CN116654970A - Method for preparing high-purity scandium oxide by scandium hydroxide purification - Google Patents
Method for preparing high-purity scandium oxide by scandium hydroxide purification Download PDFInfo
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- CN116654970A CN116654970A CN202310726842.4A CN202310726842A CN116654970A CN 116654970 A CN116654970 A CN 116654970A CN 202310726842 A CN202310726842 A CN 202310726842A CN 116654970 A CN116654970 A CN 116654970A
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- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 22
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000746 purification Methods 0.000 title abstract description 5
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 110
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 109
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012074 organic phase Substances 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012043 crude product Substances 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 17
- OMMFSGNJZPSNEH-UHFFFAOYSA-H oxalate;scandium(3+) Chemical compound [Sc+3].[Sc+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OMMFSGNJZPSNEH-UHFFFAOYSA-H 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 235000011008 sodium phosphates Nutrition 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 73
- 238000003756 stirring Methods 0.000 description 8
- 239000003350 kerosene Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01F17/212—Scandium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing high-purity scandium oxide by scandium hydroxide purification, which comprises the following steps: s1, re-dissolving a scandium hydroxide crude product with acid liquor to obtain scandium re-solution; s2, adding phosphate into the scandium return solution to perform chemical impurity removal, and filtering to obtain scandium purified solution; wherein the molar quantity of the added phosphate is 1.5 to 3 times of the molar total quantity of iron, zirconium and calcium in the scandium return solution; s3, selectively extracting scandium in the scandium purified solution by using an organic extractant to obtain a scandium-rich organic phase; s4, washing the scandium-rich organic phase with acid liquor; s5, back-extracting scandium in the scandium-rich organic phase by using alkali liquor to obtain scandium hydroxide; s6, re-dissolving scandium hydroxide obtained by back extraction by using acid liquor to obtain a secondary scandium re-solution; s7, adding oxalic acid into the scandium secondary return solution to obtain scandium oxalate precipitate; and S8, calcining scandium oxalate precipitate to obtain high-purity scandium oxide with purity of more than 99.9%. The invention can realize short-flow and high-efficiency scandium recovery.
Description
Technical Field
The invention relates to the technical field of scandium recovery, in particular to a method for preparing high-purity scandium oxide by purifying scandium hydroxide.
Background
Scandium is an important strategic metal element and has wide application in the fields of aerospace, electronic industry, special materials and the like. In industry, titanium white waste acid and chloridized smoke dust are used as main raw materials for extracting scandium, scandium-containing solution is obtained through pretreatment, and scandium hydroxide crude product is obtained through extraction by an organic extractant, washing by a scandium-rich organic phase and alkali back extraction. Because scandium hydroxide generally contains impurities such as iron, zirconium, titanium, calcium, magnesium and the like, the scandium hydroxide cannot meet the application requirements of the high-end field. Therefore, scandium hydroxide purification to produce high purity scandium oxide is a hot spot of research.
In the prior art, when high-purity scandium oxide is recovered and prepared, multiple extractions are needed to separate metal impurity ions, so that the preparation process is complex and the flow is long.
Disclosure of Invention
The invention mainly aims to provide a method for preparing high-purity scandium oxide by purifying scandium hydroxide, which aims to solve the problems of complex preparation process and longer flow caused by the fact that multiple times of extraction are needed to separate metal impurity ions when the high-purity scandium oxide is recovered and prepared in the prior art.
According to one aspect of the present invention, there is provided a method for preparing high purity scandium oxide by purifying scandium hydroxide, comprising the steps of:
s1, re-dissolving a scandium hydroxide crude product with acid liquor to obtain scandium re-solution;
s2, adding phosphate into the scandium return solution to perform chemical impurity removal, and filtering to obtain scandium purified solution; wherein the molar quantity of the added phosphate is 1.5-3 times of the molar total quantity of iron, zirconium and calcium in the scandium return solution;
s3, selectively extracting scandium in the scandium purified solution by using an organic extractant to obtain a scandium-rich organic phase;
s4, washing the scandium-rich organic phase with acid liquor to remove metal impurity ions of the scandium-rich organic phase;
s5, back-extracting scandium in the scandium-rich organic phase by using alkali liquor to obtain scandium hydroxide;
s6, re-dissolving scandium hydroxide obtained by back extraction by using acid liquor to obtain a secondary scandium re-solution;
s7, adding oxalic acid into the scandium secondary return solution to obtain scandium oxalate precipitate;
and S8, calcining the scandium oxalate precipitate to obtain high-purity scandium oxide with the purity of more than 99.9%.
According to one embodiment of the invention, the scandium hydroxide crude product comprises 35.0-75.0% by mass of Sc (OH) 3 Fe (OH) 1.0-5.0% 3 2.0 to 7.0 percent of Zr (OH) 4 0.5 to 1.5 percent of Ca (OH) 2 0.5 to 1.5% of Ti (OH) 4 。
According to one embodiment of the invention, in step S1, the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, H in the acid solution + The concentration is 2-6 mol/L, and the liquid-solid ratio of the acid liquid to the scandium hydroxide crude product is (20-50) mL 1g.
According to one embodiment of the invention, in step S2, the phosphate is one or more of the following: sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate.
According to one embodiment of the invention, in the step S3, the organic extractant comprises 3-10% of extractant by volume, wherein the extractant is one or more of P204, P507, P350 and TBP, and the volume ratio of the organic phase to the aqueous phase is 1 (10-20).
According to one embodiment of the present invention, in step S4, the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and H is in the acid solution + The concentration is 1-3 mol/L, and the volume ratio of the organic phase to the water phase is 1 (0.5-1.5).
According to one embodiment of the invention, in the step S5, the alkali solution is one or two of sodium hydroxide and potassium hydroxide, the alkali concentration is 5-10% by mass, and the volume ratio of the organic phase to the aqueous phase is 1 (5-15).
According to one embodiment of the present invention, in step S6, the acid solution is one or more of sulfuric acid, hydrochloric acid, and nitric acid, and H is in the acid solution + The concentration is 1-3 mol/L, and the liquid-solid ratio of the acid solution to scandium hydroxide is (20-50) mL to 1g.
According to one embodiment of the invention, in step S7, the molar ratio of scandium to oxalic acid is 1 (3-5).
According to one embodiment of the present invention, in step S8, the calcination temperature is 750 to 950 ℃ and the calcination time is 30 to 150 minutes.
In the method for preparing high-purity scandium oxide by purifying scandium hydroxide according to the embodiment of the invention, most cations such as iron, zirconium, calcium and the like can be removed by adding phosphate into scandium return solution for chemical impurity removal, and then extraction is only needed once, so that the process can be simplified, the flow is shortened, and the scandium can be recovered efficiently.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments of the present invention will be described in further detail with reference to specific embodiments.
It should be noted that, in the embodiments of the present invention, all the expressions "first" and "second" are used to distinguish two entities with the same name but different entities or different parameters, and it is noted that the "first" and "second" are only used for convenience of expression, and should not be construed as limiting the embodiments of the present invention, and the following embodiments are not described one by one.
The invention provides a method for preparing high-purity scandium oxide by scandium hydroxide purification, which comprises the following steps:
s1, re-dissolving a scandium hydroxide crude product with acid liquor to obtain scandium re-solution;
s2, adding phosphate into the scandium return solution to perform chemical impurity removal, and filtering to obtain scandium purified solution; wherein the molar quantity of the added phosphate is 1.5-3 times of the molar total quantity of iron, zirconium and calcium in the scandium return solution;
s3, selectively extracting scandium in the scandium purified solution by using an organic extractant to obtain a scandium-rich organic phase;
s4, washing the scandium-rich organic phase with acid solution;
s5, back-extracting scandium in the scandium-rich organic phase by using alkali liquor to obtain scandium hydroxide;
s6, re-dissolving scandium hydroxide obtained by back extraction by using acid liquor to obtain a secondary scandium re-solution;
s7, adding oxalic acid into the scandium secondary return solution to obtain scandium oxalate precipitate;
and S8, calcining the scandium oxalate precipitate to obtain high-purity scandium oxide with the purity of more than 99.9%.
In the embodiment of the method, the phosphate is added into scandium returning solution to perform chemical impurity removal, so that most cations such as iron, zirconium and calcium can be removed, and only one extraction is needed, thereby simplifying the process, shortening the flow and realizing the efficient recovery of scandium.
In an embodiment of the invention, the scandium hydroxide crude product can be obtained from titanium white waste acid and/or chlorinated soot by preliminary treatment. In some embodiments, the scandium hydroxide crude product comprises, by mass%, 35.0 to 75.0% Sc (OH) 3 Fe (OH) 1.0-5.0% 3 2.0 to 7.0 percent of Zr (OH) 4 0.5 to 1.5 percent of Ca (OH) 2 0.5 to 1.5% of Ti (OH) 4 。
In some embodiments, in step S1, the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and H in the acid solution + The concentration is 2-6 mol/L, and the liquid-solid ratio of the acid liquid to the scandium hydroxide crude product is (20-50) mL to 1g, thereby ensuring that the scandium hydroxide crude product is fully dissolved. The scandium hydroxide crude product can be dissolved by re-dissolving under the temperature condition of 20-100 ℃ and stirring for 1-24 h, and then scandium re-solution is obtained by filtering.
In the step S2, phosphate is added according to 1.5-3 times of the molar total amount of iron, zirconium and calcium in the scandium return solution, so that the iron, zirconium and calcium in the scandium return solution are fully precipitated and separated. In some embodiments, the phosphate is one or more of the following: sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate. Phosphate can be added into scandium solution at the temperature of 20-100 ℃ and precipitated for 0.5-12 h, and then scandium purified solution is obtained by filtration.
In some embodiments, in step S3, the organic extractant comprises 3-10% by volume of extractant, wherein the extractant is one or more of P204, P507, P350, TBP, and the volume ratio (O/a) of the organic phase to the aqueous phase is 1 (10-20). The organic extractant also comprises sulfonated kerosene, and the sulfonated kerosene is used for diluting the extractant to the concentration of 3-10%. The scandium-rich organic phase can be obtained by extracting for 1 to 12 hours at the temperature of 20 to 60 ℃ and then separating the organic phase.
In some embodiments, in step S4, the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and H in the acid solution + The concentration is 1-3 mol/L, and the volume ratio (O/A) of the organic phase to the water phase is 1 (0.5-1.5). Can be washed for 1 to 12 hours at the temperature of 20 to 60 ℃ to remove trace metal impurity ions such as iron, titanium, calcium and the like in the organic phase, and the organic phase is separated to obtain the scandium-rich organic phase with impurities removed by washing.
In some embodiments, in step S5, the alkali solution is one or both of sodium hydroxide and potassium hydroxide, the alkali concentration is 5-10% by mass, and the volume ratio (O/A) of the organic phase to the aqueous phase is 1 (5-15). The scandium hydroxide can be obtained by stripping for 0.5 to 12 hours at the temperature of 20 to 100 ℃ and then separating the organic phase.
In some embodiments, in step S6, the acid solution is one or more of sulfuric acid, hydrochloric acid, and nitric acid, and H is in the acid solution + The concentration is 1-3 mol/L, and the liquid-solid ratio of the acid solution to scandium hydroxide is (20-50) mL to 1g. The scandium secondary solution can be obtained by stirring and dissolving for 1-24 h at the temperature of 20-100 ℃ and then filtering.
In some embodiments, in step S7, the molar ratio of scandium to oxalic acid is 1 (3-5), ensuring that scandium oxalate is sufficiently precipitated, and may be precipitated at 20-60℃for 1-24 h.
In some embodiments, in step S8, the calcination temperature is 750 to 950 ℃ and the calcination time is 30 to 150 minutes.
In summary, the invention provides a method for preparing high-purity scandium oxide by removing impurities from scandium hydroxide through phosphate chemistry and selectively extracting scandium, and performing back extraction and oxalic acid precipitation scandium calcination, which can realize short-flow and high-efficiency recovery of scandium.
The following description is made with reference to specific examples.
Example 1
Taking 100g of scandium hydroxide crude product, adding 2000mL of H + Hydrochloric acid solution with the concentration of 1mol/L is stirred and dissolved for 1h at the temperature of 100 ℃ and filtered to obtain scandium return solution. Adding sodium phosphate according to 3 times of the molar weight of iron, zirconium and calcium in the scandium return solution, stirring for 12 hours at 60 ℃, and filtering to obtain scandium purified solution. P204 (3%) + sulfonated kerosene (97%) was used as extractant, extracted at O/a=1:10, 20 ℃ for 2h, and the aqueous phase was separated to give scandium-rich organic phase. H was added at O/A=1:0.5 + Hydrochloric acid solution with the concentration of 3mol/L is washed for 6 hours at the temperature of 60 ℃, and the water phase is separated to obtain a scandium-rich organic phase with impurities removed by washing. Adding 10% NaOH solution into the scandium-rich organic phase according to O/A=1:5, carrying out back extraction for 0.5h at 100 ℃, and separating the organic phase to obtain scandium hydroxide. Adding H into scandium hydroxide according to a liquid-solid ratio of 20:1 + Hydrochloric acid solution with the concentration of 1mol/L is stirred and dissolved for 12 hours at the temperature of 100 ℃ and filtered to obtain scandium secondary return solution. Finally, scandium: oxalic acid=1:5 (molar ratio) oxalic acid is added into scandium secondary solution, precipitation is carried out for 24 hours at 20 ℃, scandium oxalate precipitation is obtained, scandium oxalate is calcined for 90 minutes at 850 ℃, and a high-purity scandium oxide product with the purity of 99.95% is obtained.
Example 2
Taking 100g of scandium hydroxide crude product, adding 1500mL of H + The sulfuric acid solution with the concentration of 3mol/L is stirred and dissolved for 12 hours at the temperature of 20 ℃ and filtered to obtain scandium return solution. Adding potassium phosphate according to 1.5 times of the molar weight of iron, zirconium and calcium in the scandium return solution, stirring for 2 hours at 100 ℃, and filtering to obtain scandium purified solution. TBP (5%) + sulfonated kerosene (95%) is used as extractant, and extracted for 6h at 60 ℃ according to O/A=1:15, and the scandium-rich organic phase is obtained by separating the aqueous phase. H was added at O/A=1:1 + Washing the mixture for 1h at 80 ℃ by using a sulfuric acid solution with the concentration of 1mol/L, and separating an aqueous phase to obtain a scandium-rich organic phase with impurities removed by washing. Adding 5% KOH solution into the scandium-rich organic phase according to O/A=1:10, carrying out back extraction for 12h at 20 ℃, and separating the organic phase to obtain scandium hydroxide. Adding H into scandium hydroxide according to a liquid-solid ratio of 10:1 + The sulfuric acid solution with the concentration of 3mol/L is stirred and dissolved for 1h at the temperature of 100 ℃ and filtered to obtain a secondary scandium return solution. Finally, scandium: oxalic acid=1:3 (molar ratio) oxalic acid is added into scandium secondary solution, and the mixture is precipitated for 1h at 60 ℃ to obtain scandium oxalate precipitate, and scandium oxalate is calcined for 150min at 750 ℃ to obtain a high-purity scandium oxide product with purity of 99.98%.
Example 3
Taking 100g of scandium hydroxide crude product, adding 1000mL of H + And (3) stirring and dissolving the nitric acid solution with the concentration of 2mol/L at 60 ℃ for 10 hours, and filtering to obtain scandium return solution. Adding mixed salt of potassium phosphate and sodium phosphate (molar ratio 1:1) according to 2 times of the molar weight of iron, zirconium and calcium in the scandium return solution, stirring for 6h at 40 ℃, and filtering to obtain scandium purified solution. P350 (5%) + sulfonated kerosene (95%) was used as extractant, extracted at O/a=1:20, 60 ℃ for 6h, and the aqueous phase was separated to give scandium-rich organic phase. H was added at O/A=1:1 + And (3) washing the organic phase for 1h at 60 ℃ by using a nitric acid solution with the concentration of 2mol/L, and separating the aqueous phase to obtain a scandium-rich organic phase with impurities removed by washing. Adding 3% KOH solution into the scandium-rich organic phase according to O/A=1:15, carrying out back extraction for 12h at 40 ℃, and separating the organic phase to obtain scandium hydroxide. Adding H into scandium hydroxide according to a liquid-solid ratio of 10:1 + And (3) stirring and dissolving the nitric acid solution with the concentration of 2mol/L at 80 ℃ for 3 hours, and filtering to obtain a scandium secondary return solution. Finally, scandium: oxalic acid=1:4 (molar ratio) oxalic acid is added into scandium secondary solution, precipitation is carried out for 12 hours at 30 ℃ to obtain scandium oxalate precipitate, and scandium oxalate is calcined for 120 minutes at 950 ℃ to obtain a high-purity scandium oxide product with purity of 99.94%.
Example 4
Taking 100g of scandium hydroxide crude product, adding 1000mL of H + The mixed solution of hydrochloric acid and sulfuric acid with the concentration of 1mol/L (molar ratio of 1:1) is stirred and dissolved for 6 hours at 80 ℃, and scandium return solution is obtained by filtration. Adding mixed salt of dipotassium hydrogen phosphate and disodium hydrogen phosphate (molar ratio 1:1) according to 2.5 times of the molar weight of iron, zirconium and calcium in the scandium return solution, stirring for 10 hours at 80 ℃, and filtering to obtain scandium purified solution. P350 (3%) +tbp (5%) +sulfonated kerosene (92%) was used as extractant, extracted at O/a=1:15, 40 ℃ for 6h, and the aqueous phase was separated to give scandium-rich organic phase. H was added at O/A=1:1.5 + The mixed solution of hydrochloric acid and sulfuric acid with the concentration of 1mol/L (molar ratio of 1:1) is washed for 4 hours at the temperature of 30 ℃, and the water phase is separated to obtain a scandium-rich organic phase with impurities removed by washing. Adding 10% KOH and NaOH mixed solution (molar ratio 1:1) into the scandium-rich organic phase according to O/A=1:10, back-extracting for 12 hours at 60 ℃, and separating the organic phase to obtain scandium hydroxide. Adding H into scandium hydroxide according to a liquid-solid ratio of 10:1 + At a concentration of 2molThe mixed solution of hydrochloric acid and sulfuric acid (molar ratio 1:1) of/L is stirred and dissolved for 6 hours at 80 ℃, and the scandium secondary return solution is obtained by filtering. Finally, scandium: oxalic acid=1:3 (molar ratio) oxalic acid is added into scandium secondary solution, precipitation is carried out for 12 hours at 20 ℃ to obtain scandium oxalate precipitate, and scandium oxalate is calcined for 120 minutes at 900 ℃ to obtain a high-purity scandium oxide product with purity of 99.99%.
Those of ordinary skill in the art will appreciate that: the above discussion of any embodiment is merely exemplary and is not intended to imply that the scope of the disclosure of embodiments of the invention, including the claims, is limited to such examples; combinations of features of the above embodiments or in different embodiments are also possible within the idea of an embodiment of the invention, and there are many other variations of the different aspects of the embodiments of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, equivalent substitutions, improvements, and the like, which are made within the spirit and principles of the embodiments of the invention, are included within the scope of the embodiments of the invention.
Claims (10)
1. The method for preparing high-purity scandium oxide by purifying scandium hydroxide is characterized by comprising the following steps of:
s1, re-dissolving a scandium hydroxide crude product with acid liquor to obtain scandium re-solution;
s2, adding phosphate into the scandium return solution to perform chemical impurity removal, and filtering to obtain scandium purified solution; wherein the molar quantity of the added phosphate is 1.5-3 times of the molar total quantity of iron, zirconium and calcium in the scandium return solution;
s3, selectively extracting scandium in the scandium purified solution by using an organic extractant to obtain a scandium-rich organic phase;
s4, washing the scandium-rich organic phase with acid solution;
s5, back-extracting scandium in the scandium-rich organic phase by using alkali liquor to obtain scandium hydroxide;
s6, re-dissolving scandium hydroxide obtained by back extraction by using acid liquor to obtain a secondary scandium re-solution;
s7, adding oxalic acid into the scandium secondary return solution to obtain scandium oxalate precipitate;
and S8, calcining the scandium oxalate precipitate to obtain high-purity scandium oxide with the purity of more than 99.9%.
2. The method according to claim 1, characterized in that the scandium hydroxide crude product comprises 35.0-75.0% by mass of Sc (OH) 3 Fe (OH) 1.0-5.0% 3 2.0 to 7.0 percent of Zr (OH) 4 0.5 to 1.5 percent of Ca (OH) 2 0.5 to 1.5% of Ti (OH) 4 。
3. The method according to claim 1, wherein in step S1, the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and H in the acid solution + The concentration is 2-6 mol/L, and the liquid-solid ratio of the acid liquid to the scandium hydroxide crude product is (20-50) mL 1g.
4. The method according to claim 1, wherein in step S2, the phosphate is one or more of the following: sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate.
5. The method according to claim 1, wherein in step S3, the organic extractant comprises 3 to 10% by volume of extractant, and the extractant is one or more of P204, P507, P350, TBP, and the volume ratio of organic phase to aqueous phase is 1 (10 to 20).
6. The method according to claim 1, wherein in step S4, the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and H in the acid solution + The concentration is 1-3 mol/L, and the volume ratio of the organic phase to the water phase is 1 (0.5-1.5).
7. The method according to claim 1, wherein in step S5, the alkali solution is one or both of sodium hydroxide and potassium hydroxide, the alkali concentration is 5 to 10% by mass, and the volume ratio of the organic phase to the aqueous phase is 1 (5 to 15).
8. The method according to claim 1, wherein in step S6, the acid solution is one or more of sulfuric acid, hydrochloric acid, and nitric acid, and H is contained in the acid solution + The concentration is 1-3 mol/L, and the liquid-solid ratio of the acid solution to scandium hydroxide is (20-50) mL to 1g.
9. The method according to claim 1, wherein in step S7 the molar ratio of scandium to oxalic acid is 1 (3-5).
10. The method according to claim 1, wherein in step S8, the calcination temperature is 750 to 950 ℃ and the calcination time is 30 to 150min.
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