CN112357945A - Method for preparing high-purity yttrium oxyfluoride - Google Patents
Method for preparing high-purity yttrium oxyfluoride Download PDFInfo
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- CN112357945A CN112357945A CN202011229509.5A CN202011229509A CN112357945A CN 112357945 A CN112357945 A CN 112357945A CN 202011229509 A CN202011229509 A CN 202011229509A CN 112357945 A CN112357945 A CN 112357945A
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- yttrium
- yttrium oxyfluoride
- purity
- preparing high
- oxyfluoride
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- CHBIYWIUHAZZNR-UHFFFAOYSA-N [Y].FOF Chemical compound [Y].FOF CHBIYWIUHAZZNR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000010304 firing Methods 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- ULEWOPXGNWLKFY-UHFFFAOYSA-M oxygen(2-) yttrium(3+) fluoride Chemical compound [O--].[F-].[Y+3] ULEWOPXGNWLKFY-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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
- C01F17/259—Oxyhalides
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a preparation method of yttrium oxyfluoride, belonging to a material preparation process. A method for preparing high-purity yttrium oxyfluoride comprises the following steps: (1) adding a precipitator into the yttrium-containing material liquid reaction container, and then adding an HF solution to completely precipitate the rare earth; (2) aging for 1h, filtering and washing with deionized water until the pH is 6-8; (3) and (4) transferring the yttrium oxide fluoride into an oven for drying, firing, heating and preserving heat to obtain the yttrium oxyfluoride. The invention has the following advantages: 1. the process flow is simple, and large-scale production can be realized; 2. the absolute purity is high, the particle has certain characteristic morphology (small and uniform particles, dispersion and no agglomeration), and the use of special industries can be met.
Description
Technical Field
The invention relates to a preparation method of yttrium oxyfluoride, belonging to a material preparation process.
Background
Yttrium oxyfluoride is widely applied to luminescent materials, permanent magnetic materials, catalytic materials, polishing materials, solid electrolyte materials and the like, and products prepared from the yttrium oxyfluoride have specific optical, magnetic, catalytic and polishing performances and the like, so that the application of the yttrium oxyfluoride enters a brand-new development stage, and higher requirements are provided for the production process, the product quality and the performance along with the increase of diversified demands of the market.
Disclosure of Invention
The invention aims to provide a method for preparing high-purity yttrium oxyfluoride, which has simple process, high absolute purity and certain morphological characteristics.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for preparing high-purity yttrium oxyfluoride comprises the following steps:
(1) adding a precipitator into the yttrium-containing material liquid reaction container, and then adding an HF solution to completely precipitate the rare earth;
(2) aging for 1h, filtering and washing with deionized water until the pH is 6-8;
(3) and (4) transferring the yttrium oxide fluoride into an oven for drying, firing, heating and preserving heat to obtain the yttrium oxyfluoride.
Preferably, in the step (1), the yttrium solution is a hydrochloric acid system, a nitric acid system, or a sulfuric acid system.
Preferably, in the step (1), the precipitant is refined oxalic acid, and the molar ratio of the yttrium chloride metal amount to the refined oxalic acid to the hydrofluoric acid is 1: 0.5-1: 1-3.
Preferably, the yttrium chloride is 5N yttrium chloride.
Preferably, the HF solution is an electronic grade HF solution.
Preferably, in step (2), the yttrium oxyfluoride precursor obtained after aging is washed with deionized water to PH = 7.
Preferably, in the step (2), the washing time is 48-96 h.
Preferably, in the step (3), the drying temperature is 60-500 ℃, the firing temperature is 600-1200 ℃, the heating rate is 10-50 ℃/min, and the heat preservation time is 2-20 h.
Preferably, in step (3), the yttrium oxyfluoride produced is single YO1-XF1+2X、YnOn-1Fn+2Or a mixture of two or more.
The principle is as follows: precipitating a raw material yttrium chloride solution by adopting a precipitation synthesis method to obtain a yttrium oxyfluoride precursor; then washing until the PH =7, and washing non-rare earth impurity ions in the yttrium oxyfluoride precursor to a very low level, thereby ensuring that the burnt yttrium oxyfluoride product has low impurities; and (3) transferring the yttrium oxide powder into an oven for drying, firing, heating and preserving heat to obtain the yttrium oxyfluoride which has certain morphological characteristics (small and uniform particles, dispersion and no agglomeration) and can meet the requirements of special industries.
Compared with the prior art, the invention has the following advantages:
1. the process flow is simple, and large-scale production can be realized;
2. the absolute purity is high, the particle has certain characteristic morphology (small and uniform particles, dispersion and no agglomeration), and the use of special industries can be met.
Drawings
FIG. 1 is a graphic of XRD data for the analytical detection of example 1 in accordance with the present invention;
FIG. 2 is a graphic of XRD data for the analytical detection of example 2 in accordance with the present invention;
figure 3 is a graph of analytical detection XRD data for example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying figures 1-3:
example 1
Taking 100g/L of 5N yttrium chloride as a raw material; 2L, filling into a reaction container, adding 100g/L and 1.7L of auxiliary material refined oxalic acid solution into the reaction container, adding 3mol/L and 0.9L of hydrofluoric acid solution, and precipitating until the supernatant is free of rare earth. Washed by deionized water filtration to PH = 7. And (3) transferring the powder into an oven for drying at 180 ℃, burning and heating the powder for 2h to 950 ℃, and preserving the heat for 4h to obtain yttrium oxyfluoride (100 percent YOF) powder. The XRD detection data are shown in figure 1, and the chemical analysis results are as follows:
example 2
Taking 200g/L of 5N yttrium chloride as a raw material; 10L, filling into a reaction container, adding 250g/L and 8.92L of auxiliary material refined oxalic acid solution into the reaction container, adding 14mol/L and 1.3L of hydrofluoric acid solution, and precipitating until the supernatant is free of rare earth. Washed by deionized water filtration to PH = 7. And (3) transferring the powder into an oven for drying at 180 ℃, burning and heating the powder for 2h to 950 ℃, and keeping the temperature for 4h to obtain yttrium oxyfluoride (100% Y5O4F7) powder. The XRD detection data are shown in figure 2, and the chemical analysis results are as follows:
example 3
Taking 100g/L of 5N yttrium chloride as a raw material; 1m3Putting into a reaction vessel, adding 112g/L, 1m of the auxiliary material refined oxalic acid solution into the reaction vessel3Then adding 0.94mol/L, 1m hydrofluoric acid solution3And precipitating until supernatant is free of rare earth. Washed by deionized water filtration to PH = 7. And (3) transferring the mixture into an oven for drying at 180 ℃, burning and heating the mixture for 2h to 950 ℃, and preserving the heat for 4h to obtain yttrium oxyfluoride (66% YOF and 34% Y7O6F9) powder. The XRD detection data are shown in FIG. 3, and the chemical analysis results are as follows:
the above examples are merely preferred embodiments of the present invention and are not to be construed as limiting the invention. In the whole process, the yttrium oxyfluoride precursor is slowly heated, dried and dehydrated, and then calcined at high temperature, so that the product particles are small and uniform, and are dispersed without agglomeration, and the like, thereby obtaining a good powder material.
Claims (9)
1. A method for preparing high-purity yttrium oxyfluoride is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a precipitator into the yttrium-containing material liquid reaction container, and then adding an HF solution to completely precipitate the rare earth;
(2) aging for 1h, filtering and washing with deionized water until the pH is 6-8;
(3) and (4) transferring the yttrium oxide fluoride into an oven for drying, firing, heating and preserving heat to obtain the yttrium oxyfluoride.
2. The method for preparing high-purity yttrium oxyfluoride according to claim 1, wherein: in the step (1), the yttrium feed liquid is a hydrochloric acid system, a nitric acid system or a sulfuric acid system.
3. The method for producing a high purity yttrium oxyfluoride according to claim 1 or 2, characterized in that: the yttrium feed liquid is 5N yttrium chloride.
4. The method for preparing high-purity yttrium oxyfluoride according to claim 3, wherein: in the step (1), the precipitator is refined oxalic acid, and the molar ratio of yttrium chloride metal amount to refined oxalic acid to hydrofluoric acid is 1: 0.5-1: 1-3.
5. The method for producing a high purity yttrium oxyfluoride according to claim 1 or 2, characterized in that: the HF solution is an electronic grade HF solution.
6. The method for preparing high-purity yttrium oxyfluoride according to claim 1, wherein: in step (2), the yttrium oxyfluoride precursor obtained after precipitation aging is washed with deionized water to PH = 7.
7. The method for producing high-purity yttrium oxyfluoride according to claim 1 or 6, wherein: in the step (2), the washing time is 48-96 h.
8. The method for preparing high-purity yttrium oxyfluoride according to claim 1, wherein: in the step (3), the drying temperature is 60-500 ℃, the firing temperature is 600-1200 ℃, the heating rate is 10-50 ℃/min, and the heat preservation time is 2-20 h.
9. The method for preparing high-purity yttrium oxyfluoride according to claim 1, wherein: in step (3), the yttrium oxyfluoride produced is single YO1-XF1+2X、YnOn-1Fn+2Or a mixture of two or more.
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| CN202011229509.5A CN112357945B (en) | 2020-11-06 | 2020-11-06 | Method for preparing high-purity yttrium oxyfluoride |
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| CN202011229509.5A CN112357945B (en) | 2020-11-06 | 2020-11-06 | Method for preparing high-purity yttrium oxyfluoride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117430977A (en) * | 2023-12-21 | 2024-01-23 | 苏州高芯众科半导体有限公司 | Preparation method of yttrium oxyfluoride spray powder and yttrium oxyfluoride spray powder |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201441A (en) * | 1995-09-18 | 1998-12-09 | 罗狄亚化学公司 | Rare-earth and alkali metal sulphide, method for preparing same and use thereof as pigment |
| JP2010138067A (en) * | 2006-02-21 | 2010-06-24 | Ube Material Industries Ltd | Method for producing fluorine-containing magnesium oxide powder |
| CN101805008A (en) * | 2010-04-26 | 2010-08-18 | 赣州虔东稀土集团股份有限公司 | Anhydrous high-purity rare earth fluoride and preparation method thereof |
| CN102925106A (en) * | 2012-11-14 | 2013-02-13 | 内蒙古科技大学 | Rare earth polishing powder and preparation method thereof |
| CN103803630A (en) * | 2014-01-27 | 2014-05-21 | 福建省长汀金龙稀土有限公司 | Method for preparing yttria of different sizes and different appearances |
| US20180175382A1 (en) * | 2016-12-15 | 2018-06-21 | Honda Motor Co., Ltd. | Composite electrode materials for fluoride-ion electrochemical cells |
| CN110372026A (en) * | 2019-07-18 | 2019-10-25 | 赣州湛海新材料科技有限公司 | A kind of rare earth fluoride preparation method applied to crystalline material |
-
2020
- 2020-11-06 CN CN202011229509.5A patent/CN112357945B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201441A (en) * | 1995-09-18 | 1998-12-09 | 罗狄亚化学公司 | Rare-earth and alkali metal sulphide, method for preparing same and use thereof as pigment |
| JP2010138067A (en) * | 2006-02-21 | 2010-06-24 | Ube Material Industries Ltd | Method for producing fluorine-containing magnesium oxide powder |
| CN101805008A (en) * | 2010-04-26 | 2010-08-18 | 赣州虔东稀土集团股份有限公司 | Anhydrous high-purity rare earth fluoride and preparation method thereof |
| CN102925106A (en) * | 2012-11-14 | 2013-02-13 | 内蒙古科技大学 | Rare earth polishing powder and preparation method thereof |
| CN103803630A (en) * | 2014-01-27 | 2014-05-21 | 福建省长汀金龙稀土有限公司 | Method for preparing yttria of different sizes and different appearances |
| US20180175382A1 (en) * | 2016-12-15 | 2018-06-21 | Honda Motor Co., Ltd. | Composite electrode materials for fluoride-ion electrochemical cells |
| CN110372026A (en) * | 2019-07-18 | 2019-10-25 | 赣州湛海新材料科技有限公司 | A kind of rare earth fluoride preparation method applied to crystalline material |
Non-Patent Citations (1)
| Title |
|---|
| 李维华等: ""沉淀法制备氟氧化钇粉体及其表征"", 《材料导报》, vol. 25, pages 137 - 138 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117430977A (en) * | 2023-12-21 | 2024-01-23 | 苏州高芯众科半导体有限公司 | Preparation method of yttrium oxyfluoride spray powder and yttrium oxyfluoride spray powder |
| CN117430977B (en) * | 2023-12-21 | 2024-02-23 | 苏州高芯众科半导体有限公司 | Preparation method of yttrium oxyfluoride spray powder and yttrium oxyfluoride spray powder |
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