CN113493874A - Method for purifying high-purity scandium salt - Google Patents
Method for purifying high-purity scandium salt Download PDFInfo
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- CN113493874A CN113493874A CN202010271910.9A CN202010271910A CN113493874A CN 113493874 A CN113493874 A CN 113493874A CN 202010271910 A CN202010271910 A CN 202010271910A CN 113493874 A CN113493874 A CN 113493874A
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- ions
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- purity scandium
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- scandium
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- 150000003325 scandium Chemical class 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 35
- -1 thorium ions Chemical class 0.000 claims abstract description 226
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000007787 solid Substances 0.000 claims abstract description 74
- 229910052742 iron Inorganic materials 0.000 claims abstract description 70
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 68
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 67
- 239000007864 aqueous solution Substances 0.000 claims abstract description 58
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 238000000746 purification Methods 0.000 claims abstract description 22
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 49
- 238000000605 extraction Methods 0.000 claims description 42
- 239000002244 precipitate Substances 0.000 claims description 33
- 150000007522 mineralic acids Chemical class 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- APPHYFNIXVIIJR-UHFFFAOYSA-K scandium bromide Chemical compound Br[Sc](Br)Br APPHYFNIXVIIJR-UHFFFAOYSA-K 0.000 claims description 3
- 229910000346 scandium sulfate Inorganic materials 0.000 claims description 3
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 3
- QHYMYKHVGWATOS-UHFFFAOYSA-H scandium(3+);trisulfate Chemical compound [Sc+3].[Sc+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QHYMYKHVGWATOS-UHFFFAOYSA-H 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052706 scandium Inorganic materials 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000006959 Williamson synthesis reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- YIGXGYDKDDWZLS-UHFFFAOYSA-N 2-(2-methylphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=CC=C1C YIGXGYDKDDWZLS-UHFFFAOYSA-N 0.000 description 4
- UACJUJUXGHXSEM-UHFFFAOYSA-N 2-(3-propan-2-ylphenoxy)butanoic acid Chemical compound CCC(C(O)=O)OC1=CC=CC(C(C)C)=C1 UACJUJUXGHXSEM-UHFFFAOYSA-N 0.000 description 4
- YVDCGOWSUYVCSD-UHFFFAOYSA-N 2-[4-(2-methylbutan-2-yl)phenoxy]acetic acid Chemical group CCC(C)(C)C1=CC=C(OCC(O)=O)C=C1 YVDCGOWSUYVCSD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- WXCNYZLVYNQBFA-UHFFFAOYSA-N 2-(4-tert-butylphenoxy)pentanoic acid Chemical compound CCCC(C(O)=O)OC1=CC=C(C(C)(C)C)C=C1 WXCNYZLVYNQBFA-UHFFFAOYSA-N 0.000 description 3
- STBZKORYMFFXNI-UHFFFAOYSA-N CCC(C(O)=O)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C Chemical compound CCC(C(O)=O)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C STBZKORYMFFXNI-UHFFFAOYSA-N 0.000 description 3
- CRTNWEIJWQWDJM-UHFFFAOYSA-N CCC1=CC(CC)=CC(OC(C)C(O)=O)=C1 Chemical compound CCC1=CC(CC)=CC(OC(C)C(O)=O)=C1 CRTNWEIJWQWDJM-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- MMDSMWGHQSXYMV-UHFFFAOYSA-N 3-methyl-2-phenoxynonanoic acid Chemical compound CCCCCCC(C)C(C(O)=O)OC1=CC=CC=C1 MMDSMWGHQSXYMV-UHFFFAOYSA-N 0.000 description 2
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BUWFFPDGEWZKSC-UHFFFAOYSA-N CCCC(C(O)=O)OC1=C(C(C)C)C=C(C(C)(C)CC(C)(C)C)C=C1 Chemical compound CCCC(C(O)=O)OC1=C(C(C)C)C=C(C(C)(C)CC(C)(C)C)C=C1 BUWFFPDGEWZKSC-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001243 acetic acids Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WUEFGQXWIWCINJ-UHFFFAOYSA-N 2-(4-tert-butylphenoxy)butanoic acid Chemical compound CCC(C(O)=O)OC1=CC=C(C(C)(C)C)C=C1 WUEFGQXWIWCINJ-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- DBYJUVIAYRFLEJ-UHFFFAOYSA-N CCCC(C(O)=O)OC1=C(C(C)C)C=CC(C(C)(C)CC(C)(C)C)=C1 Chemical compound CCCC(C(O)=O)OC1=C(C(C)C)C=CC(C(C)(C)CC(C)(C)C)=C1 DBYJUVIAYRFLEJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- VBVPJECFJNBWEN-UHFFFAOYSA-M sodium 2-chloropentanoate Chemical compound ClC(C(=O)[O-])CCC.[Na+] VBVPJECFJNBWEN-UHFFFAOYSA-M 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- GNBYZUQCDMNXML-UHFFFAOYSA-M sodium;2-chlorobutanoate Chemical compound [Na+].CCC(Cl)C([O-])=O GNBYZUQCDMNXML-UHFFFAOYSA-M 0.000 description 1
- RPOHBMAQTOJHKM-UHFFFAOYSA-M sodium;2-chloropropanoate Chemical compound [Na+].CC(Cl)C([O-])=O RPOHBMAQTOJHKM-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of metal separation and purification, in particular to a method for purifying high-purity scandium salt, which comprises the following steps: stirring and mixing the high-purity scandium salt aqueous solution with a solid extractant, and extracting to obtain a scandium salt solution after impurity precipitation and purification; the impurity ions in the high-purity scandium salt comprise thorium ions, zirconium ions and iron ions; the solid extractant is selected from one or more of mono-substituted alkyl phenoxy carboxylic acid and di-substituted alkyl phenoxy carboxylic acid; the mono-substituted alkyl phenoxy carboxylic acid has a structure shown in a formula (I), and the di-substituted alkyl phenoxy carboxylic acid has a structure shown in a formula (II); wherein m and n are independently selected from natural numbers of 1-5, R1，R2，R3Independently selected from methyl, ethyl, isopropyl, tert-butyl, tert-amyl or tert-octyl. The purification method provided by the invention can efficiently remove thorium ions, zirconium ions and iron ions in high-purity scandium salt.
Description
Technical Field
The invention relates to the technical field of metal separation and purification, in particular to a method for purifying high-purity scandium salt.
Background
Scandium element is widely applied to key strategic materials such as special alloy for high-end equipment, new energy materials and the like. China has abundant scandium resources, but independent scandium ores are few, so that scandium elements are mainly extracted and recovered from titanium white waste acid, tungsten slag, tin slag, red mud, nickel ore and uranium ore at present. Scandium products on the market contain various metal ion impurities, such as iron, aluminum, manganese, magnesium and the like, and also contain certain tetravalent transition metal ions such as Ti4+、Zr4+Equal, and minute amount of Th4+、U4+And the like actinides. When scandium is used for applications such as fuel cell electrolytes and piezoelectric thin films, it is necessary to separate various impurity elements to a permissible limit or less. Therefore, it has become a very critical technology to efficiently and easily remove certain specific impurity ions from scandium products so as to make the purity of the scandium products meet the requirements of specific applications.
Patent CN105793447A discloses a scandium separation method. Mixing an acidic aqueous solution containing scandium with pH <4 and containing impurities with alkali, adjusting the pH to be more than 4 and less than 7, and extracting scandium ions by using naphthenic acid and/or neodecanoic acid as an extracting agent and sulfonated kerosene as a diluting agent. The purity of the finally obtained scandium product reaches more than 99%.
The mechanism of the extractive separation of scandium from rare earths by sec-octylphenoxyacetic acid (CA-12) has also been published in the literature ([ J ]. analytical chemistry, 2001, 29 (1): 45-48). Patent CN1397653A discloses scandium enrichment and purification by liquid-liquid extraction method with secondary octylphenoxy substituted acetic acid or secondary nonylphenoxy substituted acetic acid saponified with inorganic base as extractant, mixed alcohol as additive, sulfonated kerosene as diluent. Patent CN106702180A discloses a method for extracting scandium, which comprises saponifying an organic phase containing alkoxy phenoxy carboxylic acid, tributyl phosphate and diluent with inorganic base to extract scandium solution.
As can be seen from the above disclosure, in the existing methods for purifying scandium, the extractant used is mainly to extract scandium preferentially, and no method for preferentially extracting impurity ions is available; inorganic alkali is generally used for saponifying the extracting agent, the process is complex, and the medicament consumption is large. Therefore, it is necessary to develop a novel extraction method for preferentially removing impurity ions to purify scandium, thereby saving chemical raw materials and simplifying industrial processes.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a method for purifying high-purity scandium salt, which can efficiently remove impurity ions in high-purity scandium salt.
The invention provides a method for purifying high-purity scandium salt, which comprises the following steps:
stirring and mixing the high-purity scandium salt aqueous solution with a solid extractant, and extracting to obtain a scandium salt solution after impurity precipitation and purification; the impurity ions in the high-purity scandium salt comprise thorium ions, zirconium ions and iron ions;
the solid extractant is selected from one or more of mono-substituted alkyl phenoxy carboxylic acid and di-substituted alkyl phenoxy carboxylic acid; the mono-substituted alkyl phenoxy carboxylic acid has a structure shown in a formula (I), and the di-substituted alkyl phenoxy carboxylic acid has a structure shown in a formula (II);
wherein m and n are independently selected from natural numbers of 1-5, R1，R2，R3Independently selected from methyl, ethyl, isopropyl, tert-butyl, tert-amyl or tert-octyl.
Preferably, the solid extractant has a melting point of greater than 50 ℃.
Preferably, in the formula (i), m is 1, 2, 3 or 4, R1Is 4-tert-amyl, 2-methyl, 3-isopropyl or 4-tert-butyl;
in the formula (II), n is 2, 3 or 4, R2Is 2-tert-butyl, 3-ethyl or 2-isopropyl; r3Is 6-tert-butyl, 5-ethyl or 4-tert-octyl.
Preferably, the purity of the high-purity scandium salt is 99.8-99.9999%;
the high-purity scandium salt comprises high-purity scandium chloride, high-purity scandium bromide, high-purity scandium sulfate or high-purity scandium nitrate.
Preferably, the pH value of the aqueous solution of the high-purity scandium salt is 4-7.
Preferably, the mass ratio of the aqueous solution of the high-purity scandium salt to the solid extractant is 1-500: 1 to 3.
Preferably, the extraction time is 1-360 min.
Preferably, after the impurities are precipitated, the method further comprises:
and mixing the impurity precipitate with an inorganic acid solution, and performing back extraction to obtain an inorganic acid solution containing impurity ions and a regenerated solid extracting agent.
Preferably, the inorganic acid solution is selected from one or more of hydrochloric acid solution, sulfuric acid solution and nitric acid solution;
the concentration of the inorganic acid solution is 0.5-12 mol/L.
Preferably, the mass ratio of the inorganic acid solution to the impurity precipitate is 0.1-20: 1-3;
the back extraction time is 1-60 min.
In the invention, the solid extractant has high selectivity on thorium ions, zirconium ions and iron ions which are impurities, when the solid extractant is contacted with a high-purity scandium salt solution containing the thorium ions, the zirconium ions and the iron ions, the extractant preferentially performs extraction reaction with the thorium ions, the zirconium ions and the iron ions to form precipitates but does not react with the scandium ions, and the separation coefficient of the impurity ions and the scandium ions is high. After the solid extractant is used, the solid extractant can be regenerated by inorganic acid, and can be recycled. Meanwhile, in the method for purifying the high-purity scandium salt, a saponifier (such as ammonia water and the like) is not needed, a diluent (such as n-heptane or kerosene and other flammable and explosive organic solvents) is not needed, the consumption of chemical raw materials is low, and the method is environment-friendly.
Experimental results show that the purification method provided by the invention can ensure that the removal rate of thorium ions in high-purity scandium salt is not less than 95.5%, the removal rate of zirconium ions is higher than 94%, and the removal rate of iron ions is higher than 51%.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for purifying high-purity scandium salt, which comprises the following steps:
stirring and mixing the high-purity scandium salt aqueous solution with a solid extractant, and extracting to obtain a scandium salt solution after impurity precipitation and purification; the impurity ions in the high-purity scandium salt comprise thorium ions, zirconium ions and iron ions;
the solid extractant is selected from one or more of mono-substituted alkyl phenoxy carboxylic acid and di-substituted alkyl phenoxy carboxylic acid; the mono-substituted alkyl phenoxy carboxylic acid has a structure shown in a formula (I), and the di-substituted alkyl phenoxy carboxylic acid has a structure shown in a formula (II);
wherein m and n are independently selected from natural numbers of 1-5, R1，R2，R3Independently selected from methyl, ethyl, isopropyl, tert-butyl, tert-amyl or tert-octyl.
In certain embodiments of the invention, the solid extractant has a melting point greater than 50 ℃.
In certain embodiments of the present invention, in formula (i), m ═ 1, 2, 3, or 4, R1Is 4-tert-amyl, 2-methyl, 3-isopropyl or 4-tert-butyl.
In certain embodiments of the present invention, in formula (ii), n ═ 2, 3, or 4, R2Is 2-tert-butyl, 3-ethyl or 2-isopropyl; r3Is 6-tert-butyl, 5-ethyl or 4-tert-octyl.
In certain embodiments of the invention, the solid extractant is selected from 4-tert-pentylphenoxyacetic acid, 2-methylphenoxypropionic acid, 3-isopropylphenoxybutyric acid, 4-tert-butylphenoxypentanoic acid, 2, 6-di-tert-butylphenoxybutyric acid, 3, 5-diethylphenoxypropionic acid, or 2-isopropyl-4-tert-octylphenoxypentanoic acid.
The sources of the mono-substituted alkyl phenoxy carboxylic acid with the structure shown in the formula (I) and the di-substituted alkyl phenoxy carboxylic acid with the structure shown in the formula (II) are not particularly limited, and the mono-substituted alkyl phenoxy carboxylic acid and the di-substituted alkyl phenoxy carboxylic acid can be generally sold in the market or self-prepared by adopting Williamson reaction.
In certain embodiments of the present invention, monosubstituted alkylphenoxy carboxylic acids having the structure shown in formula (i) are prepared by the williamson reaction, specifically, according to the following method:
A) reacting ethanol, a phenolic compound with a structure shown in a formula (III) and sodium hydroxide to obtain a first product;
wherein R is1Selected from methyl, ethyl, isopropyl, tert-butyl, tert-amyl or tert-octyl;
B) reacting the first reaction product with a compound with a structure shown in a formula (IV) to obtain a second product;
Cl-(CH2)mCOONa (Ⅳ)；
wherein m is a natural number of 1-5;
C) and (3) cooling the second reaction product, and then acidifying and distilling under reduced pressure to obtain the mono-substituted alkyl phenoxy carboxylic acid with the structure shown in the formula (I).
In certain embodiments of the present invention, the molar ratio of ethanol, phenolic compound having the structure of formula (iii), sodium hydroxide, and compound having the structure of formula (iv) is 10: 1.0: 1.2: 1.2, 10: 1.0: 1.1: 1.1.
in certain embodiments of the invention, R1Is 4-tert-amyl, 2-methyl, 3-isopropyl or 4-tert-butyl. In certain embodiments of the present invention, m is 1, 2, 3 or 4.
In some embodiments of the invention, in the step a), the reaction temperature is 90 to 95 ℃ and the reaction time is 0.5 to 1 hour. In certain embodiments, the reaction temperature in step a) is 90 ℃, 95 ℃ and the reaction time is 0.5h, 1 h.
In some embodiments of the invention, in the step B), the reaction temperature is 90 to 95 ℃ and the reaction time is 2 to 3 hours. In certain embodiments, the reaction temperature in step B) is 90 ℃, 95 ℃ and the reaction time is 2h or 3 h.
In certain embodiments of the present invention, the temperature after cooling in step C) is room temperature.
In certain embodiments of the invention, the acid solution used for the acidification is a hydrochloric acid solution. In certain embodiments, the concentration of the hydrochloric acid solution is 6 mol/L. In some embodiments of the invention, the ratio of the amount of the hydrochloric acid solution to the amount of the compound having the structure shown in formula (iv) is 90-100 mL: 1.0 to 1.2 mol. In certain embodiments, the ratio of the amount of the hydrochloric acid solution to the amount of the compound having the structure represented by formula (iv) is 90 mL: 1.2mol, 100 mL: 1.1 mol. In some embodiments of the present invention, the time for acidification is 5-10 min. In certain embodiments, the time for acidification is 5min, 10 min.
In certain embodiments of the present invention, disubstituted alkyl phenoxy carboxylic acids having the structure shown in formula (II) are available from Fujian Changtong rare earth Co.
In certain embodiments of the invention, the mono-substituted alkyl phenoxy carboxylic acid having the structure of formula (i) has a purity of greater than 95% or greater than 98%; the purity of the disubstituted alkyl phenoxy carboxylic acid with the structure shown in the formula (II) is more than 95 percent.
In some embodiments of the invention, the high-purity scandium salt has a purity of 99.8% to 99.9999%. In certain embodiments of the invention, the high-purity scandium salt has a purity of 99.91% or 99.95%.
In certain embodiments of the present invention, the high purity scandium salt comprises high purity scandium chloride, high purity scandium bromide, high purity scandium sulfate, or high purity scandium nitrate.
The invention is not limited to the preparation method of the aqueous solution of high-purity scandium salt, and the aqueous solution can be prepared by the preparation method which is well known to those skilled in the art. In some embodiments of the present invention, the aqueous solution of high-purity scandium salt has a pH of 4 to 7. In some embodiments, the aqueous solution of high purity scandium salt has a pH of 4 or 5. In some embodiments of the present invention, the pH of the aqueous solution of high-purity scandium salt can be adjusted by conventional acid-base reagents, which is not particularly limited by the present invention.
In some embodiments of the present invention, the concentration of scandium ions in the aqueous solution of high-purity scandium salt is 3-13 g/L. In some embodiments, the concentration of scandium ions in the aqueous solution of high purity scandium salt is 3.07g/L or 12.3 g/L.
In the invention, the impurity ions in the high-purity scandium salt comprise thorium ions, zirconium ions and iron ions. In some embodiments of the present invention, the concentration of thorium ions in the aqueous solution of high-purity scandium salt is 0.7-3.1 mg/L. In some embodiments, the concentration of thorium ions in the aqueous solution of high purity scandium salt is 0.777mg/L or 3.1 mg/L. In some embodiments of the present invention, the concentration of zirconium ions in the aqueous solution of high-purity scandium salt is 0.5-2.6 mg/L. In some embodiments, the aqueous solution of high purity scandium salt has a concentration of zirconium ions of 0.567mg/L or 2.6 mg/L. In some embodiments of the present invention, the concentration of iron ions in the aqueous solution of high-purity scandium salt is 0.09-0.39 mg/L. In some embodiments, the aqueous solution of high purity scandium salt has a concentration of iron ions of 0.0958mg/L or 0.381 mg/L.
In some embodiments of the present invention, the mass ratio of the aqueous solution of high-purity scandium salt to the solid extractant is 1-500: 1 to 3. In some embodiments, the mass ratio of the aqueous solution of high-purity scandium salt to the solid extractant is 7.5: 1. 15: 1. 30: 1. 50: 1. 50: 3.
the invention firstly stirs and mixes the high-purity scandium salt aqueous solution and the solid extractant, and extracts to obtain the scandium salt solution after impurity precipitation and purification.
The stirring method for the stirring and mixing is not particularly limited in the present invention, and a stirring method known to those skilled in the art may be employed.
When the solid extractant is contacted with a high-purity scandium salt solution containing thorium ions, zirconium ions and iron ions, the extractant preferentially reacts with the thorium ions, the zirconium ions and the iron ions to form precipitates, but does not react with the scandium ions.
In some embodiments of the present invention, the extraction time is 1-360 min. In certain embodiments, the time of extraction is 30min or 5 min.
In some embodiments of the present invention, after obtaining the impurity precipitate, further comprising:
and mixing the impurity precipitate with an inorganic acid solution, and performing back extraction to obtain an inorganic acid solution containing impurity ions and a regenerated solid extracting agent.
In certain embodiments of the present invention, the inorganic acid solution is selected from one or more of a hydrochloric acid solution, a sulfuric acid solution, and a nitric acid solution. In some embodiments of the present invention, the concentration of the inorganic acid solution is 0.5 to 12 mol/L. In certain embodiments, the concentration of the inorganic acid solution is 6mol/L, 9mol/L, or 10 mol/L.
In some embodiments of the invention, the mass ratio of the inorganic acid solution to the impurity precipitate is 0.1-20: 1 to 3. In certain embodiments, the mass ratio of the inorganic acid solution to the impurity precipitate is 5: 1. 10: 1. 2: 1. 20: 3.
in some embodiments of the invention, the back extraction time is 1-60 min. In certain embodiments, the time for the back-extraction is 30min, 5min, or 60 min.
During back extraction, the precipitate extracted with thorium ion, zirconium ion and iron ion reacts with inorganic acid to make thorium, zirconium and iron enter high-acidity inorganic acid solution, and the extractant is regenerated.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In the invention, the solid extractant is convenient to obtain, the preparation process of the solid extractant is simple, the chemical raw materials required by the synthesis of the solid extractant are wide in source, and the synthesis cost is low; the solid extractant has high selectivity on thorium ions, zirconium ions and iron ions as impurities, and the separation coefficient of the impurity ions and scandium ions is high; after the solid extractant is used, the solid extractant is regenerated by inorganic acid and can be recycled; in the purification method of the high-purity scandium salt solution, a saponifier (such as ammonia water and the like) is not needed, a diluent (such as n-heptane or kerosene and other flammable and explosive organic solvents) is not needed, the consumption of chemical raw materials is low, and the method is environment-friendly.
In order to further illustrate the present invention, the following examples are provided to describe the purification method of high purity scandium salt in detail, but they should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
In the following examples and comparative examples, the content of thorium, zirconium and iron in the aqueous phase was measured using an inductively coupled plasma emission spectrometer. The instrument model is JY ULTIMA 2, produced by France. The analysis method adopts a chemical analysis method of non-rare earth impurities in rare earth metals and oxides thereof for measuring aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc and lead (GB/T12690.5-2003). ICP excitation power is 1.3kW, atomizer flow is 0.75L/min, solution lifting amount is 1.50mL/min, and observation height is 1.4 cm.
Example 1
The solid extractant adopts 4-tert-pentylphenoxyacetic acid, R1 is 4-tert-amyl, and m is 1. The source of the solid extracting agent is self-made by adopting Williamson reaction: adding 10mol of ethanol, 1.0mol of 4-tert-amylphenol and 1.2mol of sodium hydroxide into a reaction vessel, setting the reaction temperature at 95 ℃, and reacting for 0.5 h; slowly adding 1.2mol of sodium chloroacetate into a reaction container, and maintaining the reaction temperature at 95 ℃ for 2 hours to obtain reaction liquid; cooling to room temperature, adding 90mL of 6mol/L hydrochloric acid, acidifying for 5min, and distilling under reduced pressure to obtain 4-tert-pentylphenoxyacetic acid with purity higher than 95%.
(1) The extraction process comprises the following steps: 15mL of a high-purity scandium chloride aqueous solution containing thorium ions, zirconium ions and iron ions (the relative density is 1, the mass ratio of the high-purity scandium chloride aqueous solution to the solid extractant is 7.5: 1) was taken, the purity of the high-purity scandium chloride was 99.91%, the concentration of scandium ions in the high-purity scandium chloride aqueous solution was 3.07g/L, the pH was 4, and the contents of thorium ions, zirconium ions and iron ions were 0.777mg/L, 0.567mg/L and 0.0958mg/L, respectively. Taking 2g of solid extractant (4-tert-pentylphenoxyacetic acid solid), mixing with the aqueous solution of high-purity scandium chloride, stirring, extracting, reacting thorium ions, zirconium ions and iron ions with the solid extractant to form precipitate, and extracting for 30 min.
(2) Back extraction process: and (3) carrying out back extraction on the precipitate extracted with the thorium ions, the zirconium ions and the iron ions by using 10g of 6mol/L hydrochloric acid solution (the mass ratio of the hydrochloric acid solution to the precipitate is 5: 1), wherein the back extraction time is 30min, and the extractant is regenerated.
Through determination, the concentrations of thorium ions, zirconium ions and iron ions in the purified high-purity scandium chloride aqueous solution are respectively reduced to 0.0125mg/L, 0.0149mg/L and 0.0429mg/L, and the removal rates of the thorium ions, the zirconium ions and the iron ions respectively reach 98.4%, 97.4% and 55.2%. Therefore, thorium ions, zirconium ions and iron ions in the high-purity scandium chloride are better removed.
Example 2
The solid extractant adopts 2-methyl phenoxy propionic acid, R1 is 2-methyl, and m is 2. The source of the solid extracting agent is self-made by adopting Williamson reaction: adding 10mol of ethanol, 1.0mol of 2-methylphenol and 1.1mol of sodium hydroxide into a reaction vessel, setting the reaction temperature to be 90 ℃, and reacting for 1.0 h; slowly adding 1.1mol of sodium chloropropionate into a reaction container, and maintaining the reaction temperature at 90 ℃ for 2 hours to obtain a reaction solution; cooling to room temperature, adding 100mL of 6mol/L hydrochloric acid, acidifying for 10min, and distilling under reduced pressure to obtain 2-methylphenoxypropionic acid with purity of more than 98%.
(1) The extraction process comprises the following steps: 30mL of a high-purity scandium chloride aqueous solution containing thorium ions, zirconium ions and iron ions (the relative density is 1, the mass ratio of the high-purity scandium chloride aqueous solution to the solid extractant is 15: 1) is taken, the purity of the high-purity scandium chloride is 99.91%, the concentration of scandium ions in the high-purity scandium chloride aqueous solution is 3.07g/L, the pH value is 4, and the contents of the thorium ions, the zirconium ions and the iron ions are 0.777mg/L, 0.567mg/L and 0.0958mg/L respectively. Taking 2g of solid extractant (2-methylphenoxypropionic acid solid), mixing with an aqueous solution of high-purity scandium chloride, stirring, extracting, reacting thorium ions, zirconium ions and iron ions with the solid extractant to form precipitates, and extracting for 30 min.
(2) Back extraction process: and (3) carrying out back extraction on the precipitate extracted with the thorium ions, the zirconium ions and the iron ions by using 20g of 6mol/L hydrochloric acid solution (the mass ratio of the hydrochloric acid solution to the precipitate is 10: 1), wherein the back extraction time is 30min, and the extractant is regenerated.
Through determination, the concentrations of thorium ions, zirconium ions and iron ions in the purified high-purity scandium chloride aqueous solution are respectively reduced to 0.0062mg/L, 0.0057mg/L and 0.0331mg/L, and the removal rates of the thorium ions, the zirconium ions and the iron ions respectively reach 99.2%, 99.0% and 65.4%. Therefore, thorium ions, zirconium ions and iron ions in the high-purity scandium chloride are better removed.
Example 3
3-isopropylphenoxy butyric acid is adopted as a solid extracting agent, R1 is 3-isopropyl, and m is 3. The source of the solid extracting agent is self-made by adopting Williamson reaction: adding 10mol of ethanol, 1.0mol of 3-isopropylphenol and 1.2mol of sodium hydroxide into a reaction vessel, setting the reaction temperature at 95 ℃, and reacting for 1.0 h; slowly adding 1.2mol of sodium chlorobutyrate into a reaction container, and maintaining the reaction temperature at 95 ℃ for 3 hours to obtain reaction liquid; and cooling to room temperature, adding 90mL of 6mol/L hydrochloric acid, acidifying for 10min, and carrying out reduced pressure distillation to obtain the 3-isopropylphenoxy butyric acid with the purity of more than 95%.
(1) The extraction process comprises the following steps: 30mL of a high-purity scandium chloride aqueous solution containing thorium ions, zirconium ions and iron ions (the relative density is 1, the mass ratio of the high-purity scandium chloride aqueous solution to the solid extractant is 30: 1) is taken, the purity of the high-purity scandium chloride is 99.91%, the concentration of scandium ions in the high-purity scandium chloride aqueous solution is 3.07g/L, the pH value is 4, and the contents of the thorium ions, the zirconium ions and the iron ions are 0.777mg/L, 0.567mg/L and 0.0958mg/L respectively. Taking 1g of solid extractant (3-isopropylphenoxy butyric acid solid), mixing with the aqueous solution of high-purity scandium chloride, stirring, extracting, reacting thorium ions, zirconium ions and iron ions with the solid extractant to form precipitates, and extracting for 30 min.
(2) Back extraction process: and (3) carrying out back extraction on the precipitate extracted with the thorium ions, the zirconium ions and the iron ions by using 2g of 6mol/L hydrochloric acid solution (the mass ratio of the hydrochloric acid solution to the precipitate is 2: 1), wherein the back extraction time is 60min, and the extractant is regenerated.
Through determination, the concentrations of thorium ions, zirconium ions and iron ions in the purified high-purity scandium chloride aqueous solution are respectively reduced to 0.0248mg/L, 0.0244mg/L and 0.0453mg/L, and the removal rates of the thorium ions, the zirconium ions and the iron ions respectively reach 96.8%, 95.7% and 52.7%. Therefore, thorium ions, zirconium ions and iron ions in the high-purity scandium chloride are better removed.
Example 4
The solid extractant adopts 4-tert-butyl phenoxy pentanoic acid, R1 is 4-tert-butyl, and m is 4. The source of the solid extracting agent is self-made by adopting Williamson reaction: adding 10mol of ethanol, 1.0mol of 4-tert-butylphenol and 1.2mol of sodium hydroxide into a reaction vessel, setting the reaction temperature at 95 ℃, and reacting for 0.5 h; slowly adding 1.2mol of sodium chloropentanoate into a reaction vessel, and maintaining the reaction temperature at 95 ℃ for 2 hours to obtain reaction liquid; cooling to room temperature, adding 90mL of 6mol/L hydrochloric acid, acidifying for 5min, and distilling under reduced pressure to obtain 4-tert-butylphenoxypentanoic acid with purity higher than 95%.
(1) The extraction process comprises the following steps: 100mL of an aqueous solution of high-purity scandium chloride containing thorium ions, zirconium ions and iron ions (the relative density is 1, the mass ratio of the aqueous solution of the high-purity scandium chloride to the solid extractant is 50: 1) was taken, the purity of the high-purity scandium chloride was 99.91%, the concentration of scandium ions in the aqueous solution of the high-purity scandium chloride was 3.07g/L, the pH was 4, and the contents of the thorium ions, the zirconium ions and the iron ions were 0.777mg/L, 0.567mg/L and 0.0958mg/L, respectively. Taking 2g of a solid extracting agent (4-tert-butyl phenoxy butyric acid solid), mixing the solid extracting agent with an aqueous solution of high-purity scandium chloride, stirring, extracting, reacting thorium ions, zirconium ions and iron ions with the solid extracting agent to form precipitates, and extracting for 30 min.
(2) Back extraction process: and (3) carrying out back extraction on the precipitate extracted with the thorium ions, the zirconium ions and the iron ions by using 10g of 6mol/L hydrochloric acid solution (the mass ratio of the hydrochloric acid solution to the precipitate is 5: 1), wherein the back extraction time is 30min, and the extractant is regenerated.
Through determination, the concentrations of thorium ions, zirconium ions and iron ions in the purified high-purity scandium chloride aqueous solution are respectively reduced to 0.0349mg/L, 0.0323mg/L and 0.0467mg/L, and the removal rates of the thorium ions, the zirconium ions and the iron ions respectively reach 95.5%, 94.3% and 51.2%. Therefore, thorium ions, zirconium ions and iron ions in the high-purity scandium chloride are better removed.
Example 5
The solid extractant adopts 2, 6-bisT-butylphenoxybutyric acid, i.e. n ═ 3, R2Is 2-tert-butyl, R3Is 6-tert-butyl. The solid extractant is purchased from Fujian province Changting gold dragon rare earth Co Ltd, and the purity is more than 95%.
(1) The extraction process comprises the following steps: 15mL of a high-purity scandium chloride aqueous solution containing thorium ions, zirconium ions and iron ions (the relative density is 1, the mass ratio of the high-purity scandium chloride aqueous solution to the solid extractant is 5: 1) was taken, the purity of the high-purity scandium chloride was 99.95%, the concentration of scandium ions in the high-purity scandium chloride aqueous solution was 12.3g/L, the pH was 5, and the contents of thorium ions, zirconium ions and iron ions were 3.10mg/L, 2.60mg/L and 0.381mg/L, respectively. Taking 3.0g of solid extractant (2, 6-di-tert-butyl phenoxy butyric acid solid), mixing with the aqueous solution of high-purity scandium chloride, stirring, extracting, reacting thorium ions, zirconium ions and iron ions with the solid extractant to form precipitate, and extracting for 30 min.
(2) Back extraction process: and (3) carrying out back extraction on the precipitate extracted with the thorium ions, the zirconium ions and the iron ions by using 20g of 9mol/L hydrochloric acid (the mass ratio of the hydrochloric acid solution to the precipitate is 20: 3), wherein the back extraction time is 5min, and the extractant is regenerated.
Through determination, the concentrations of thorium ions, zirconium ions and iron ions in the purified high-purity scandium chloride aqueous solution are respectively reduced to 0.0589mg/L, 0.0655mg/L and 0.181mg/L, and the removal rates of the thorium ions, the zirconium ions and the iron ions respectively reach 98.1%, 97.1% and 52.5%. Therefore, thorium ions, zirconium ions and iron ions in the high-purity scandium chloride are better removed.
Example 6
The solid extractant is 3, 5-diethylphenoxypropionic acid, namely, n-2, R2Is 3-ethyl, R3Is 5-ethyl. The solid extractant is purchased from Fujian province Changting gold dragon rare earth Co Ltd, and the purity is more than 95%.
(1) The extraction process comprises the following steps: 50mL of a high-purity scandium chloride solution containing thorium ions, zirconium ions and iron ions (the relative density is 1, the mass ratio of the aqueous solution of the high-purity scandium chloride to the solid extractant is 50: 3) is taken, the purity of the high-purity scandium chloride is 99.95%, the concentration of the scandium ions in the aqueous solution of the high-purity scandium chloride is 12.3g/L, the pH value is 5, and the contents of the thorium ions, the zirconium ions and the iron ions are 3.10mg/L, 2.60mg/L and 0.381mg/L respectively. Mixing 3g of solid extractant (3, 5-diethyl phenoxy propionic acid solid) with the aqueous solution of high-purity scandium chloride, stirring, extracting, reacting thorium ions, zirconium ions and iron ions with the solid extractant to form precipitate, and extracting for 30 min.
(2) Back extraction process: and (3) carrying out back extraction on the precipitate extracted with the thorium ions, the zirconium ions and the iron ions by using 20g of 9mol/L hydrochloric acid (the mass ratio of the hydrochloric acid solution to the precipitate is 20: 3), wherein the back extraction time is 5min, and the extractant is regenerated.
Through determination, the concentrations of thorium ions, zirconium ions and iron ions in the purified high-purity scandium chloride aqueous solution are respectively reduced to 0.0713mg/L, 0.0910mg/L and 0.160mg/L, and the removal rates of the thorium ions, the zirconium ions and the iron ions respectively reach 97.7%, 96.5% and 57.9%. Therefore, thorium ions, zirconium ions and iron ions in the high-purity scandium chloride are better removed.
Example 7
The solid extractant is 2-isopropyl-4-tert-octyl phenoxy pentanoic acid, namely, n is 4, R2Is 2-isopropyl, R3Is 4-tert-octyl. The solid extractant is purchased from Fujian province Changting gold dragon rare earth Co Ltd, and the purity is more than 95%.
(1) The extraction process comprises the following steps: 50mL of a high-purity scandium chloride solution containing thorium ions, zirconium ions and iron ions (the relative density is 1, and the mass ratio of the high-purity scandium chloride aqueous solution to the solid extractant is 50: 1) is taken, the purity of the high-purity scandium chloride is 99.95%, the concentration of scandium ions in the high-purity scandium chloride aqueous solution is 12.3g/L, the pH value is 5, and the contents of the thorium ions, the zirconium ions and the iron ions are 3.10mg/L, 2.60mg/L and 0.381mg/L respectively. Taking 1g of solid extractant (2-isopropyl-5-tert-octylphenoxyvaleric acid solid), mixing with a high-purity scandium chloride aqueous solution, stirring, extracting, reacting thorium ions, zirconium ions and iron ions with the solid extractant to form a precipitate, and extracting for 30 min.
(2) Back extraction process: and (3) carrying out back extraction on the precipitate extracted with the thorium ions, the zirconium ions and the iron ions by using 2g of 10mol/L hydrochloric acid (the mass ratio of the hydrochloric acid solution to the precipitate is 2: 1), wherein the back extraction time is 5min, and the extractant is regenerated.
Through determination, the concentrations of thorium ions, zirconium ions and iron ions in the purified high-purity scandium chloride aqueous solution are respectively reduced to 0.0496mg/L, 0.0468mg/L and 0.157mg/L, and the removal rates of the thorium ions, the zirconium ions and the iron ions respectively reach 98.4%, 98.2% and 58.8%. Therefore, thorium ions, zirconium ions and iron ions in the high-purity scandium chloride are better removed.
Experimental results show that the purification method provided by the invention can ensure that the removal rate of thorium ions in high-purity scandium salt is not less than 95.5%, the removal rate of zirconium ions is higher than 94%, and the removal rate of iron ions is higher than 51%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for purifying high-purity scandium salt comprises the following steps:
stirring and mixing the high-purity scandium salt aqueous solution with a solid extractant, and extracting to obtain a scandium salt solution after impurity precipitation and purification; the impurity ions in the high-purity scandium salt comprise thorium ions, zirconium ions and iron ions;
the solid extractant is selected from one or more of mono-substituted alkyl phenoxy carboxylic acid and di-substituted alkyl phenoxy carboxylic acid; the mono-substituted alkyl phenoxy carboxylic acid has a structure shown in a formula (I), and the di-substituted alkyl phenoxy carboxylic acid has a structure shown in a formula (II);
wherein the content of the first and second substances,m and n are independently selected from natural numbers of 1-5, R1，R2，R3Independently selected from methyl, ethyl, isopropyl, tert-butyl, tert-amyl or tert-octyl.
2. The purification method of claim 1, wherein the solid extractant has a melting point greater than 50 ℃.
3. The purification method according to claim 1,
in the formula (I), m is 1, 2, 3 or 4, R1Is 4-tert-amyl, 2-methyl, 3-isopropyl or 4-tert-butyl;
in the formula (II), n is 2, 3 or 4, R2Is 2-tert-butyl, 3-ethyl or 2-isopropyl; r3Is 6-tert-butyl, 5-ethyl or 4-tert-octyl.
4. The purification method according to claim 1, wherein the high-purity scandium salt has a purity of 99.8% to 99.9999%;
the high-purity scandium salt comprises high-purity scandium chloride, high-purity scandium bromide, high-purity scandium sulfate or high-purity scandium nitrate.
5. The purification method according to claim 1, wherein the aqueous solution of high-purity scandium salt has a pH of 4 to 7.
6. The purification method according to claim 1, wherein the mass ratio of the aqueous solution of high-purity scandium salt to the solid extractant is 1-500: 1 to 3.
7. The purification method according to claim 1, wherein the extraction time is 1 to 360 min.
8. The purification method of claim 1, wherein after obtaining the impurity precipitate, further comprising:
and mixing the impurity precipitate with an inorganic acid solution, and performing back extraction to obtain an inorganic acid solution containing impurity ions and a regenerated solid extracting agent.
9. The purification method according to claim 8, wherein the inorganic acid solution is one or more selected from a hydrochloric acid solution, a sulfuric acid solution and a nitric acid solution;
the concentration of the inorganic acid solution is 0.5-12 mol/L.
10. The purification method according to claim 8, wherein the mass ratio of the inorganic acid solution to the impurity precipitate is 0.1 to 20: 1-3;
the back extraction time is 1-60 min.
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