CN117344161A - Method for recycling scandium from scandium-containing calcium fluoride material - Google Patents
Method for recycling scandium from scandium-containing calcium fluoride material Download PDFInfo
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- CN117344161A CN117344161A CN202311309742.8A CN202311309742A CN117344161A CN 117344161 A CN117344161 A CN 117344161A CN 202311309742 A CN202311309742 A CN 202311309742A CN 117344161 A CN117344161 A CN 117344161A
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- scandium
- organic phase
- solution
- calcium fluoride
- containing calcium
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- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 94
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 50
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 33
- 229910001634 calcium fluoride Inorganic materials 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title description 8
- 239000012074 organic phase Substances 0.000 claims abstract description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002253 acid Substances 0.000 claims abstract description 30
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 claims abstract description 26
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims abstract description 21
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000004090 dissolution Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000003350 kerosene Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 57
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 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 description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 238000002386 leaching Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- -1 scandium sodium halogen Chemical class 0.000 description 8
- 239000010881 fly ash Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229940063656 aluminum chloride Drugs 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000005185 salting out Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Chemical class 0.000 description 4
- 239000011575 calcium Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 description 2
- 229910001646 scandium mineral Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910000542 Sc alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical group [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The application belongs to the technical field of rare earth element recovery, and discloses a method for recovering scandium from scandium-containing calcium fluoride materials, which comprises the steps of crushing and grinding the scandium-containing calcium fluoride materials to below 200 meshes to obtain powder; adding the powder into an aluminum chloride hexahydrate solution, wherein the mass ratio of the powder to the aluminum chloride hexahydrate solution is 1: 8-12, then raising the temperature to 80-90 ℃, stirring and reacting for 2-4 hours, and filtering to obtain a filter cake and scandium-containing filtrate; adjusting the pH value of scandium-containing filtrate to 1-2 by sulfuric acid; extracting scandium-containing filtrate by using a mixture of P204 and sulfonated kerosene to obtain an organic phase I; washing the first organic phase by using sulfuric acid solution to obtain a second organic phase; back-extracting the organic phase II by using sodium hydroxide solution to obtain scandium hydroxide; and finally, sequentially carrying out acid dissolution, precipitation and calcination on scandium hydroxide to obtain scandium oxide.
Description
Technical Field
The invention relates to the technical field of rare earth element recovery, in particular to a method for recovering scandium from scandium-containing calcium fluoride materials.
Background
Scandium (Sc) is widely found in nature, with a low average abundance, and in the crust of the earth an abundance of about 36X 10 -4 The distribution of scandium is extremely dispersed, so that extremely rare impressions are often given, and independent scandium mineral resources are extremely rare, and most scandium is mineralThe associated forms are dispersed in tungsten, aluminum, vanadium, titanium, zirconium ore deposits and partial rare earth ores, and the research on extraction and deep processing is difficult. Scandium and compounds thereof are mainly applied to the aspects of Al-Sc alloy materials, scandium sodium halogen lamps, solid oxide fuel cells and the like, and the price of the scandium is relatively high due to the extremely rare scandium mineral resources, so that the scandium is limited to be widely applied in the fields of aviation, laser, electronics and the like. Although companies producing scandium and related products at home and abroad are more but the total yield is not high, according to the international Hadamard information research center data, the demand for scandium is huge in the future internationally, and the situation of supply and demand is long-term. Therefore, in order to relieve the unbalanced supply and demand relationship of scandium, the recycling of scandium from different materials in various channels has important significance.
When scandium is recovered from industrial waste, common raw materials mainly comprise red mud, tungsten smelting slag, smelting slag of sedimentary iron ore, chloridized smoke dust and fly ash generated during chloridizing roasting of ilmenite, and the like, a treatment method mainly comprises a wet method, and the technical route mainly comprises the steps of enriching scandium by adopting a physical or chemical floatation method and the like, leaching scandium concentrate by acid, and extracting, purifying and calcining the leached liquid to obtain scandium oxide products. However, the method has the problems of complex material treatment, multiple impurity elements, large wastewater amount, high production energy consumption and the like.
The existing process for preparing the metal scandium mainly adopts a metallothermic reduction method, scandium oxide needs to be fluorinated before thermal reduction, scandium fluoride is obtained by mixing and reacting scandium oxide with fluoride under certain conditions, a large amount of calcium fluoride materials are produced in the process, and a small amount of scandium fluoride is mixed with the materials, and although the scandium content in the calcium fluoride is only 0.8-5%, the waste of scandium resources is increased along with the increase of the amount of the calcium fluoride materials, so that the recycling of scandium from the calcium fluoride has important economic value.
Meanwhile, because the fluorine content in the scandium-containing calcium fluoride material is high, the treatment is relatively difficult, no mature and simple process is available at present for recycling scandium from the scandium-containing calcium fluoride material, and the scandium-containing calcium fluoride material is simply piled up, so that the scandium-containing calcium fluoride material occupies land and causes scandium resource waste. If the material is treated by adopting the acid leaching method, the problems of poor acid leaching effect, no effect and the like exist, hydrofluoric acid is easy to generate in the acid leaching process, and the problems of serious environmental pollution, higher equipment requirement, severe working environment and the like are generated.
Chinese patent application 200910090880.5 discloses a process for extracting and separating rare earth elements, which comprises the steps of mixing and pre-extracting acidic organic extractants such as P507, P204, C272, naphthenic acid and the like with aqueous solutions of organic acid salts of magnesium and/or calcium and rare earth solutions, extracting rare earth ions into an organic phase, and clarifying to obtain a rare earth ion-containing loaded organic phase for extracting and separating mixed rare earth feed liquid. Through multistage extraction, washing and back extraction, single rare earth compound or enrichment of several rare earth elements is obtained. The magnesium and/or calcium organic acid salt aqueous solution is prepared from magnesite, limestone, calcite, dolomite and other minerals through roasting-organic acid dissolution, the content of impurities such as silicon, iron, aluminum and the like is low, three-phase matters are not generated in the pre-extraction and extraction separation processes, the purity of rare earth products is not influenced, the organic phase is not saponified by ammonia, ammonia nitrogen wastewater is not generated, the production cost of the rare earth products is greatly reduced, and a large amount of three-waste treatment cost is saved;
also, as can be seen from an examination of the examples of the scheme, the scheme is more suitable for extracting rare earth elements from rare earth solutions than from minerals or other waste materials.
Chinese patent application 201911378530.9 discloses a method for producing alumina and recovering rare earth elements by using fly ash hydrochloric acid method, comprising the following steps:
1) Pre-removing impurities from fly ash;
2) Leaching to obtain an aluminum chloride immersion liquid and residues which mainly comprise aluminum chloride;
3) Evaporating and concentrating to obtain a concentrated solution with the mass concentration of aluminum chloride of 22-27%;
4) Salting out crystallization I: obtaining aluminum chloride hexahydrate crystal I and salting-out mother liquor I;
5) Washing and dissolving;
6) Salting out crystallization II and washing: salting out and crystallizing II the aluminum chloride solution obtained in the step 5), and carrying out solid-liquid separation to obtain aluminum chloride hexahydrate crystal II and salting-out mother liquor II; washing the aluminum chloride hexahydrate crystal II with a hydrochloric acid solution to obtain a washed solution II;
7) Roasting to obtain an alumina product;
8) Extracting with solvent to recover rare earth element;
according to the scheme, firstly, the coal ash is pre-decontaminated, more than 69% of calcium and sulfur in the coal ash can be removed by using dilute hydrochloric acid with the concentration of 1-3%, the content of calcium and sulfur in subsequent materials is reduced, and the quality of alumina products is improved; the concentration of calcium ions and sulfate radicals in the subsequent materials is reduced, the scaling of a heat exchanger (the component is calcium sulfate) in the subsequent evaporation and concentration step is avoided, and the heat transfer efficiency of the heat exchanger is improved; the hydrochloric acid concentration is only 1-3%, the aluminum leaching rate (loss rate) in the fly ash is less than 3%, and the aluminum loss in the pre-impurity removal step is small, but at the same time, the scheme is observed, because the scheme is to extract scandium in the fly ash, the acid leaching by using dilute hydrochloric acid has the advantages, but if the raw materials in the scheme are replaced by calcium fluoride by the fly ash, and then the acid leaching by using dilute hydrochloric acid can generate hydrofluoric acid harmful to the environment, so that the treatment difficulty is increased, and therefore, although the scheme has a plurality of advantages in the extraction process of scandium in the fly ash, the method is more beneficial in recycling scandium in the calcium fluoride.
The problem that this scheme needs to solve: how to provide a method for recovering scandium from scandium-containing calcium fluoride material, and the method does not use acid to leach scandium in the calcium fluoride so as to prevent the generation of hydrofluoric acid.
Disclosure of Invention
The object of the present invention is to provide a method for recovering scandium from a scandium-containing calcium fluoride material, while the method does not use acid to leach scandium in the calcium fluoride to prevent the formation of hydrofluoric acid.
To achieve the above object, the present application discloses a method for recovering scandium from scandium-containing calcium fluoride material, comprising the steps of:
step 1: crushing and grinding scandium-containing calcium fluoride materials to below 200 meshes to obtain powder;
step 2: adding the powder prepared in the step 1 into 1-3 mol/L aluminum chloride hexahydrate solution, wherein the mass ratio of the powder to the aluminum chloride hexahydrate solution is 1: 8-12, then raising the temperature to 80-90 ℃, stirring and reacting for 2-4 hours, and filtering to obtain a filter cake and scandium-containing filtrate; adjusting the pH value of scandium-containing filtrate to 1-2 by sulfuric acid;
step 3: extracting scandium-containing filtrate prepared in the step 2 by using a mixture of P204 and sulfonated kerosene to obtain an organic phase I;
step 4: washing the organic phase I prepared in the step 3 by using 1-3 mol/L sulfuric acid solution to obtain an organic phase II;
step 5: back-extracting the organic phase II prepared in the step 4 by using 2-3 mol/L sodium hydroxide solution to obtain scandium hydroxide;
step 6: and (3) sequentially carrying out acid dissolution, precipitation and calcination on scandium hydroxide prepared in the step (5) to obtain scandium oxide.
Preferably, the step 3 specifically comprises: adding a mixture of P204 and sulfonated kerosene into scandium-containing filtrate, wherein the mass ratio of the P204 to the sulfonated kerosene is (10-15): 85-90, the volume ratio of the organic phase to the water phase is 1:10 to 22, stirring for 4 to 6 minutes and clarifying for 25 to 35 minutes in the first-stage scandium extraction process to obtain an organic phase I.
Preferably, the step 4 specifically comprises: washing the organic phase prepared in the step 3 by using 1-3 mol/L sulfuric acid solution to obtain an organic phase II, wherein the volume ratio of the organic phase I to the water phase in the washing process is 14-16: 1.
preferably, the step 5 specifically comprises: adding the second organic phase prepared in the step 4 into 2-3 mol/L sodium hydroxide solution and reacting for 0.5-2 h at the temperature of 70-80 ℃ to obtain scandium hydroxide, wherein the volume ratio of the second organic phase to the water phase in the reaction process is 0.8-1.2: 1.
preferably, the acid used in the acid dissolution process of the step 6 is sulfuric acid solution with the concentration of 100-200 g/L, and the solid solution ratio is 1: 4-6, scandium hydroxide is mixed with sulfuric acid solution, and after scandium hydroxide is dissolved, the acid dissolution process is finished, so that a mixed solution I is obtained.
Preferably, the precipitation process is specifically: and (3) precipitating the acid-dissolved mixed solution I by using an oxalic acid solution with the concentration of 75-80 g/L to obtain scandium oxalate precipitate.
Preferably, the calcination temperature in the calcination process is 650-850 ℃ and the calcination time is 2-4 h.
Preferably, the purity of scandium oxide in step 6 is greater than or equal to 99%.
The beneficial effects of this application are: according to the method for recycling scandium from scandium-containing calcium fluoride materials, scandium is leached through aluminum salt coordination, scandium hydroxide is obtained through P204 extraction and sodium hydroxide back extraction, scandium is efficiently recycled in scandium oxide form through dissolution, precipitation and calcination of scandium hydroxide, and the scandium oxide purity can reach more than 99%, and meanwhile, the technical problem of low recycling rate when scandium is recycled from low-content scandium-containing fluoride materials is solved; moreover, because no acid is used in the coordination leaching stage, scandium can be leached efficiently, hydrofluoric acid is not generated, the generation and escape of hydrogen fluoride gas in the traditional extraction method are avoided, the requirements on production equipment are further reduced, and the body harm to production personnel is reduced.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which specific conditions, either conventional or manufacturer-suggested, are not explicitly stated. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Step 1: crushing and grinding scandium-containing calcium fluoride materials to below 200 meshes to obtain powder;
step 2: adding the powder prepared in the step 1 into 3mol/L aluminum chloride hexahydrate solution, wherein the mass ratio of the powder to the aluminum chloride hexahydrate solution is 1:8, then raising the temperature to 80 ℃, stirring and reacting for 2 hours, and filtering to obtain a filter cake and scandium-containing filtrate; adjusting the pH value of scandium-containing filtrate to 1 by adopting sulfuric acid;
step 3: adding a mixture of P204 and sulfonated kerosene into the scandium-containing filtrate prepared in the step 2, wherein the mass ratio of the P204 to the sulfonated kerosene is 15:85, the volume ratio of the organic phase to the aqueous phase is 1:10, in the process of first-stage scandium extraction, stirring for 4min, and clarifying for 25min to obtain an organic phase I;
step 4: washing the organic phase prepared in the step 3 by using a sulfuric acid solution with the concentration of 3mol/L to obtain an organic phase II, wherein the volume ratio of the organic phase I to the water phase in the washing process is 14:1, a step of;
step 5: adding the organic phase II obtained in the step 4 into 3mol/L sodium hydroxide solution and reacting for 2 hours at the temperature of 80 ℃ to obtain scandium hydroxide, wherein the volume ratio of the organic phase II to the water phase in the reaction process is 0.8:1, a step of;
step 6: sequentially carrying out acid dissolution, precipitation and calcination on scandium hydroxide prepared in the step 5, wherein the acid used in the acid dissolution process is sulfuric acid solution with the concentration of 200g/L, and the solid solution ratio is 1: mixing scandium hydroxide with sulfuric acid solution, wherein the reaction temperature is 80 ℃, and after scandium hydroxide is dissolved, ending the acid dissolution process to obtain a mixed solution I;
precipitating the acid-dissolved mixed solution I by using an oxalic acid solution with the concentration of 80g/L to obtain scandium oxalate precipitate, wherein the reaction temperature in the precipitation process is 70 ℃, and the precipitation time is 4 hours;
scandium oxalate was calcined at a high temperature of 650 ℃ for 2 hours to obtain scandium oxide having a purity of 99.1%, and the recovery rate of scandium oxide was calculated to be 96.8%.
Example 2
Step 1: crushing and grinding scandium-containing calcium fluoride materials to below 200 meshes to obtain powder;
step 2: adding the powder prepared in the step 1 into 1mol/L aluminum chloride hexahydrate solution, wherein the mass ratio of the powder to the aluminum chloride hexahydrate solution is 1:12, then raising the temperature to 90 ℃, stirring and reacting for 4 hours, and filtering to obtain a filter cake and scandium-containing filtrate; adjusting the pH value of scandium-containing filtrate to 2 by adopting sulfuric acid;
step 3: adding a mixture of P204 and sulfonated kerosene into the scandium-containing filtrate prepared in the step 2, wherein the mass ratio of the P204 to the sulfonated kerosene is 10:90, the volume ratio of the organic phase to the aqueous phase is 1:22, in the process of extracting scandium at first, stirring for 5min, and clarifying for 30min to obtain an organic phase I;
step 4: washing the organic phase prepared in the step 3 by using a sulfuric acid solution with the concentration of 1mol/L to obtain an organic phase II, wherein the volume ratio of the organic phase I to the water phase in the washing process is 15:1, a step of;
step 5: adding the organic phase II obtained in the step 4 into 2mol/L sodium hydroxide solution and reacting for 0.5h at the temperature of 70 ℃ to obtain scandium hydroxide, wherein the volume ratio of the organic phase II to the water phase in the reaction process is 1:1, a step of;
step 6: sequentially carrying out acid dissolution, precipitation and calcination on scandium hydroxide prepared in the step 5, wherein acid used in the acid dissolution process is sulfuric acid solution with the concentration of 100g/L, and the solid solution ratio is 1:4, mixing scandium hydroxide with sulfuric acid solution, wherein the reaction temperature is 80 ℃, and after scandium hydroxide is dissolved, ending the acid dissolution process to obtain a mixed solution I;
precipitating the acid-dissolved mixed solution I by using an oxalic acid solution with the concentration of 75g/L to obtain scandium oxalate precipitate, wherein the reaction temperature in the precipitation process is 70 ℃, and the precipitation time is 4 hours;
scandium oxalate was calcined at a high temperature of 850 ℃ for 4 hours to obtain scandium oxide having a purity of 99.1%, and the recovery rate of scandium oxide was calculated to be 95.5%.
Example 3
Step 1: crushing and grinding scandium-containing calcium fluoride materials to below 200 meshes to obtain powder;
step 2: adding the powder prepared in the step 1 into 2mol/L aluminum chloride hexahydrate solution, wherein the mass ratio of the powder to the aluminum chloride hexahydrate solution is 1:10, then raising the temperature to 85 ℃, stirring and reacting for 3 hours, and filtering to obtain a filter cake and scandium-containing filtrate; adjusting the pH value of scandium-containing filtrate to 1.5 by adopting sulfuric acid;
step 3: adding a mixture of P204 and sulfonated kerosene into the scandium-containing filtrate prepared in the step 2, wherein the mass ratio of the P204 to the sulfonated kerosene is 12:88, the volume ratio of organic phase to aqueous phase is 1:15, in the process of extracting scandium at first stage, stirring for 6min, and clarifying for 35min to obtain an organic phase I;
step 4: washing the organic phase prepared in the step 3 by using 2mol/L sulfuric acid solution to obtain an organic phase II, wherein the volume ratio of the organic phase I to the water phase in the washing process is 16:1, a step of;
step 5: adding the organic phase II obtained in the step 4 into 2.5mol/L sodium hydroxide solution and reacting for 1h at the temperature of 75 ℃ to obtain scandium hydroxide, wherein the volume ratio of the organic phase II to the water phase in the reaction process is 1.2:1, a step of;
step 6: sequentially carrying out acid dissolution, precipitation and calcination on scandium hydroxide prepared in the step 5, wherein the acid used in the acid dissolution process is sulfuric acid solution with the concentration of 150g/L, and the solid solution ratio is 1:5, mixing scandium hydroxide with sulfuric acid solution, wherein the reaction temperature is 80 ℃, and after scandium hydroxide is dissolved, ending the acid dissolution process to obtain a mixed solution I;
precipitating the acid-dissolved mixed solution I by using an oxalic acid solution with the concentration of 78g/L to obtain scandium oxalate precipitate, wherein the reaction temperature in the precipitation process is 70 ℃, and the precipitation time is 4 hours;
scandium oxalate was calcined at a high temperature of 750 ℃ for 3 hours to obtain scandium oxide having a purity of 99.8%, and the recovery rate of scandium oxide was calculated to be 97.5%.
Comparative example 1
Substantially the same as in example 1, except that 2mol/L of dilute hydrochloric acid solution was used in place of 2mol/L of aluminum chloride hexahydrate solution in step 2, scandium oxide having a purity of 96.5% was finally obtained, and the recovery rate of scandium oxide was calculated to be 4.55%.
Comparative example 2
Substantially the same as in example 1, except that in step 2, 1mol/L of aluminum sulfate solution was used instead of 2mol/L of aluminum chloride hexahydrate solution, scandium oxide having a purity of 95.9% was finally obtained, and the recovery rate of scandium oxide was calculated to be 5.10%.
Comparative example 3
Substantially the same as in example 1, except that in step 2, a mixed solution of a sodium chloride solution of 2mol/L and an aluminum sulfate solution of 1mol/L was used in place of the aluminum chloride hexahydrate solution of 2mol/L, scandium oxide having a purity of 96.8% was finally obtained, and the recovery rate of scandium oxide was calculated to be 56.8%.
Comparative example 4
Substantially the same as in example 1, except that in step 2, a mixed solution of a chlorine solution of 2mol/L and a dilute hydrochloric acid solution of 2mol/L was used in place of the aluminum chloride hexahydrate solution of 2mol/L, scandium oxide having a purity of 96.8% was finally obtained, and the recovery rate of scandium oxide was calculated to be 91.6%.
Analysis of results:
as can be seen from examples 1 and comparative examples 1 to 2, when the aluminum chloride hexahydrate was replaced with an aluminum salt solution containing aluminum ions or a solution containing chloride ions, respectively, the recovery rate of scandium oxide was not high although scandium oxide was extracted to a high degree from comparative examples 1 and 2, and at the same time, when the aluminum chloride hexahydrate was replaced with a mixed solution of sodium chloride containing both chloride ions and aluminum sulfate from comparative example 3, good extraction effect was not ensured, and therefore, it was considered that the simultaneous presence of aluminum ions and chloride ions in the solution only ensured that scandium oxide could be extracted, but the extraction effect of scandium oxide was not made more excellent, and it was observed that comparative example 4 was observed that although the recovery rate of scandium oxide was improved to some extent from the use of a mixed solution of aluminum chloride and hydrochloric acid instead of aluminum chloride, a certain difference was still obtained between the recovery rate after the improvement and example 1, and the use of hydrochloric acid also resulted in the formation of hydrofluoric acid.
Claims (8)
1. A method for recovering scandium from a scandium-containing calcium fluoride material, comprising the steps of:
step 1: crushing and grinding scandium-containing calcium fluoride materials to below 200 meshes to obtain powder;
step 2: adding the powder prepared in the step 1 into 1-3 mol/L aluminum chloride hexahydrate solution, wherein the mass ratio of the powder to the aluminum chloride hexahydrate solution is 1: 8-12, then raising the temperature to 80-90 ℃, stirring and reacting for 2-4 hours, and filtering to obtain a filter cake and scandium-containing filtrate; adjusting the pH value of scandium-containing filtrate to 1-2 by sulfuric acid;
step 3: extracting scandium-containing filtrate prepared in the step 2 by using a mixture of P204 and sulfonated kerosene to obtain an organic phase I;
step 4: washing the organic phase I prepared in the step 3 by using 1-3 mol/L sulfuric acid solution to obtain an organic phase II;
step 5: back-extracting the organic phase II prepared in the step 4 by using 2-3 mol/L sodium hydroxide solution to obtain scandium hydroxide;
step 6: and (3) sequentially carrying out acid dissolution, precipitation and calcination on scandium hydroxide prepared in the step (5) to obtain scandium oxide.
2. The method for recovering scandium from a scandium-containing calcium fluoride material according to claim 1, wherein said step 3 is specifically: adding a mixture of P204 and sulfonated kerosene into scandium-containing filtrate, wherein the mass ratio of the P204 to the sulfonated kerosene is (10-15): 85-90, the volume ratio of the organic phase to the water phase is 1:10 to 22, stirring for 4 to 6 minutes and clarifying for 25 to 35 minutes in the first-stage scandium extraction process to obtain an organic phase I.
3. The method for recovering scandium from a scandium-containing calcium fluoride material according to claim 1, wherein said step 4 is specifically: washing the organic phase prepared in the step 3 by using 1-3 mol/L sulfuric acid solution to obtain an organic phase II, wherein the volume ratio of the organic phase I to the water phase in the washing process is 14-16: 1.
4. the method for recovering scandium from a scandium-containing calcium fluoride material according to claim 1, wherein said step 5 is specifically: adding the second organic phase prepared in the step 4 into 2-3 mol/L sodium hydroxide solution and reacting for 0.5-2 h at the temperature of 70-80 ℃ to obtain scandium hydroxide, wherein the volume ratio of the second organic phase to the water phase in the reaction process is 0.8-1.2: 1.
5. the method for recovering scandium from scandium-containing calcium fluoride according to claim 1, wherein the acid used in the acid dissolution process of step 6 is sulfuric acid solution with concentration of 100-200 g/L, and the solid solution ratio is 1: 4-6, scandium hydroxide is mixed with sulfuric acid solution, and after scandium hydroxide is dissolved, the acid dissolution process is finished, so that a mixed solution I is obtained.
6. The method according to claim 5, characterized in that the precipitation process is in particular: and (3) precipitating the acid-dissolved mixed solution I by using an oxalic acid solution with the concentration of 75-80 g/L to obtain scandium oxalate precipitate.
7. The method for recovering scandium from scandium-containing calcium fluoride according to claim 1, wherein the calcination temperature in the calcination process is 650-850 ℃ and the calcination time is 2-4 hours.
8. The method for recovering scandium from a scandium-containing calcium fluoride material according to claim 1, wherein the purity of scandium oxide in step 6 is greater than or equal to 99%.
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