CN114836637B - Rare earth oxide acid-soluble grouping method - Google Patents
Rare earth oxide acid-soluble grouping method Download PDFInfo
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 93
- 239000002253 acid Substances 0.000 claims abstract description 77
- 238000004090 dissolution Methods 0.000 claims abstract description 49
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 28
- -1 hydrogen ions Chemical class 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 abstract description 25
- 238000000605 extraction Methods 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 12
- 238000002386 leaching Methods 0.000 description 11
- 229910001122 Mischmetal Inorganic materials 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 229910052771 Terbium Inorganic materials 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000919 ceramic Substances 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
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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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
- Y02P10/20—Recycling
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for acid-soluble grouping of rare earth oxides, belonging to the field of rare earth hydrometallurgy. The method comprises the following steps: mixing a rare earth oxide raw material, water and a first inorganic acid for first acid dissolution to obtain first filter residues, wherein the concentration of hydrogen ions in the first inorganic acid is 1mol/L; mixing the first filter residue with a second inorganic acid to perform second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3mol/L; and mixing the second filter residue with a third inorganic acid to perform third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5mol/L. According to the invention, the inorganic acid with different concentrations is used by controlling acid dissolution, the rare earth elements are grouped in the acid dissolution process, and each rare earth element is grouped according to the different concentrations of the dissolved inorganic acid, so that the subsequent extraction and separation effects of reducing the extraction pressure and the extraction stage number are achieved, the space resource is saved, and the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of rare earth hydrometallurgy, in particular to a method for acid-soluble grouping of rare earth oxides.
Background
Rare earth is a generic term for 17 rare earth elements. Rare earth has unique properties and uses, and has wide application in the fields of petrochemical industry, glass, ceramics, steel, luminescent materials, hydrogen storage materials, magnetic materials and the like. The mineral resources for producing rare earth in China are rich, and the rare earth mineral varieties are various, including monazite, bastnaesite, xenotime, southern ionic rare earth ore and the like. The rare earth elements in the rare earth minerals are mostly in the form of isomorphous and ion adsorption, so that the rare earth elements in the rare earth minerals need to be pretreated to break the crystal lattice, the rare earth elements are separated out in the form of free rare earth ions and sent to a rare earth separation plant in the form of rare earth compounds, and single rare earth chloride with higher purity is produced through extraction separation.
The rare earth raw material mainly contains rare earth oxide, iron, silicon, calcium and other elements. The common treatment flow of the common rare earth raw materials is as follows: acid dissolution, extraction, precipitation and roasting. Wherein acid dissolution is to decompose rare earth raw materials and convert rare earth elements into free rare earth ions; the extraction is to group the rare earth elements according to the difference of the distribution ratio of the rare earth elements in an organic phase and a water phase to obtain each rare earth feed liquid; precipitating by adding precipitants such as oxalic acid, carbonate and the like to precipitate the rare earth from the aqueous solution to obtain rare earth oxalate or carbonate; and the roasting is to put the rare earth precipitate into a roasting kiln for roasting, and finally, the rare earth oxide product is obtained.
Because the rare earth elements are various and the separation coefficients are close, the number of stages of the extraction tank is very large when the rare earth elements are separated by a solvent extraction method, so that the number of stages of the extraction tank is large, the occupied space is large, and meanwhile, the acid-base consumption and the extractant consumption are large, so that the production cost is increased.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for acid-dissolving and grouping rare earth oxides. The invention groups rare earth elements in the acid dissolution process by controlling the acid dissolution condition, reduces the pressure of the subsequent extraction process, reduces the extraction stage number, saves space resources and reduces the production cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for acid-soluble grouping of rare earth oxides, which comprises the following steps:
mixing a rare earth oxide raw material, water and a first inorganic acid for first acid dissolution to obtain first filter residues, wherein the concentration of hydrogen ions in the first inorganic acid is 1mol/L;
mixing the first filter residue with a second inorganic acid to perform second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3mol/L;
and mixing the second filter residue with a third inorganic acid to perform third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5mol/L.
Preferably, the rare earth elements contained in the rare earth oxide raw material include La, ce, pr, nd, sm, eu, gd, tb, dy, ho, Y, er, tm, yb and Lu.
Preferably, the liquid-solid ratio of the first acid solution, the second acid solution and the third acid solution is independently 3 to 6:1.
preferably, the first, second and third inorganic acids are independently hydrochloric acid, nitric acid or sulfuric acid.
Preferably, the temperature of the first acid dissolution is 0-20 ℃.
Preferably, the temperature of the second acid dissolution is 20-50 ℃.
Preferably, the temperature of the third acid dissolution is 60-80 ℃.
Preferably, the first acid dissolution further provides a first filtrate, and rare earth elements in the first filtrate include La, pr and Nd.
Preferably, the second acid dissolution also yields a second filtrate, the rare earth elements in the second filtrate comprising Sm, eu, gd and Dy.
Preferably, the third acid dissolution also gives a third filtrate, the rare earth elements in the third filtrate comprising Ho, Y, er, tm, yb and Lu.
The invention provides a method for acid-soluble grouping of rare earth oxides, which comprises the following steps: mixing a rare earth oxide raw material, water and a first inorganic acid for first acid dissolution to obtain first filter residues, wherein the concentration of hydrogen ions in the first inorganic acid is 1mol/L; mixing the first filter residue with a second inorganic acid to perform second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3mol/L; and mixing the second filter residue with a third inorganic acid to perform third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5mol/L.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the inorganic acid with different concentrations is used by controlling acid dissolution, rare earth elements are grouped in the acid dissolution process, and each rare earth element is grouped differently according to the concentration of the dissolved inorganic acid, so that the subsequent extraction and separation effects of reducing the extraction pressure and the extraction stage number are achieved, the space resource is saved, the production cost is reduced, and meanwhile, the purity of a single product is ensured after the separated feed liquid is extracted, so that the method has a certain positive effect on reducing the production cost. The rare earth oxide treated by direct acid leaching in actual production needs 60-level extraction tanks, and the invention only needs 60-level extraction tanks.
Detailed Description
The invention provides a method for acid-soluble grouping of rare earth oxides, which comprises the following steps:
mixing a rare earth oxide raw material, water and a first inorganic acid for first acid dissolution to obtain first filter residues, wherein the concentration of hydrogen ions in the first inorganic acid is 1mol/L;
mixing the first filter residue with a second inorganic acid to perform second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3mol/L;
and mixing the second filter residue with a third inorganic acid to perform third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5mol/L.
Unless otherwise specified, all materials used are commercially available in the art.
The method comprises the steps of mixing a rare earth oxide raw material, water and a first inorganic acid for first acid dissolution to obtain first filter residues, wherein the concentration of hydrogen ions in the first inorganic acid is 1mol/L. The source of the rare earth oxide raw material is not particularly limited in the present invention.
In the present invention, the rare earth elements contained in the rare earth oxide raw material preferably include La (lanthanum, ce (cerium), pr (praseodymium), nd (neodymium), sm (samarium), eu (europium), gd (gadolinium), tb (terbium), dy (dysprosium), ho (holmium), Y (yttrium), er (erbium), tm (thulium), yb (ytterbium), and Lu (lutetium).
In the present invention, the liquid-solid ratio of the first acid solution is preferably 3 to 6:1, more preferably 4 to 5:1.
in the present invention, the first inorganic acid is preferably hydrochloric acid, nitric acid or sulfuric acid.
In the present invention, the temperature of the first acid-dissolution is preferably 0 to 20 ℃, more preferably 10 ℃.
In the invention, the method for grouping the rare earth oxide acid solutions is applied to actual production, the stirring speed of the first acid solutions is preferably 20-30 r/min, the method for grouping the rare earth oxide acid solutions is applied to laboratories, and the stirring speed of the first acid solutions is preferably 200-300 r/min, more preferably 250r/min.
After the first acid dissolution is completed, the present invention preferably performs filtration to obtain the first filter residue.
In the present invention, the first acid-dissolution preferably also gives a first filtrate, and the rare earth elements in the first filtrate preferably include La, pr, and Nd.
After the first filter residue is obtained, the first filter residue is preferably washed by weak acid water, subjected to solid-liquid separation and then mixed with the second inorganic acid.
In the present invention, the mass ratio of the first filter residue to the weak acid water is preferably 3 to 5:1.
in the invention, the concentration of hydrogen ions in the weak acid water is preferably 0.001-0.01 mol/L, and the washing function is complete liquid-solid separation, so that the solid phase is not occluded to carry away the liquid phase.
In the present invention, the temperature of the washing is preferably room temperature.
In the present invention, the number of times of washing is preferably 3 to 5 times.
In the invention, the liquid phase obtained by the solid-liquid separation is preferably used as water added during the first acid dissolution, so that the recycling is realized.
After the first filter residue is obtained, the first filter residue and the second inorganic acid are mixed for second acid dissolution, so that the second filter residue is obtained, and the concentration of hydrogen ions in the second inorganic acid is 3mol/L.
In the present invention, the second acid-soluble liquid-solid ratio is preferably 3 to 6:1, more preferably 4 to 5:1.
in the present invention, the second inorganic acid is preferably hydrochloric acid, nitric acid or sulfuric acid.
In the present invention, the temperature of the second acid dissolution is preferably 20 to 50 ℃, more preferably 40 ℃.
In the invention, the method for grouping the rare earth oxide acid solutions is applied to actual production, the stirring speed of the second acid solutions is preferably 40-50 r/min, the method for grouping the rare earth oxide acid solutions is applied to laboratories, and the stirring speed of the second acid solutions is preferably 400-500 r/min, more preferably 450r/min.
After the second acid dissolution is completed, the present invention preferably performs filtration to obtain the second filter residue.
In the present invention, the second acid-dissolution preferably also gives a second filtrate, and the rare earth elements in the second filtrate preferably include Sm, eu, gd, and Dy.
After the second filter residue is obtained, the second filter residue is preferably washed by weak acid water, subjected to solid-liquid separation and then mixed with the third inorganic acid.
In the present invention, the mass ratio of the second filter residue to the weak acid water is preferably 3 to 5:1.
in the invention, the concentration of hydrogen ions in the weak acid water is preferably 0.001-0.01 mol/L, and the washing function is complete liquid-solid separation, so that the solid phase is not occluded to carry away the liquid phase.
In the present invention, the temperature of the washing is preferably room temperature.
In the present invention, the number of times of washing is preferably 3 to 5 times.
In the invention, the liquid phase obtained by the solid-liquid separation is preferably used as water added during the first acid dissolution, so that the recycling is realized.
After the second filter residue is obtained, the second filter residue and a third inorganic acid are mixed for third acid dissolution, so that the third filter residue is obtained, and the concentration of hydrogen ions in the third inorganic acid is 5mol/L.
In the present invention, the liquid-solid ratio of the third acid solution is preferably 3 to 6:1, more preferably 4 to 5:1.
in the present invention, the third inorganic acid is preferably hydrochloric acid, nitric acid or sulfuric acid.
In the present invention, the temperature of the third acid dissolution is preferably 60 to 80 ℃, more preferably 65 to 75 ℃.
In the invention, the method for grouping the rare earth oxide acid solutions is applied to actual production, the stirring speed of the third acid solutions is preferably 70-80 r/min, the method for grouping the rare earth oxide acid solutions is applied to a laboratory, and the stirring speed of the third acid solutions is preferably 600-700 r/min, and more preferably 650r/min.
After the third acid dissolution is completed, the present invention preferably performs filtration to obtain the third filter residue.
In the present invention, the rare earth elements in the third filter residue preferably include Ce and Tb.
In the present invention, the third acid-dissolution preferably also gives a third filtrate, and the rare earth elements in the third filtrate preferably include Ho, Y, er, tm, yb and Lu.
In order to further illustrate the present invention, the method of acid-soluble grouping of rare earth oxides provided herein is described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
Step 1: weighing 100g of mixed rare earth raw materials:
step 2: 400mL of 1mol/L HCl was added;
step 3: controlling the temperature to be 10 ℃, starting stirring, wherein the stirring speed is 250r/min, and the leaching time is as follows: 30min;
step 4: the filtrate was filtered and the first filtrate was sampled and analyzed, wherein the rare earth elements are shown in table 1. Adding 0.2 mol/L50 mL weak acid water into the first filter residue, and repeatedly washing for 3 times;
TABLE 1 the content of rare earth elements in the first filtrate is the mass percent of rare earth elements in the misch metal raw material
Step 5: adding 400mL of 3mol/L HCl into the first filter residue, controlling the temperature to be 35 ℃, setting the stirring speed to be 450r/min, and leaching out for the time: 60min;
step 6: the filtrate was filtered and the second filtrate was sampled and analyzed, wherein the rare earth elements are shown in table 2. Adding 0.2 mol/L50 mL weak acid water into the second filter residue, and repeatedly washing for 3 times;
TABLE 2 the content of rare earth elements in the second filtrate is the mass percent of rare earth elements in the misch metal raw material
Step 7: adding 5mol/L HCl 500mL into the second filter residue, controlling the temperature to 65 ℃, setting the stirring speed to 650r/min, and leaching for the time: for 90min;
step 8: the third filtrate was filtered and sampled for analysis, wherein the rare earth elements are shown in table 3. And thirdly, sampling and analyzing filter residues, wherein the filter residues are mainly Ce and Tb, as shown in a rare earth element table 4.
TABLE 3 the content of rare earth elements in the third filtrate is the mass percent of rare earth elements in the mixed rare earth raw material
Table 4 the content of rare earth element in the third residue is the mass percentage of rare earth element in the mixed rare earth raw material
Example 2
Step 1: weighing 100g of mixed rare earth raw materials:
step 2: 0.5mol/L H is added 2 SO 4 300mL；
Step 3: controlling the temperature to be 10 ℃, starting stirring, wherein the stirring speed is 250r/min, and the leaching time is as follows: 30min;
step 4: the filtrate was filtered and the first filtrate was sampled and analyzed, wherein the rare earth elements are shown in table 5. Adding 0.2 mol/L50 mL weak acid water into the first filter residue, and repeatedly washing for 3 times;
TABLE 5 the content of rare earth elements in the first filtrate is the mass percent of rare earth elements in the misch metal raw material
Step 5: adding 1.5mol/L H into the first filter residue 2 SO 4 400mL, controlling the temperature to be 35 ℃, setting the stirring speed to be 450r/min, and leaching the leaching time: 60min;
step 6: the filtrate was filtered and the second filtrate was sampled and analyzed, wherein the rare earth elements are shown in table 6. Adding 0.2 mol/L50 mL weak acid water into the second filter residue, and repeatedly washing for 3 times;
TABLE 6 the content of rare earth elements in the second filtrate is the mass percent of rare earth elements in the misch metal raw material
Step 7: adding 2.5mol/L H to the second filter residue 2 SO 4 500mL, the temperature is controlled to be 65 ℃, the stirring speed is set to be 650r/min, and the leaching time is set to be: for 90min;
step 8: the third filtrate was filtered and sampled for analysis, wherein the rare earth elements are shown in table 7. And thirdly, sampling and analyzing filter residues, wherein the filter residues are mainly Ce and Tb, as shown in a rare earth element table 8.
TABLE 7 the content of rare earth elements in the third filtrate is the mass percent of rare earth elements in the misch metal raw material
Table 8 the content of rare earth element in the third residue is the mass percentage of rare earth element in the mixed rare earth raw material
Example 3
Step 1: weighing 100g of mixed rare earth raw materials:
step 2: adding 300mL of 1mol/L HCl;
step 3: controlling the temperature to be 15 ℃, starting stirring, wherein the stirring speed is 250r/min, and the leaching time is as follows: 30min;
step 4: the filtrate was filtered and the first filtrate was sampled and analyzed, wherein the rare earth elements are shown in table 9. Adding 0.2 mol/L50 mL weak acid water into the first filter residue, and repeatedly washing for 3 times;
TABLE 9 the content of rare earth elements in the first filtrate is the mass percent of rare earth elements in the misch metal raw material
Step 5: adding 400mL of 3mol/L HCl into the first filter residue, controlling the temperature to be 40 ℃, setting the stirring speed to be 450r/min, and leaching out for the time: 60min;
step 6: the filtrate was filtered and the second filtrate was sampled and analyzed, wherein the rare earth elements are shown in table 10. Adding 0.2 mol/L50 mL weak acid water into the second filter residue, and repeatedly washing for 3 times;
table 10 the content of rare earth element in the second filtrate is the mass percentage of rare earth element in the mixed rare earth raw material
Step 7: adding 5mol/L HCl 500mL into the second filter residue, controlling the temperature to 65 ℃, setting the stirring speed to 650r/min, and leaching for the time: for 90min;
step 8: the third filtrate was filtered and sampled for analysis, wherein the rare earth elements are shown in table 11. And a third filter residue sample analysis, wherein the samples are mainly Ce and Tb, as shown in a rare earth element table 12.
Table 11 the content of rare earth element in the third filtrate is the mass percentage of rare earth element in the mixed rare earth raw material
Table 12 the content of rare earth element in the third residue is the mass percentage of rare earth element in the mixed rare earth raw material
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (3)
1. A method for acid-soluble grouping of rare earth oxides, comprising the steps of:
mixing a rare earth oxide raw material, water and a first inorganic acid for first acid dissolution to obtain first filter residues, wherein the concentration of hydrogen ions in the first inorganic acid is 1mol/L;
mixing the first filter residue with a second inorganic acid to perform second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3mol/L;
mixing the second filter residue with a third inorganic acid to perform third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5mol/L;
the rare earth elements contained in the rare earth oxide raw material comprise La, ce, pr, nd, sm, eu, gd, tb, dy, ho, Y, er, tm, yb and Lu;
the temperature of the first acid dissolution is 0-20 ℃;
the temperature of the second acid dissolution is 20-50 ℃;
the temperature of the third acid dissolution is 60-80 ℃;
the first acid dissolution also obtains first filtrate, and rare earth elements in the first filtrate are La, pr and Nd;
the second acid dissolution also obtains second filtrate, and rare earth elements in the second filtrate are Sm, eu, gd and Dy;
and the third acid dissolution also obtains third filtrate, wherein rare earth elements in the third filtrate are Ho, Y, er, tm, yb and Lu.
2. The method of claim 1, wherein the first, second, and third acid solutions independently have a liquid to solid ratio of 3 to 6:1.
3. the method of claim 1, wherein the first, second, and third mineral acids are independently hydrochloric acid, nitric acid, or sulfuric acid.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041384A (en) * | 2011-01-07 | 2011-05-04 | 内蒙古科技大学 | Synergistic extraction separation method of rare-earth elements |
| CN104245973A (en) * | 2012-04-09 | 2014-12-24 | 工艺研究欧泰克公司 | Process for extraction of rare earth elements |
| CN104775026A (en) * | 2015-03-31 | 2015-07-15 | 江西洁球环保科技有限公司 | Method for extracting high-purity uranium, thorium and mixed rare earths from excellent molten slag |
| CN107208177A (en) * | 2014-07-21 | 2017-09-26 | 搜索矿物公司 | The acidleach of rare earth element is carried |
| CN108559842A (en) * | 2018-07-11 | 2018-09-21 | 钢研集团稀土科技有限公司 | A kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate |
| CN109136538A (en) * | 2018-08-22 | 2019-01-04 | 包头稀土研究院 | The processing method of rare earth ore concentrate |
| CN109971946A (en) * | 2019-05-10 | 2019-07-05 | 江西铜业技术研究院有限公司 | A kind of method of rare earth and fluorine in synthetical recovery bastnaesite |
| CN110241309A (en) * | 2019-05-08 | 2019-09-17 | 湖南景翌湘台环保高新技术开发有限公司 | A kind of method that useless polishing powder from rare earth extracts white carbon black and rare earth water purification agent |
-
2022
- 2022-05-20 CN CN202210554314.0A patent/CN114836637B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041384A (en) * | 2011-01-07 | 2011-05-04 | 内蒙古科技大学 | Synergistic extraction separation method of rare-earth elements |
| CN104245973A (en) * | 2012-04-09 | 2014-12-24 | 工艺研究欧泰克公司 | Process for extraction of rare earth elements |
| CN107208177A (en) * | 2014-07-21 | 2017-09-26 | 搜索矿物公司 | The acidleach of rare earth element is carried |
| CN104775026A (en) * | 2015-03-31 | 2015-07-15 | 江西洁球环保科技有限公司 | Method for extracting high-purity uranium, thorium and mixed rare earths from excellent molten slag |
| CN108559842A (en) * | 2018-07-11 | 2018-09-21 | 钢研集团稀土科技有限公司 | A kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate |
| CN109136538A (en) * | 2018-08-22 | 2019-01-04 | 包头稀土研究院 | The processing method of rare earth ore concentrate |
| CN110241309A (en) * | 2019-05-08 | 2019-09-17 | 湖南景翌湘台环保高新技术开发有限公司 | A kind of method that useless polishing powder from rare earth extracts white carbon black and rare earth water purification agent |
| CN109971946A (en) * | 2019-05-10 | 2019-07-05 | 江西铜业技术研究院有限公司 | A kind of method of rare earth and fluorine in synthetical recovery bastnaesite |
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