CN114836637A - Acid dissolution grouping method for rare earth oxide - Google Patents
Acid dissolution grouping method for rare earth oxide Download PDFInfo
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- CN114836637A CN114836637A CN202210554314.0A CN202210554314A CN114836637A CN 114836637 A CN114836637 A CN 114836637A CN 202210554314 A CN202210554314 A CN 202210554314A CN 114836637 A CN114836637 A CN 114836637A
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- 239000002253 acid Substances 0.000 title claims abstract description 89
- 238000004090 dissolution Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 89
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 28
- -1 hydrogen ions Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims description 36
- 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
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium 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
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 25
- 238000000605 extraction Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 18
- 238000001914 filtration Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000002386 leaching Methods 0.000 description 10
- 238000005070 sampling Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 229910001122 Mischmetal 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
- 239000000047 product Substances 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
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004064 recycling 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 230000006978 adaptation Effects 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
- 239000003795 chemical substances by application Substances 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
- 239000000463 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
- 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
- 239000007858 starting material Substances 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
Classifications
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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
-
- 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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- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (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 an acid-soluble grouping method 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, and carrying out first acid dissolution to obtain a first filter residue, wherein the concentration of hydrogen ions in the first inorganic acid is 1 mol/L; mixing the first filter residue and a second inorganic acid for second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3 mol/L; and mixing the second filter residue and a third inorganic acid for third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5 mol/L. According to the invention, the acid dissolution is controlled to use the inorganic acids with different concentrations, the rare earth elements are grouped in the acid dissolution process, and the rare earth elements are grouped according to different concentrations of the dissolved inorganic acids, so that the effects of reducing the extraction pressure and the extraction stages are achieved for the subsequent extraction separation, 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 name for 17 rare earth elements. The rare earth has unique properties and purposes, and is widely applied to 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 minerals are various in variety and comprise monazite, bastnaesite, xenotime, southern ionic rare earth ore and the like. The rare earth elements in the rare earth minerals mostly exist in the form of isomorphism and ion adsorption, so that in order to fully utilize the rare earth elements, pretreatment is firstly carried out to destroy crystal lattices, the rare earth elements are separated out in the form of free rare earth ions and are sent to a rare earth separation plant in the form of rare earth compounds, and single rare earth chlorides with higher purity are produced through extraction and separation.
The rare earth raw materials mainly contain rare earth oxides, iron, silicon, calcium and other elements. The common processing flow of the common rare earth raw material is as follows: acid dissolution, extraction, precipitation and roasting. Wherein the 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 precipitating agent such as oxalic acid and carbonate to precipitate rare earth from water solution to obtain rare earth oxalate or carbonate; 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 of multiple rare earth elements and close separation coefficient, the solvent extraction method for separating the rare earth elements during extraction needs very large extraction tank stages, so that the extraction tanks have large stages for separating the various rare earth elements, occupy more space, and simultaneously have large acid-base consumption and extractant consumption, thereby increasing the production cost.
Disclosure of Invention
In view of the above, the present invention provides a method for acid-dissolving and grouping rare earth oxides. According to the invention, the acid dissolution conditions are controlled, and the rare earth elements are grouped in the acid dissolution process, so that the pressure of the subsequent extraction process is reduced, the extraction stages are reduced, the space resource is saved, and the production cost is reduced.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a rare earth oxide acid dissolution grouping method, which comprises the following steps:
mixing a rare earth oxide raw material, water and a first inorganic acid, and carrying out first acid dissolution to obtain a first filter residue, wherein the concentration of hydrogen ions in the first inorganic acid is 1 mol/L;
mixing the first filter residue and a second inorganic acid for second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3 mol/L;
and mixing the second filter residue and a third inorganic acid for third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5 mol/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 to the second acid solution to the third acid solution is independently 3-6: 1.
preferably, the first, second and third mineral 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 solution is 60-80 ℃.
Preferably, the first acid dissolving also produces a first filtrate, and the rare earth elements in the first filtrate comprise La, Pr and Nd.
Preferably, the second acid solution also produces a second filtrate, and the rare earth elements in the second filtrate comprise Sm, Eu, Gd and Dy.
Preferably, the third acid solution also obtains a third filtrate, and the rare earth elements in the third filtrate comprise Ho, Y, Er, Tm, Yb and Lu.
The invention provides a rare earth oxide acid dissolution grouping method, which comprises the following steps: mixing a rare earth oxide raw material, water and a first inorganic acid, and carrying out first acid dissolution to obtain a first filter residue, wherein the concentration of hydrogen ions in the first inorganic acid is 1 mol/L; mixing the first filter residue and a second inorganic acid for second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3 mol/L; and mixing the second filter residue and a third inorganic acid for third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the acid dissolution is controlled to use inorganic acids with different concentrations, the rare earth elements are grouped in the acid dissolution process, and the rare earth elements are grouped according to different concentrations of the dissolved inorganic acids, so that the effects of reducing extraction pressure and extraction stages for subsequent extraction and separation are achieved, space resources are saved, the production cost is reduced, and meanwhile, after the separated feed liquid is extracted, the purity of a single product is guaranteed, and a certain positive effect is achieved on the reduction of the production cost. In actual production, the rare earth oxide directly treated by acid leaching needs a 60-level extraction tank, and the invention only needs the 60-level extraction tank.
Detailed Description
The invention provides a rare earth oxide acid dissolution grouping method, which comprises the following steps:
mixing a rare earth oxide raw material, water and a first inorganic acid, and carrying out first acid dissolution to obtain a first filter residue, wherein the concentration of hydrogen ions in the first inorganic acid is 1 mol/L;
mixing the first filter residue and a second inorganic acid for second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3 mol/L;
and mixing the second filter residue and a third inorganic acid for third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5 mol/L.
Unless otherwise specified, all starting materials used are commercial products in the art.
The method comprises the steps of mixing a rare earth oxide raw material, water and a first inorganic acid, and carrying out first acid dissolution to obtain a first filter residue, wherein the concentration of hydrogen ions in the first inorganic acid is 1 mol/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 element contained in the rare earth oxide raw material preferably includes 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 invention, the liquid-solid ratio of the first acid solution is preferably 3-6: 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 invention, the temperature of the first acid is preferably 0-20 ℃, and more preferably 10 ℃.
In the invention, the method for acid dissolution grouping of the rare earth oxides is applied to actual production, the stirring speed of the first acid solution is preferably 20-30 r/min, the method for acid dissolution grouping of the rare earth oxides is applied to a laboratory, and the stirring speed of the first acid solution is preferably 200-300 r/min, and more preferably 250 r/min.
After the first acid is dissolved, the filtering is preferably carried out to obtain the first filter residue.
In the present invention, the first acid solution preferably also yields 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 invention preferably uses weak acid water to wash the first filter residue, then carries out solid-liquid separation, and then is mixed with the second inorganic acid.
In the invention, the mass ratio of the first filter residue to the weak acid water is preferably 3-5: 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 has the function of completely separating liquid from solid without carrying the liquid phase away by the solid phase.
In the present invention, the temperature of the washing is preferably room temperature.
In the present invention, the number of washing is preferably 3 to 5.
In the present invention, the liquid phase obtained by the solid-liquid separation is preferably used as water added when the first acid is dissolved, so that recycling is realized.
After the first filter residue is obtained, the first filter residue and a second inorganic acid are mixed for second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3 mol/L.
In the invention, the liquid-solid ratio of the second acid solution is preferably 3-6: 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 invention, the temperature of the second acid is preferably 20-50 ℃, and more preferably 40 ℃.
In the invention, the method for acid dissolution grouping of rare earth oxides is applied to actual production, the stirring speed of the second acid solution is preferably 40-50 r/min, the method for acid dissolution grouping of rare earth oxides is applied to a laboratory, and the stirring speed of the second acid solution is preferably 400-500 r/min, more preferably 450 r/min.
After the second acid is dissolved, the filtering is preferably performed to obtain the second filter residue.
In the present invention, the second acid solution preferably also yields 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 invention preferably uses weak acid water to wash the second filter residue, then carries out solid-liquid separation, and then is mixed with the third inorganic acid.
In the invention, the mass ratio of the second filter residue to the weak acid water is preferably 3-5: 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 has the function of completely separating liquid from solid without carrying the liquid phase away by the solid phase.
In the present invention, the temperature of the washing is preferably room temperature.
In the present invention, the number of washing is preferably 3 to 5.
In the present invention, the liquid phase obtained by the solid-liquid separation is preferably used as water added when the first acid is dissolved, so that recycling is realized.
After the second filter residue is obtained, mixing the second filter residue with a third inorganic acid for third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5 mol/L.
In the invention, the liquid-solid ratio of the third acid solution is preferably 3-6: 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 invention, the temperature of the third acid is preferably 60-80 ℃, and more preferably 65-75 ℃.
In the invention, the rare earth oxide acid dissolution grouping method is applied to actual production, the stirring speed of the third acid dissolution is preferably 70-80 r/min, the rare earth oxide acid dissolution grouping method is applied to a laboratory, and the stirring speed of the third acid dissolution is preferably 600-700 r/min, and more preferably 650 r/min.
After the third acid is dissolved, the filtering is preferably performed to obtain the third filter residue.
In the present invention, the rare earth element in the third filter residue preferably includes Ce and Tb.
In the present invention, the third acid solution preferably further produces 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 following detailed description of the methods for acid dissolution grouping of rare earth oxides provided by the present invention is given with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Step 1: weighing 100g of mixed rare earth raw materials:
step 2: adding 400mL of 1mol/L HCl;
and step 3: controlling the temperature to be 10 ℃, starting stirring, wherein the stirring speed is 250r/min, and the leaching time is as follows: 30 min;
and 4, step 4: filtering, and sampling and analyzing the first filtrate, wherein the rare earth elements are shown in the table 1. Adding 0.2 mol/L50 mL weak acid water into the first filter residue, and repeatedly washing for 3 times;
TABLE 1 content of rare earth element in the first filtrate in the mass percent of rare earth element in the misch metal raw material
And 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 for: 60 min;
step 6: filtering, and sampling and analyzing the second filtrate, wherein the rare earth elements are shown in the 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 in the mass percent of the rare earth elements in the misch metal raw material
And 7: adding 500mL of 5mol/L HCl into the second filter residue, controlling the temperature to be 65 ℃, setting the stirring speed to be 650r/min, and leaching time to be as follows: 90 min;
and 8: filtering, and sampling and analyzing the third filtrate, wherein the rare earth elements are shown in the table 3. The third residue was sampled and analyzed, wherein Ce and Tb were predominant, as shown in table 4 for rare earth elements.
TABLE 3 Mass percents of the rare earth elements in the third filtrate in the mixed rare earth raw material
TABLE 4 Mass percents of the rare earth elements in the third residue 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 was added 2 SO 4 300mL；
And step 3: controlling the temperature to be 10 ℃, starting stirring, wherein the stirring speed is 250r/min, and the leaching time is as follows: 30 min;
and 4, step 4: filtering, and sampling and analyzing the first filtrate, wherein the rare earth elements are shown in the table 5. Adding 0.2 mol/L50 mL weak acid water into the first filter residue, and repeatedly washing for 3 times;
TABLE 5 weight percent of the rare earth element in the first filtrate to the rare earth element in the misch metal raw material
And 5: adding 1.5mol/L of first filter residue H 2 SO 4 400mL, the temperature is controlled to be 35 ℃, the stirring speed is set to be 450r/min, and the leaching time is as follows: 60 min;
step 6: and (4) filtering, and sampling and analyzing a second filtrate, wherein the rare earth elements are shown in the 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 element in the second filtrate accounts for the mass percent of the rare earth element in the misch metal raw material
And 7: adding 2.5mol/L H into 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 as follows: 90 min;
and 8: filtering, and sampling and analyzing the third filtrate, wherein the rare earth elements are shown in the table 7. The third residue was sampled and analyzed, wherein Ce and Tb were predominant, as shown in table 8 for rare earth elements.
TABLE 7 Mass percents of the rare earth elements in the third filtrate in the mixed rare earth raw material
TABLE 8 Mass percents of the rare earth elements in the third residue 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;
and step 3: controlling the temperature to be 15 ℃, starting stirring, wherein the stirring speed is 250r/min, and the leaching time is as follows: 30 min;
and 4, step 4: filtering, and sampling and analyzing the first filtrate, wherein the rare earth elements are shown in the table 9. Adding 0.2 mol/L50 mL weak acid water into the first filter residue, and repeatedly washing for 3 times;
TABLE 9 Mass percents of the rare earth elements in the first filtrate based on the rare earth elements in the mixed rare earth raw material
And 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 for: 60 min;
step 6: filtering, and sampling and analyzing the second filtrate, wherein the rare earth elements are shown in the table 10. Adding 0.2 mol/L50 mL weak acid water into the second filter residue, and repeatedly washing for 3 times;
TABLE 10 content of rare earth element in the second filtrate in percentage by mass of rare earth element in the misch metal raw material
And 7: adding 500mL of 5mol/L HCl into the second filter residue, controlling the temperature to be 65 ℃, setting the stirring speed to be 650r/min, and leaching time to be as follows: 90 min;
and 8: filtering, and sampling and analyzing the third filtrate, wherein the rare earth elements are shown in the table 11. The third residue was sampled and analyzed, wherein Ce and Tb were predominant, as shown in table 12 for rare earth elements.
TABLE 11 Mass percents of the rare earth elements in the third filtrate based on the rare earth elements in the mixed rare earth raw material
TABLE 12 Mass percents of the rare earth elements in the third residue in the mixed rare earth raw material
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that modifications and adaptations can be made by those skilled in the art without departing from the principle of the present invention, and should be considered as within the scope of the present invention.
Claims (10)
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, and carrying out first acid dissolution to obtain a first filter residue, wherein the concentration of hydrogen ions in the first inorganic acid is 1 mol/L;
mixing the first filter residue and a second inorganic acid for second acid dissolution to obtain a second filter residue, wherein the concentration of hydrogen ions in the second inorganic acid is 3 mol/L;
and mixing the second filter residue and a third inorganic acid for third acid dissolution to obtain a third filter residue, wherein the concentration of hydrogen ions in the third inorganic acid is 5 mol/L.
2. The method according to claim 1, wherein 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.
3. The method of claim 1, wherein the first, second, and third acid solutions independently have a liquid-to-solid ratio of 3-6: 1.
4. the method of claim 1, wherein the first, second, and third mineral acids are independently hydrochloric acid, nitric acid, or sulfuric acid.
5. The method according to claim 1, wherein the temperature of the first acid dissolution is 0 to 20 ℃.
6. The method according to claim 1, wherein the temperature of the second acid dissolution is 20 to 50 ℃.
7. The method according to claim 1, wherein the temperature of the third acid dissolution is 60 to 80 ℃.
8. The method according to claim 1 or 5, characterized in that the first acid dissolution also yields a first filtrate, the rare earth elements in the first filtrate comprising La, Pr and Nd.
9. The method of claim 1 or 6, wherein the second acid solution further produces a second filtrate, and the rare earth elements in the second filtrate comprise Sm, Eu, Gd, and Dy.
10. The method of claim 1 or 7, wherein the third acid dissolution also yields a third filtrate, the rare earth elements in the third filtrate comprising Ho, Y, Er, Tm, Yb and Lu.
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