CN115010165A - Preparation method of rare earth carbonate and preparation method of rare earth oxide - Google Patents
Preparation method of rare earth carbonate and preparation method of rare earth oxide Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 91
- -1 rare earth carbonate Chemical class 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 30
- 238000001556 precipitation Methods 0.000 claims abstract description 45
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 25
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 25
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000620 organic polymer Polymers 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 26
- 239000012266 salt solution Substances 0.000 abstract description 12
- 238000001914 filtration Methods 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- MBWYBKVRSONYRS-UHFFFAOYSA-N C([O-])(O)=O.[NH4+].[C] Chemical compound C([O-])(O)=O.[NH4+].[C] MBWYBKVRSONYRS-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 13
- KBLRIGLPGMRISA-UHFFFAOYSA-N neodymium(3+) oxygen(2-) praseodymium(3+) Chemical compound [O-2].[Pr+3].[Nd+3].[O-2].[O-2] KBLRIGLPGMRISA-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- XKCJIWHFQBSXPX-UHFFFAOYSA-H neodymium(3+) praseodymium(3+) tricarbonate Chemical compound [Nd+3].C([O-])([O-])=O.[Pr+3].C([O-])([O-])=O.C([O-])([O-])=O XKCJIWHFQBSXPX-UHFFFAOYSA-H 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- WTQUHLHXFJEOTI-UHFFFAOYSA-H trichloroneodymium;trichloropraseodymium Chemical compound Cl[Pr](Cl)Cl.Cl[Nd](Cl)Cl WTQUHLHXFJEOTI-UHFFFAOYSA-H 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 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 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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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
- C01F17/247—Carbonates
-
- 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
- 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
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/218—Yttrium oxides or hydroxides
-
- 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
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/241—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion containing two or more rare earth metals, e.g. NdPrO3 or LaNdPrO3
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention belongs to the technical field of rare earth hydrometallurgy, and particularly relates to a preparation method of rare earth carbonate and a preparation method of rare earth oxide. The invention provides a preparation method of rare earth carbonate, which is characterized by comprising the following steps: mixing soluble rare earth salt, ammonium bicarbonate and water to obtain a mixed solution; and mixing the mixed solution with an organic polymer flocculant to obtain the rare earth carbonate. According to the preparation method provided by the invention, in the traditional ammonium bicarbonate carbon precipitation process, after the ammonium bicarbonate is mixed with the soluble rare earth salt solution, the polymeric flocculant is added into the mixed solution, the problems of slow precipitation and difficult filtration of the traditional ammonium bicarbonate precipitation method are effectively solved by adding the polymeric flocculant, and the prepared rare earth carbonate has large granularity and good crystal form.
Description
Technical Field
The invention belongs to the technical field of rare earth hydrometallurgy, and particularly relates to a preparation method of rare earth carbonate and a preparation method of rare earth oxide.
Background
The rare earth oxide is a common product in rare earth materials on the market as a raw material for preparing rare earth metals or rare earth alloys by a rare earth molten salt electrolysis method.
At present, the preparation method of rare earth oxide mainly comprises a liquid phase method, specifically a precipitation method, a sol-gel method, a hydrothermal method, a microemulsion method and the like, wherein the precipitation method is the most extensive and practical. When the rare earth oxide is industrially prepared by a precipitation method, ammonium bicarbonate is generally adopted to precipitate a rare earth chloride solution to obtain a rare earth carbonate precipitate, and the rare earth carbonate precipitate is roasted to obtain the rare earth oxide. Ammonium bicarbonate is used as a cheap industrial precipitant, can reduce the production cost of rare earth oxides, and is widely used in turn.
However, when the ammonium bicarbonate is used for precipitating the rare earth chloride, large-volume flocculent precipitates are easily generated, so that the filtering difficulty is increased, the generated rare earth oxide has small granularity, is easy to agglomerate and has poor liquidity, and the product quality is unqualified due to the possibility of inclusion of feed liquid. Therefore, the application of the ammonium bicarbonate precipitation method in the production of rare earth oxides is limited to a certain extent.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing rare earth carbonate and a method for preparing rare earth oxide. The preparation method provided by the invention can be used for preparing the rare earth carbonate with large granularity and good crystal form, and further preparing the rare earth oxide with large particle size, sand shape and high dissolution speed.
In order to solve the technical problems, the invention provides a preparation method of rare earth carbonate, which is characterized by comprising the following steps:
mixing soluble rare earth salt, ammonium bicarbonate and water to obtain a mixed solution, wherein the precipitating agent comprises any one of ammonium bicarbonate, alkali metal carbonate and alkali metal bicarbonate;
and mixing the mixed solution with an organic polymer flocculant to perform a precipitation reaction to obtain the rare earth carbonate.
Preferably, the organic polymeric flocculant comprises polyethylene oxide and/or polyacrylamide.
Preferably, the mixed solution further comprises, before being mixed with the organic polymeric flocculant: and aging the mixed solution.
Preferably, the aging temperature is 25-60 ℃, and the aging heat preservation time is 20-50 min.
Preferably, the mass ratio of the soluble rare earth salt to the precipitator is (1-3) to (1-2).
Preferably, the mass ratio of the organic polymeric flocculant to the soluble rare earth salt is 0.15-0.95 per mill.
Preferably, the temperature of the precipitation reaction is 25-60 ℃; the heat preservation time of the precipitation reaction is 15-30 min; the precipitation reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 250-400 r/min.
Preferably, the aging is carried out under the condition of stirring, and the rotating speed of the stirring is 250-400 r/min.
The invention provides a preparation method of rare earth oxide, which comprises the following steps:
preparing rare earth carbonate according to the preparation method of the technical scheme;
and calcining the rare earth carbonate to obtain the rare earth oxide.
Preferably, the calcining temperature is 900-950 ℃, and the calcining heat preservation time is 8-24 h.
The invention provides a preparation method of rare earth carbonate, which is characterized by comprising the following steps: mixing soluble rare earth salt, ammonium bicarbonate and water to obtain a mixed solution, wherein the precipitating agent comprises any one of ammonium bicarbonate, alkali metal carbonate and alkali metal bicarbonate; and mixing the mixed solution with an organic polymer flocculant to perform a precipitation reaction to obtain the rare earth carbonate. According to the preparation method provided by the invention, in the traditional carbon precipitation process, a precipitator is mixed with a soluble rare earth salt solution, and then a polymeric flocculant is added into the mixed solution.
The invention provides a preparation method of rare earth oxide, which comprises the following steps: preparing rare earth carbonate according to the preparation method of the technical scheme; and calcining the rare earth carbonate to obtain the rare earth oxide. The preparation method provided by the invention adopts the scheme to prepare the rare earth carbonate with large granularity and good crystal form as the calcining raw material, the rare earth carbonate is sintered into the rare earth oxide in the calcining process, meanwhile, the organic polymer flocculant carried in the rare earth carbonate is removed at high temperature, the prepared rare earth oxide is large-particle sandy powder, the direct yield is high, the purity is high, and the dissolving speed of the rare earth oxide in the rare earth molten salt is effectively improved.
Drawings
FIG. 1 is a drawing of a praseodymium neodymium carbonate embodiment prepared in example 1 of the present invention;
FIG. 2 is a diagram showing a cerium carbonate prepared in example 2 of the present invention;
FIG. 3 is a pictorial representation of an embodiment of yttrium carbonate prepared in example 3 of the present invention.
Detailed Description
The invention provides a preparation method of rare earth carbonate, which comprises the following steps:
mixing soluble rare earth salt, ammonium bicarbonate and water to obtain a mixed solution, wherein the precipitating agent comprises any one of ammonium bicarbonate, alkali metal carbonate and alkali metal bicarbonate;
and mixing the mixed solution with an organic polymer flocculant to perform a precipitation reaction to obtain the rare earth carbonate.
In the present invention, the starting materials used are, unless otherwise specified, commercially available products well known to those skilled in the art.
The present invention mixes a soluble rare earth salt, a precipitant including any one of ammonium bicarbonate, alkali metal carbonate, and alkali metal bicarbonate, and water (hereinafter, referred to as a first mixing) to obtain a mixed solution.
In the present invention, the soluble rare earth salt is particularly preferably rare earth chloride.
In the present invention, the soluble rare earth salt is specifically praseodymium neodymium chloride, cerium chloride or yttrium chloride.
In the present invention, the precipitant includes any one of ammonium bicarbonate, alkali metal carbonate and alkali metal bicarbonate, and more preferably ammonium bicarbonate.
In the invention, the mass ratio of the soluble rare earth salt to the precipitant is preferably (1-3) to (1-2), more preferably (3-7) to (3-5), and further preferably (15-35) to (15-22).
In a specific embodiment of the present invention, the mass ratio of the soluble rare earth salt to the precipitant is preferably 2:1, 3.18:1, or 3.33: 1.
In the present invention, the first mixture is preferably, specifically, a soluble rare earth salt solution and a precipitant solution.
In the present invention, the soluble rare earth salt solution is particularly preferably a rare earth chloride solution.
In the invention, the mass concentration of the soluble rare earth salt solution is preferably 40-80 g/L.
In a specific embodiment of the present invention, the mass concentration of the soluble rare earth salt solution is preferably 50g/L or 70 g/L.
In a specific embodiment of the present invention, the volume of the soluble rare earth salt solution is particularly preferably 300mL or 500 mL.
In the invention, the mass concentration of the precipitant solution is preferably 70-120 g/L.
In a specific embodiment of the invention, the mass concentration of the precipitant solution is preferably 75g/L or 110 g/L.
In a specific embodiment of the present invention, the volume of the precipitant solution is particularly preferably 300mL or 500 mL.
In the present invention, the order of the first mixing is preferably:
dissolving the soluble rare earth salt in partial water to form a soluble rare earth salt solution;
dissolving the precipitant in the residual water to obtain precipitant solution;
mixing the soluble rare earth salt solution and the precipitant solution.
In the invention, the mixing temperature of the soluble rare earth salt solution and the precipitant solution is preferably 20-60 ℃, and more preferably 25-60 ℃.
In a specific embodiment of the present invention, the temperature at which the soluble rare earth salt solution and the precipitant solution are mixed is particularly preferably 25 ℃, 40 ℃, or 60 ℃.
In the invention, the soluble rare earth salt solution and the precipitant solution are preferably mixed under stirring, and the stirring speed is preferably 250-400 r/min, and more preferably 300 r/min.
In the present invention, after obtaining the mixed solution, the present invention preferably further comprises aging the mixed solution to obtain an aged solution, and mixing the aged solution with the organic polymeric flocculant.
In the invention, the aging temperature is preferably 20-60 ℃, and more preferably 25-60 ℃.
In a particular embodiment of the invention, the temperature of the aging is particularly preferably 25 ℃, 40 ℃ or 60 ℃.
In the invention, the heat preservation time for aging is preferably 20-50 min, and more preferably 30 min.
In the invention, the aging is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 250-400 r/min, and more preferably 300 r/min.
After obtaining the mixed solution or the aged solution, the present invention mixes the mixed solution or the aged solution with an organic polymeric flocculant (hereinafter referred to as a second mixture) to perform a precipitation reaction, thereby obtaining a rare earth carbonate.
In the present invention, the organic polymeric flocculant preferably includes polyethylene oxide and/or polyacrylamide, more preferably polyethylene oxide or polyacrylamide.
In the present invention, in the second mixing, the organic polymeric flocculant is preferably subjected to the second mixing in the form of an aqueous solution of an organic polymeric flocculant.
In the present invention, the mass concentration of the aqueous solution of the organic polymeric flocculant is preferably 2 g/L.
In the invention, the volume of the organic polymeric flocculant aqueous solution is preferably 3-7 mL.
In a specific embodiment of the present invention, the volume of the aqueous solution of the organic polymeric flocculant is specifically preferably 3mL, 5mL or 7 mL.
In the invention, the mass ratio of the organic polymeric flocculant to the soluble rare earth salt is preferably 0.15-0.95 per mill. More preferably 0.17 to 0.93%.
In an embodiment of the present invention, the mass ratio of the organic polymeric flocculant to the soluble rare earth salt is preferably 0.4%, 0.93%, and 0.17%.
In the invention, the temperature of the second mixing is preferably 20-60 ℃, and more preferably 25-60 ℃.
In a specific embodiment of the present invention, the temperature of the second mixing is specifically preferably 25 ℃, 40 ℃ or 60 ℃.
In the invention, the second mixing is preferably carried out under stirring conditions, and the rotation speed of the stirring is preferably 250-400 r/min, and more preferably 300 r/min.
In the invention, the temperature of the precipitation reaction is preferably 20-60 ℃, and more preferably 25-60 ℃.
In a particular embodiment of the invention, the temperature of the precipitation reaction is particularly preferably 25 ℃, 40 ℃ or 60 ℃.
In the invention, the heat preservation time of the precipitation reaction is preferably 15-30 min.
In a specific embodiment of the present invention, the incubation time of the precipitation reaction is preferably 15min, 20min or 25 min.
In the invention, the precipitation reaction is preferably carried out under the condition of stirring, and the rotation speed of the stirring is preferably 250-400 r/min, and more preferably 300 r/min.
In the invention, solid-liquid separation is carried out after the precipitation reaction to obtain a solid-phase product of the precipitation reaction, and the invention preferably carries out post-treatment on the solid-phase product to obtain the rare earth carbonate. In the present invention, the solid-liquid separation is preferably filtration, and the present invention does not particularly require a specific embodiment of the filtration. In the present invention, the post-treatment preferably comprises: and washing and drying are sequentially carried out. The invention has no special requirements on the specific implementation process of the water washing. According to the invention, the solid-phase product washed by water is preferably subjected to vacuum pumping to obtain the rare earth carbonate.
The invention effectively solves the problems of slow precipitation and difficult filtration of the traditional ammonium bicarbonate precipitation method by adding the polymeric flocculant, and the prepared rare earth carbonate has large granularity and good crystal form.
The invention provides a preparation method of rare earth oxide, which comprises the following steps:
preparing rare earth carbonate according to the preparation method of the technical scheme;
and calcining the rare earth carbonate to obtain the rare earth oxide.
In the invention, the calcination temperature is preferably 900-950 ℃.
In the invention, the calcination heat preservation time is preferably 8-24 h.
The preparation method provided by the invention adopts the scheme to prepare the rare earth carbonate with large granularity and good crystal form as the calcining raw material, the rare earth carbonate is sintered into the rare earth oxide in the calcining process, meanwhile, the organic polymer flocculant carried in the rare earth carbonate is removed at high temperature, the prepared rare earth oxide is large-particle sandy powder, the direct yield is high, the purity is high, and the dissolving speed of the rare earth oxide in the rare earth molten salt is effectively improved.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking 500mL of 50g/L praseodymium neodymium chloride solution in a 2L beaker, starting stirring to adjust the rotating speed to 300r/min, keeping the temperature of the rare earth chloride solution at 25 ℃, adding 500mL of 75g/L ammonium bicarbonate solution into the beaker, keeping the temperature at 25 ℃, keeping the stirring speed unchanged, aging for 30min, adding 5mL of 2g/L polyoxyethylene aqueous solution, keeping the stirring speed unchanged, carrying out precipitation reaction for 15min, filtering, washing and drying the obtained precipitation reaction liquid to obtain praseodymium neodymium carbonate;
and calcining the praseodymium neodymium carbonate at 950 ℃ for 10h to obtain praseodymium neodymium oxide.
The performance of the praseodymium neodymium oxide prepared in this example was measured, and the praseodymium neodymium oxide prepared in this example had a uniform particle size distribution and a central particle size of 70 μm, and the SEM image showed sand-like, and a high dissolution rate in the rare earth molten salt.
Example 2
Taking 300mL of 50g/L cerium chloride solution into a 2L beaker, starting stirring, adjusting the rotating speed to 300r/min, keeping the temperature of the rare earth chloride solution at 40 ℃, adding 300mL of 75g/L ammonium bicarbonate solution into the beaker, keeping the temperature at 40 ℃, keeping the stirring speed unchanged, aging for 30min, adding 7mL of 2g/L polyacrylamide aqueous solution, keeping the stirring speed unchanged, carrying out precipitation reaction for 20min, filtering, washing and drying the obtained precipitation reaction solution to obtain cerium carbonate;
and calcining the cerium carbonate at 900 ℃ for 14h to obtain cerium oxide.
The properties of the cerium oxide prepared in this example were measured, and the cerium oxide prepared in this example had a uniform particle size distribution and a center particle size of 50 μm, and the SEM image showed sand-like shape, and the dissolution rate in the rare earth molten salt was high.
Example 3
Putting 500mL of 70g/L yttrium chloride solution into a 2L beaker, starting stirring, adjusting the rotating speed to 300r/min, keeping the temperature of the rare earth chloride solution at 60 ℃, adding 500mL of 110g/L ammonium bicarbonate solution into the beaker, keeping the temperature at 40 ℃, keeping the stirring speed unchanged, aging for 30min, adding 3mL of 2g/L polyoxyethylene aqueous solution, keeping the stirring speed unchanged, carrying out precipitation reaction for 25min, filtering, washing and drying the obtained precipitation reaction solution to obtain yttrium carbonate;
calcining the rare earth carbonate at 930 ℃ for 12h to obtain the yttrium oxide.
The properties of the yttrium oxide prepared in this example were measured, the particle size distribution of the yttrium oxide prepared in this example was uniform, the center particle size was 60 μm, and the SEM image showed sand-like, and the dissolution rate in the rare earth molten salt was fast.
Comparative example 1
Taking 500mL of 50g/L praseodymium neodymium chloride solution into a 2L beaker, starting stirring to adjust the rotating speed to be 300r/min, keeping the temperature of the rare earth chloride solution to be 25 ℃, adding 500mL of 75g/L ammonium bicarbonate solution into the beaker, keeping the temperature to be 25 ℃, keeping the stirring speed unchanged, carrying out precipitation reaction for 90min, filtering, washing and drying the obtained precipitation reaction liquid to obtain praseodymium neodymium carbonate;
and calcining the praseodymium neodymium carbonate at 950 ℃ for 10h to obtain praseodymium neodymium oxide.
The performance of the praseodymium neodymium oxide prepared by the comparative example is measured, the praseodymium neodymium oxide prepared by the comparative example has uneven particle size distribution and is easy to agglomerate, and the dissolution speed in the rare earth molten salt is slower than that of the rare earth oxide products prepared in the examples 1-3.
Comparative example 2
Taking 500mL of 50g/L praseodymium neodymium chloride solution into a 2L beaker, starting stirring to adjust the rotating speed to 300r/min, keeping the temperature of the rare earth chloride solution at 25 ℃, adding 500mL of 75g/L ammonium bicarbonate solution into the beaker, immediately adding 5mL of polyoxyethylene aqueous solution and 2g/L of polyoxyethylene aqueous solution, keeping the temperature at 25 ℃, keeping the stirring speed unchanged, carrying out precipitation reaction for 90min, filtering, washing and drying the obtained precipitation reaction liquid to obtain praseodymium neodymium carbonate;
and calcining the diluted praseodymium neodymium carbonate at 950 ℃ for 10 hours to obtain praseodymium neodymium oxide.
The performance of the praseodymium neodymium oxide prepared by the comparative example is measured, the praseodymium neodymium oxide prepared by the comparative example has uneven particle size distribution and is easy to agglomerate, and the dissolution speed in the rare earth molten salt is slower than that of the rare earth oxide products prepared in the examples 1-3. In the comparative example, the flocculation ability of the flocculant is reduced, the precipitation speed is reduced, and the precipitation time is completely the same as that of the comparative example 1 in which the flocculant is not added, so that the precipitation can be completely finished in a longer time.
Comparative example 3
Taking 500mL of 70g/L praseodymium neodymium chloride solution in a 2L beaker, starting stirring to adjust the rotating speed to 300r/min, keeping the temperature of the rare earth chloride solution at 60 ℃, adding 500mL of 110g/L ammonium bicarbonate solution into the beaker, keeping the temperature at 40 ℃, keeping the stirring speed unchanged, aging for 30min, adding 3mL of 1g/L polyoxyethylene aqueous solution, keeping the stirring speed unchanged, carrying out precipitation reaction for 60min, filtering, washing and drying the obtained precipitation reaction liquid to obtain praseodymium neodymium carbonate;
and calcining the praseodymium neodymium carbonate at 930 ℃ for 14h to obtain praseodymium neodymium oxide.
The performance of the praseodymium neodymium oxide prepared by the comparative example is measured, the praseodymium neodymium oxide prepared by the comparative example has uneven particle size distribution and is easy to agglomerate, and the dissolution speed in the rare earth molten salt is slower than that of the rare earth oxide products prepared in the examples 1-3. In this comparative example, the addition amount of the flocculant was insufficient, the flocculation ability was limited, the precipitation speed was slow, and it took a long time until the precipitation was completed although the settling time required was reduced as compared with comparative examples 1 and 2.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. The preparation method of the rare earth carbonate is characterized by comprising the following steps:
mixing soluble rare earth salt, a precipitator ammonium bicarbonate and water to obtain a mixed solution, wherein the precipitator comprises any one of ammonium bicarbonate, alkali metal carbonate and alkali metal bicarbonate;
and mixing the mixed solution with an organic polymer flocculant to perform a precipitation reaction to obtain the rare earth carbonate.
2. The production method according to claim 1, wherein the organic polymeric flocculant comprises polyethylene oxide and/or polyacrylamide.
3. The method according to claim 1, wherein the step of mixing the mixed solution with the organic polymeric flocculant further comprises: and aging the mixed solution.
4. The method according to claim 3, wherein the aging temperature is 25 to 60 ℃ and the aging holding time is 20 to 50 min.
5. The method according to claim 1, wherein the mass ratio of the soluble rare earth salt to the precipitant is (1-3) to (1-2).
6. The preparation method according to claim 1 or 2, wherein the mass ratio of the organic polymeric flocculant to the soluble rare earth salt is 0.15 to 0.95 ‰.
7. The preparation method according to claim 1, wherein the temperature of the precipitation reaction is 25-60 ℃; the heat preservation time of the precipitation reaction is 15-30 min; the precipitation reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 250-400 r/min.
8. The method according to claim 3 or 4, wherein the aging is performed under stirring at a rotation speed of 250 to 400 r/min.
9. The preparation method of the rare earth oxide is characterized by comprising the following steps:
preparing rare earth carbonate according to any one of the preparation methods of claims 1 to 8;
and calcining the rare earth carbonate to obtain the rare earth oxide.
10. The preparation method of claim 9, wherein the calcination temperature is 900-950 ℃, and the calcination holding time is 8-24 h.
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| CN117401706A (en) * | 2023-12-11 | 2024-01-16 | 赣州晨光稀土新材料有限公司 | Preparation method and application of large-particle rare earth oxide |
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