to any of claims 1 to 8, characterized in that it has an oxygen content of < 100 ppm;
preferably, the purity of the rare earth fluoride is more than or equal to 99.99%.
10. Use of rare earth fluorides according to claim 9 for preparing one of high purity metals or laser crystals.
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| CN116768635A (en) * | 2023-07-10 | 2023-09-19 | 兰溪泛翌精细陶瓷有限公司 | Modified silicon nitride composite material and preparation method thereof |
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