CN101805008A - Anhydrous high-purity rare earth fluoride and preparation method thereof - Google Patents

Anhydrous high-purity rare earth fluoride and preparation method thereof Download PDF

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CN101805008A
CN101805008A CN 201010169572 CN201010169572A CN101805008A CN 101805008 A CN101805008 A CN 101805008A CN 201010169572 CN201010169572 CN 201010169572 CN 201010169572 A CN201010169572 A CN 201010169572A CN 101805008 A CN101805008 A CN 101805008A
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rare earth
purity
fluoride
earth fluoride
anhydrous
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CN101805008B (en
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祝文才
高坡
林伟清
陈纪光
钟正天
龚斌
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Qian Dong lanthanide group limited company
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GANZHOU QIANDONG RARE EARTH GROUP CO Ltd
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Abstract

The invention discloses an anhydrous high-purity rare earth fluoride and a preparation method thereof. The anhydrous high-purity rare earth fluoride mainly comprises minim non-rare earth impurity iron (Fe2O3<=1ppm), calcium (CaO<=10ppm), silicon (SiO2<=10ppm), carbon (C<=200ppm), oxygen (O<=200ppm), chloride (Cl<=30ppm), sulfur (S<=10ppm) and the like and has ignition loss not more than 0.5%. The product is mainly applied in the field of electronic and luminescent materials. The preparation method is characterized by pre-removing the non-rare earth impurity by enhancement on the basis of the traditional process and then carrying out conversion in the form of compound fluorinating agents; strictly controlling the feed liquor concentration and acidity, fluorinating agent addition, fluorination temperature and time, etc and obtaining the rare-earth fluoride which is coarse in fluorinated particles, fast in sedimentation and easy to wash and filter; and finally obtaining the anhydrous high-purity rare earth fluoride product through subsequent drying and particle integration.

Description

Anhydrous high-purity rare earth fluoride and preparation method thereof
Technical field
The invention belongs to the technical field of solvent deposition conversion synthesizing rare-earth salt, particularly anhydrous high-purity rare earth fluoride and preparation method thereof.
Background technology
Rare earth fluorine is early stage mainly as the luminous agent of electric arc carbon-point, is filled in the centre of anode carbon stick; As the additive of iron and steel and nonferrous alloy, play desulfurization, deoxidation in addition; The bigger application of rare earth fluorine later on then is that the fluoride system electrolysis is used as fused salt, and it and lithium fluoride, barium fluoride are formed molten salt electrolyte and prepared rare earth metal, are exactly to be used for the raw material that metallothermics prepares the single rare earth metal in addition; Along with science and technology development, rare earth fluorine is used for electronic material, polishing material and changing luminous material field in recent years, more and more is subject to people's attention.
The preparation of rare earth fluorine has two kinds of wet method and dry method, and dry method is that rare earth oxide is directly fluoridized in hydrogen fluoride gas or rare earth oxide mixes with the hydrogen fluoride solid to heat up and fluoridizes; Wet method in earth solution, directly add etching acid or fluoride salt precipitate fluorochemical, drying, vacuum hydro-extraction and make anhydrous fluorochemical again.Present most of manufacturer adopts wet method, though conventional wet process technique is easy and simple to handle, but it is gluey that the rare earth fluorine that is settled out is, be difficult for filtering and washing, the precipitation settling time is long, particularly non-rare earth impurity content height can't directly apply to electronics and field of light emitting materials, thereby anhydrous high-purity rare earth fluoride and preparation method thereof is provided is very necessary.
Summary of the invention
The purpose of this invention is to provide anhydrous high-purity rare earth fluoride and preparation method thereof.The main non-rare earth impurity iron of this anhydrous high-purity rare earth fluoride product (Fe 2O 3≤ 1ppm), calcium (CaO≤10ppm), silicon (SiO 2≤ 10ppm) carbon ((((equal size of S≤10ppm) is trace extremely, and product burns mistake rate≤0.5% for Cl≤30ppm), sulphur for O≤200ppm), chlorine for C≤200ppm), oxygen.This product has that particle is thick, settling velocity is fast, is easy to clarify, filters, washing and the high characteristics of purity, and this product can directly satisfy the demand of electronics and field of light emitting materials.Rare earth fluorine preferred fluorinated yttrium or lanthanum fluoride.
For realizing this purpose, this product preparation process is to realize by following steps:
One, adopts high-purity single re chloride, in advance with N 235Impurity such as extraction agent deironing, zinc, it is stand-by to be purified liquid;
Two, the scavenging solution with step 1 is converted into carbonated rare earth with reagent ammoniacal liquor and refining carbon ammonium adjust pH, with its filter, deionized water wash, centrifuge dehydration obtain high-purity carbonated rare earth solid, this high-purity carbonated rare earth has the characters and appearances that particle is thick, specific surface area is little, and aluminium, silicon, chlorine and other non-rare earth impurity are further purified;
Three, in fluorizating apparatus, size mixing high-purity carbonated rare earth solid and deionized water Hybrid Heating that second step obtained stand-by;
Four, stand-by with deionized water, reagent ammoniacal liquor, reagent hydrofluoric acid preparation compound fluorinating;
Five, the compound fluorinating that step 4 is obtained joins in the described fluorizating apparatus of step 3 and transforms, and under continuous stirring condition, slowly adds compound fluorinating, keeps fluoridizing temperature at 50-60 ℃, fluoridizes the final pH value and is controlled at below 2;
Six, the high-purity rare earth fluoride slurry that step 5 is obtained filters, deionized water wash, centrifuge dehydration obtain the high-purity rare earth fluoride solid;
Seven, the rare earth fluorine solid drying dehydration that step 6 is obtained promptly gets anhydrous high-purity rare earth fluoride product.
Above-mentioned its technology characteristics is:
The described scavenging solution Fe＜0.05mg/L of step 1, Zn＜0.01mg/L etc.
It is 5-7 that step 2 is regulated the pH value.
The described compound fluorinating of step 4, mol ratio HF/NH 4F=1.0-1.5, F/RE=3.5-4.5, concentration HF+NH 4F=3.6-4.2mol/L.
Step 5 was added the refining oxalic acid of an amount of nucleator before transforming, thereby obtained in the improvement mode of fluoridizing that particle is thick, settling velocity is fast, is easy to clarification, washing, filtering rare earth fluorine.
Described fluorizating apparatus adopts not the non-metallic material with the hydrofluoric acid reaction, and perhaps these non-metallic material of liner are guaranteed can not introduce non-rare earth impurity because of equipment corrosion in the fluorination process.
The step 7 drying temperature is 150 ℃-180 ℃, 12-18 hour time of drying.
Follow-uply gained anhydrous high-purity rare earth fluoride particle is integrated 2 hours, sieve and mix and criticize with being not less than 24 mesh sieves, thereby obtain the stable final anhydrous high-purity rare earth fluoride product of particle homogeneity with ceramic ball mill.
Description of drawings
Accompanying drawing is an anhydrous high-purity rare earth fluoride preparation technology schema.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing.
Embodiment 1 high purity anhydrous yttrium fluoride and preparation thereof
The preparation of high-purity Yttrium trichloride scavenging solution
REO concentration: 100-120g/l
Y purity:＞99.999%
Fe 2O 3＜0.05mg/L??CaO＜0.5mg/L??Zn＜0.01mg/L??Na 2O＜0.05mg/L
Free acidity: [H +]≤0.50mol/L
Deionized water (DW)
Resistance＞12 megohms, total salinity＜1mg/l SiO 2＜70 μ g/l
Refining oxalic acid (H 2 C 2 O 4 2H 2 O)
Fe 2O 3＜0.5ppm、CaO＜0.5ppm、SiO 2＜5ppm
Analytical pure hydrofluoric acid (HF)
Content (HF)＞40%
Fe 2O 3＜0.5ppm、CaO＜0.5ppm、SiO 2＜5ppm
Muriate (Cl)＜10ppm phosphoric acid salt＜2ppm
Vitriol and sulphite are (with SO 4Meter)＜20ppm
22% reagent N H 4 OH
Concentration (equivalents): 11.87mol/L
Fe 2O 3＜0.1ppm、CaO＜0.5ppm、SiO 2＜5ppm
Ammonium Bicarbonate, Food Grade solution
[OH -]/[HCO 3 -]＝0.67-0.8
Fe 2O 3＜0.1ppm、CaO＜0.5ppm、SiO 2＜5ppm
Compound fluorinating
Mol ratio HF/NH 4F=1.0-1.5, concentration HF+NH 4F=3.6-4.2mol/L.
Preparation technology
1, at 2M 3In the PVC steel basin with 800L Yttrium trichloride rare earth feed liquid (concentration 1mol/L) and N 235Be in a ratio of the single-stage purifying that is not less than 2 hours at 1: 1 according to volume, stop to stir the clarification phase-splitting, obtain the scavenging solution of non-rare earth such as Fe less than 0.03mg/L;
2, will go up scavenging solution and forward 3M to 3In the precipitation conversion tank, will change into the yttrium carbonate xln with reagent ammoniacal liquor and refining carbon ammonium adjust pH to 5-7 respectively; With this yttrium carbonate xln through filter pocket filtrated stock, with deionized water wash to the specific conductivity＜20 μ S/cm that wash surplus liquid, centrifuge dehydration obtains totally 235 kilograms of high-purity yttrium carbonate solids (total amount of rare earth is 38%) again;
3, at the stirred autoclave (3M of liner Teflon resin 3) in, high-purity yttrium carbonate solid that previous step is obtained with size mixing at 1: 2 according to weight ratio through the deionized water of heating, slurry temperature be controlled at 55-60 ℃ stand-by;
4, the while is at the stirred autoclave (2M of another liner Teflon resin 3) middle with 35 ℃ of deionized waters, reagent ammoniacal liquor, reagent hydrofluorination acid preparation compound fluorinating HF/NH 4F=1.0, F/RE=4.0 (mol ratio), concentration (HF+NH 4F)=4.0N, cumulative volume be 800L, solution temperature be controlled at 25-35 ℃ stand-by;
5, the compound fluorinating that step 4 is obtained joins in the step 3 and transforms, add the refining oxalic acid 5Kg of nucleator before transforming, under continuous stirring condition, be no less than 60 minutes and slowly add compound fluorinating down, fluoridize temperature maintenance at 50-60 ℃, fluoridize final pH value and be controlled at 1.5; Still aging 2 hours;
6, the high-purity rare-earth yttrium fluoride slurry that step 5 is obtained is put into liner Teflon resin filter groove and is filtered, with being heated to 50-60 ℃ of deionized water wash, obtain 143.87 kilograms of high-purity rare-earth yttrium fluoride solids (total amount of rare earth is 61.2%) in the whizzer centrifuge dehydration again to pH=6-7;
7, will go up in several pallets of lining Teflon resin that rare earth yttrium fluoride solid that step obtains is placed on (20 * 30 * 10) cm equably, successive drying promptly gets 120.48 kilograms of anhydrous high-purity rare earth yttrium fluoride products (total amount of rare earth is 73.01%) after 15 hours in loft drier under 170 ± 1 ℃ of temperature;
8, at customer requirement, the ceramic ball mill of following adopted diameter 350mm carries out particle and integrates 2 hours, sieve and mix in the mixer of 500L with 40 mesh sieves, thereby obtain 120.42 kilograms of the uniform the finished product of particle (total amount of rare earth is 73.01%), the rare-earth products total recovery is 97.25%.
High purity anhydrous yttrium fluoride quality index (wt%)
EDTA?volumetric
Y 2O 3/REO--＞99.999?????????ICP???????????????????REO------------＞73
method
L.O.I.----------＜0.1??????gravimetry????????????La 2O 3-------＜0.0001??????ICP
CeO 2---------＜0.0001??????ICP???????????????????Pr 6O 11-------＜0.0001?????ICP
Nd 2O 3------＜0.0001????????ICP???????????????????Sm 2O 3------＜0.0001???????ICP
Eu 2O 3-------＜0.0001???????ICP???????????????????Gd 2O 3-------＜0.0001??????ICP
Tb 4O 7-------＜0.0001???????ICP???????????????????Dy 2O 3--------＜0.0001?????ICP
Ho 2O 3-------＜0.0001???????ICP???????????????????Er 2O 3--------＜0.0001?????ICP
Tm 2O 3------＜0.0001????????ICP???????????????????Yb 2O 3-------＜0.0001??????ICP
Lu 2O 3-------＜0.0001???????ICP???????????????????Fe 2O 3--------＜0.0001?????Spectrophotometry
Spectrophoto-
SiO 2---------＜0.0015????????????????????????????CaO-----------＜0.001?????ICP
metry
Cr 2O 3-------＜0.0003???????ICP???????????????????NiO-----------＜0.001?????ICP
MnO 2---------＜0.0003??????ICP???????????????????PbO----------＜0.0003?????ICP
S--------------＜0.001?????Infrared?absorption???Cl-------------＜0.003????Spectrophotometry
C--------------＜0.02??????Infrared?absorption???O--------------＜0.02
F---------------＞38???????electrode
High purity anhydrous yttrium fluoride detected result
As shown in Table 1.
Table one, high purity anhydrous yttrium fluoride product analysis list
Analysis project Analytical results Analytical procedure Analysis project Analytical results Analytical procedure
??REO ??≥73％ ??EDTA?volumetric??method ??La 2O 3 ??＜1ppm ??ICP
??F ??≥38％ ??electrode ??CeO 2 ??＜1ppm ??ICP
??L.O.I ??＜0.1％ ??gravimetry ??Pr 6O 11 ??＜1ppm ??ICP
??Fe 2O 3 ??＜1ppm ??Spectrophotometry ??Nd 2O 3 ??＜1ppm ??ICP
??CaO ??＜3ppm ??ICP ??Sm 2O 3 ??＜1ppm ??ICP
??SiO 2 ??＜10ppm ??Spectrophotometry ??Eu 2O 3 ??＜1ppm ??ICP
??NiO ??＜3ppm ??ICP ??Gd 2O 3 ??＜1ppm ??ICP
??Cr 2O 3 ??＜3ppm ??ICP ??Tb 4O 7 ??＜1ppm ??ICP
??MnO 2 ??＜3ppm ??ICP ??Dy 2O 3 ??＜1ppm ??ICP
??PbO ??＜3ppm ??ICP ??Ho 2O 3 ??＜1ppm ??ICP
??Cl ??＜30ppm ??Spectrophotometry ??Er 2O 3 ??＜1ppm ??ICP
??S ??＜10ppm ??Infrared?absorption ??Tm 2O 3 ??＜1ppm ??ICP
Analysis project Analytical results Analytical procedure Analysis project Analytical results Analytical procedure
??C ??＜200ppm ??Infrared?absorption ??Yb 2O 3 ??＜1ppm ??ICP
??O ??＜200ppm Oxygen-nitrogen analyzer ??Lu 2O 3 ??＜1ppm ??ICP
??D 50 ??5.5um Laser particle analyzer
Embodiment 2 high purity anhydrous lanthanum fluoride and preparations thereof
The preparation of high-purity Lanthanum trichloride scavenging solution
REO concentration: 120-130g/l
La purity:＞99.99%
Fe 2O 3＜0.05mg/L????CaO＜0.5mg/L??Zn＜0.01mg/L??Na 2O＜0.05mg/L
Free acidity: [H +]≤0.50mol/L
All the other conditions and operation are with embodiment 1.
Anhydrous high-purity rare earth lanthanum fluoride quality index
Project Unit ??LaF 3
??TREO ??％ ??≥99.99
??La 2O 3/TREO ??ppm ??≤10
??CeO 2/TREO ??ppm ??≤10
??Pr 6O 11/TREO ??ppm ??≤10
??Nd 2O 3/TREO ??ppm ??≤10
??Sm 2O 3/TREO ??ppm ??≤10
??Fe 2O 3/M ??ppm ??≤1
??CaO/M ??ppm ??≤10
??SiO 2/M ??ppm ??≤10
??Mn/M ??ppm ??≤1
??Na/M ??ppm ??≤3
??Pb/M ??ppm ??≤3
??Zn/M ??ppm ??≤3
??Al/M ??ppm ??≤3
??S/M ??ppm ??≤10
??Cl/M ??ppm ??≤30
??C/M ??ppm ??≤200
??O/M ??ppm ??≤200
??D 50 ??μm ??3-10
High purity anhydrous lanthanum fluoride detected result
As shown in Table 2.
Table two, high purity anhydrous lanthanum fluoride product analysis list
Figure GSA00000103381100091

Claims (10)

1. an anhydrous high-purity rare earth fluoride is characterized in that, main non-rare earth impurity iron (Fe 2O 3≤ 1ppm), calcium (CaO≤10ppm), silicon (SiO 2≤ 10ppm) carbon ((((equal size of S≤10ppm) is trace extremely, and product burns mistake rate≤0.5% for Cl≤30ppm), sulphur for O≤200ppm), chlorine for C≤200ppm), oxygen.
2. anhydrous high-purity rare earth fluoride as claimed in claim 1 is characterized in that, described rare earth fluorine is yttrium fluoride or lanthanum fluoride.
3. prepare the method for anhydrous high-purity rare earth fluoride as claimed in claim 1 or 2, comprise the following steps:
One, adopts high-purity single re chloride, in advance with N 235Impurity such as extraction agent deironing, zinc, it is stand-by to be purified liquid;
Two, the scavenging solution with step 1 is converted into carbonated rare earth with reagent ammoniacal liquor and refining carbon ammonium adjust pH, with its filter, deionized water wash, centrifuge dehydration obtain high-purity carbonated rare earth solid;
Three, in fluorizating apparatus, size mixing high-purity carbonated rare earth solid and deionized water Hybrid Heating that second step obtained stand-by;
Four, stand-by with deionized water, reagent ammoniacal liquor, reagent hydrofluoric acid preparation compound fluorinating;
Five, the compound fluorinating that step 4 is obtained joins in the described fluorizating apparatus of step 3 and transforms, and under continuous stirring condition, slowly adds compound fluorinating, keeps fluoridizing temperature at 50-60 ℃, fluoridizes the final pH value and is controlled at below 2;
Six, the high-purity rare earth fluoride slurry that step 5 is obtained filters, deionized water wash, centrifuge dehydration obtain the high-purity rare earth fluoride solid;
Seven, the rare earth fluorine solid drying dehydration that step 6 is obtained promptly gets anhydrous high-purity rare earth fluoride product.
4. method as claimed in claim 3 is characterized in that, the described scavenging solution Fe＜0.05mg/L of step 1, Zn＜0.01mg/L.
5. method as claimed in claim 3 is characterized in that, it is 5-7 that step 2 is regulated the pH value.
6. method as claimed in claim 3 is characterized in that, the described compound fluorinating of step 4, mol ratio HF/NH 4F=1.0-1.5, F/RE=3.5-4.5, concentration HF+NH 4F=3.6-4.2mol/L.
7. method as claimed in claim 3 is characterized in that, step 5 was added the refining oxalic acid of an amount of nucleator before transforming.
8. method as claimed in claim 3 is characterized in that, described fluorizating apparatus adopts not the non-metallic material with the hydrofluoric acid reaction, perhaps these non-metallic material of liner.
9. method as claimed in claim 3 is characterized in that, the step 7 drying temperature is 150 ℃-180 ℃, 12-18 hour time of drying.
10. method as claimed in claim 3 is characterized in that, with ceramic ball mill gained anhydrous high-purity rare earth fluoride particle is integrated 2 hours, sieves and mixes and criticize with being not less than 24 mesh sieves.
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN102230093A (en) * 2011-06-23 2011-11-02 赣州湛海工贸有限公司 Preparation method for separating and purifying single heavy rare earth by using full-extraction process
CN103922381A (en) * 2013-10-09 2014-07-16 赣州虔东稀土集团股份有限公司 Rare earth fluoride and its production method
CN105331834A (en) * 2015-09-30 2016-02-17 中铝广西国盛稀土开发有限公司 Method for removing iron and aluminum continuously from yttrium-rich feed liquid through N235
CN108264078A (en) * 2016-12-30 2018-07-10 有研稀土新材料股份有限公司 Hydrogeneous rare earth fluoride, preparation method and application
CN111170353A (en) * 2020-02-07 2020-05-19 包头稀土研究院 Method for preparing rare earth fluoride by carbon cycle
CN111204791A (en) * 2020-01-21 2020-05-29 包头稀土研究院 Method for promoting rare earth carbonate to be converted into rare earth fluoride and recycling ammonia water
CN112357945A (en) * 2020-11-06 2021-02-12 赣州湛海新材料科技有限公司 Method for preparing high-purity yttrium oxyfluoride
CN115893467A (en) * 2022-12-13 2023-04-04 包头市议源化工有限公司 Method for preparing rare earth fluoride by using ammonium fluoride solution

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102230093A (en) * 2011-06-23 2011-11-02 赣州湛海工贸有限公司 Preparation method for separating and purifying single heavy rare earth by using full-extraction process
CN103922381A (en) * 2013-10-09 2014-07-16 赣州虔东稀土集团股份有限公司 Rare earth fluoride and its production method
CN105331834A (en) * 2015-09-30 2016-02-17 中铝广西国盛稀土开发有限公司 Method for removing iron and aluminum continuously from yttrium-rich feed liquid through N235
CN108264078A (en) * 2016-12-30 2018-07-10 有研稀土新材料股份有限公司 Hydrogeneous rare earth fluoride, preparation method and application
CN108264078B (en) * 2016-12-30 2020-03-27 有研稀土新材料股份有限公司 Hydrogen-containing rare earth fluoride, preparation method and application thereof
CN111204791A (en) * 2020-01-21 2020-05-29 包头稀土研究院 Method for promoting rare earth carbonate to be converted into rare earth fluoride and recycling ammonia water
CN111204791B (en) * 2020-01-21 2022-06-14 包头稀土研究院 Method for promoting rare earth carbonate to be converted into rare earth fluoride and recycling ammonia water
CN111170353A (en) * 2020-02-07 2020-05-19 包头稀土研究院 Method for preparing rare earth fluoride by carbon cycle
CN111170353B (en) * 2020-02-07 2022-10-28 包头稀土研究院 Method for preparing rare earth fluoride by carbon cycle
CN112357945A (en) * 2020-11-06 2021-02-12 赣州湛海新材料科技有限公司 Method for preparing high-purity yttrium oxyfluoride
CN112357945B (en) * 2020-11-06 2023-12-08 赣州湛海新材料科技有限公司 Method for preparing high-purity yttrium oxyfluoride
CN115893467A (en) * 2022-12-13 2023-04-04 包头市议源化工有限公司 Method for preparing rare earth fluoride by using ammonium fluoride solution

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