CN117800380A - Method for preparing high-purity scandium oxide product from crude scandium oxide - Google Patents
Method for preparing high-purity scandium oxide product from crude scandium oxide Download PDFInfo
- Publication number
- CN117800380A CN117800380A CN202311774675.7A CN202311774675A CN117800380A CN 117800380 A CN117800380 A CN 117800380A CN 202311774675 A CN202311774675 A CN 202311774675A CN 117800380 A CN117800380 A CN 117800380A
- Authority
- CN
- China
- Prior art keywords
- scandium
- acid
- scandium oxide
- crude
- purity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 77
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 77
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000012535 impurity Substances 0.000 claims abstract description 44
- 238000000605 extraction Methods 0.000 claims abstract description 42
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 16
- 230000000536 complexating effect Effects 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 octyl-decyl Chemical group 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- QOPUBSBYMCLLKW-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]-4-hydroxybutanoic acid Chemical compound OCCC(C(O)=O)N(CC(O)=O)CCN(CC(O)=O)CC(O)=O QOPUBSBYMCLLKW-UHFFFAOYSA-N 0.000 claims description 3
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000010668 complexation reaction Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 241000968352 Scandia <hydrozoan> Species 0.000 claims 2
- 238000010304 firing Methods 0.000 claims 2
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052725 zinc Inorganic materials 0.000 abstract description 14
- 239000011701 zinc Substances 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 8
- 229940116315 oxalic acid Drugs 0.000 description 8
- 239000003350 kerosene Substances 0.000 description 6
- 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 description 6
- 238000003756 stirring Methods 0.000 description 6
- 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 5
- 238000001556 precipitation Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000003916 acid precipitation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229940116316 dihydrate oxalic acid Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 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
- 239000004408 titanium dioxide Substances 0.000 description 1
Abstract
The invention discloses a method for preparing a high-purity scandium oxide product from crude scandium oxide, which comprises the following steps: dissolving crude scandium oxide by adopting hydrochloric acid; adding an amine extractant to remove impurity iron and zinc to obtain a section of purified liquid after impurity removal; complexing agent is added into raffinate to complex scandium, and phosphate acid extractant is adopted to extract main impurities such as calcium, aluminum, magnesium, manganese and the like, so as to obtain a second-stage purified liquid after impurity removal; decomplexing is carried out by adding decomplexing agent into scandium-containing back extraction liquid, precipitating scandium by adding precipitant into decomplexing scandium-containing solution, filtering, washing, roasting to obtain refined high-purity scandium oxide (more than 99.99%). The process has the advantages of short flow, low cost and good product quality, and provides an effective impurity removal method for preparing the high-purity scandium oxide.
Description
Technical Field
The invention belongs to the field of rare earth metal metallurgy, and particularly relates to a method for preparing a high-purity scandium oxide product from crude scandium oxide.
Background
Scandium is an alloy material with excellent properties and is widely used in a plurality of fields. In nature, large independent scandium ores are very rare, so scandium is usually present with other substances. The main sources of scandium recovery in industry are secondary resources containing scandium, such as titanium white waste acid, red mud, bayan obo ore, chloridized smoke dust and the like. The low-grade scandium in the raw materials can be enriched by a hydrometallurgical method, such as a solvent extraction method, a precipitation method, an ion exchange method and the like, so that a crude scandium oxide product or an enriched scandium solution is obtained, and then a high-purity scandium oxide product is prepared by other methods.
The coarse scandium oxide contains more impurities such as calcium, iron, magnesium, lithium, zinc, aluminum, manganese, nickel and the like. Therefore, before high-purity scandium oxide is produced, the crude scandate needs to be dissolved and then converted into scandium-containing acid solution, and then impurity ions are removed.
At present, a certain research foundation is provided for deeply removing impurities from scandium-containing acid solutions. According to the invention patent 202011143998.2, a neutral extractant P350 is adopted to purify scandium in the crude scandium oxide leaching solution, and oxalic acid precipitation is carried out to prepare a high-purity scandium oxide product. However, the P350 production process causes serious environmental pollution, and thus the problem of difficulty in purchasing due to interruption of extractant production is faced. The invention patent CN201410809499.0 proposes to purify scandium-containing solution by ion exchange method, and to remove impurities such as iron, aluminum, calcium and partial titanium, zirconium, magnesium and manganese by complexing scandium and then adsorbing impurities.
Besides solvent extraction and ion exchange technology, a process for purifying scandium by using a chemical precipitation method is also available, for example, a method for preparing high-purity scandium oxide by purifying scandium hydroxide disclosed by the invention of CN202310726842.4 is to remove impurities by using a phosphate precipitation method, then select solvent extraction for further purification, and obtain a 3N-grade high-purity scandium oxide product after precipitating scandium by oxalic acid. The method has obvious effects mainly on iron, zirconium, calcium and the like, and has poor effects on other impurity ions.
The present invention has been made in view of the above problems.
Disclosure of Invention
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which has better removal effect on main impurities such as calcium, iron, magnesium, lithium, zinc, aluminum, manganese, nickel and the like, and finally prepares a high-purity scandium oxide product with purity higher than 99.99%. The method is mainly solvent extraction, has simple operation, high efficiency, good effect, low cost and excellent product quality.
The invention adopts the technical scheme that:
a method for producing high purity scandium oxide from crude scandium oxide, comprising the steps of:
(1) Acid soluble crude scandium: dissolving crude scandium oxide by adopting hydrochloric acid to obtain scandium-containing solution;
(2) And (3) extracting and removing impurities: adding inorganic acid to regulate acidity of scandium-containing solution, and extracting impurities ferric iron and zinc ions by adopting an amine extractant to obtain a first-stage purifying liquid after primary impurity removal;
(3) Complexing: adding a complexing agent into the first section of purified liquid after preliminary impurity removal in the step (2) to complex scandium;
(4) Two-stage extraction and impurity removal: adding an alkaline reagent into the scandium-containing solution subjected to complexation in the step (3), regulating the pH value of the solution, and further extracting calcium, magnesium, aluminum and manganese impurities in the solution by adopting a phosphate acidic extractant to obtain a second-stage purified solution after further impurity removal;
(5) Decomplexing and precipitating scandium: adding a decomplexing agent into the purified liquid after the impurity removal in the step (4) to decomplexate, and then adding a precipitating agent to precipitate scandium;
(6) Roasting: and (3) filtering, washing and roasting the scandium-containing precipitate obtained in the step (5) to obtain refined high-purity scandium oxide.
The technical principle of the invention is as follows:
because the complexing of Fe (III) and the complexing agent is superior to Sc (III), the Fe (III) needs to be removed before the Sc (III) is complexed, and an amine extractant is adopted to remove the Fe (III) in scandium-containing solution, and meanwhile, impurity zinc can be removed; adding a proper amount of complexing agent into scandium-containing solution with iron and zinc removed to convert cationic scandium into complex anions, so that scandium extraction by an acidic extractant is avoided; in the second-stage extraction impurity removal process, most of impurities such as calcium, magnesium, aluminum, manganese, part of lithium, nickel and the like existing in a cationic form are extracted by an acidic extractant, and scandium existing in a complex anion form is not extracted, so that scandium-containing raffinate after impurity removal is obtained; and finally, scandium is precipitated by adopting a scandium precipitation method, and the precipitate is subjected to oxidative roasting to obtain high-purity scandium oxide.
Wherein the crude scandium oxide product is a product containing Fe 2 O 3 、CaO、MgO、Li 2 O、ZnO、Al 2 O 3 、MnO 2 、Ni 2 Scandium oxide solid of one or more oxides in O, the scandium oxide content is 30% -99%.
Optionally, hydrochloric acid with the concentration of 2-12M is adopted in the step (1) to heat and dissolve crude scandium oxide solid, the liquid-solid ratio is 10:1-50:1, the temperature is room temperature-100 ℃, and the time is 5-60 min.
Preferably, in the step (1), hydrochloric acid with the concentration of 6-12M is adopted to heat and dissolve crude scandium oxide solid, the liquid-solid ratio is 15:1-20:1, the temperature is 80-90 ℃, and the time is 20-30 min.
Optionally, the inorganic acid used for adjusting the acidity in the step (2) is hydrochloric acid with the concentration of 2-12M, and the target acidity is adjusted to 1-6M; the extractant is N235 (tri (octyl-decyl) alkyl tertiary amine), the volume fraction of N235 is 1-15%, and the extraction mode is multistage countercurrent extraction compared with O/A of 1:5-5:1.
Preferably, the inorganic acid used for adjusting the acidity in the step (2) is hydrochloric acid with the concentration of 6-12M, and the target acidity is adjusted to 2-4M; n235 concentration is 5-15%, and compared with O/A of 1:1-5:1, the extraction mode is 4-6 grade countercurrent extraction.
Optionally, the complexing agent used in the step (3) is one or more of EDTA (ethylenediamine tetraacetic acid), NTA (nitrilotriacetic acid), HEDTA (hydroxyethyl ethylenediamine tetraacetic acid), diethyl Triamine Pentaacetic Acid (DTPA), trans-1, 2-cyclohexanediamine tetraacetic acid (DCTA) and lactic acid, and the addition amount is 0.8-1.0 times of the theoretical amount required for complexing Sc (III).
Preferably, the complexing agent used in step (3) is added in an amount of 0.9 to 1.0 times the amount theoretically required for complexing Sc (III).
Optionally, the alkaline reagent for adjusting the pH in the step (4) is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, and the pH is adjusted to 2-7; the acid extractant is P204 or P507, the modifier adopted in the extraction adopts one or more of TBP, sec-octanol and isooctyl alcohol, the volume fraction of the extractant is 1-10%, the volume fraction of the modifier is 0-10%, the ratio of O/A is 1:5-5:1, the extraction balance pH is 2-6, and the extraction mode is multistage countercurrent extraction.
Preferably, the pH in the step (4) is adjusted to 3-5; the volume fraction of the extractant is 5-10%, the volume fraction of the modifier is 5-10%, the ratio of the O/A to the O/A is 1:1-5:1, the extraction equilibrium pH is 4.8-5.0, and the extraction mode is 3-5-stage countercurrent extraction.
Optionally, one or more of hydrochloric acid, sulfuric acid and nitric acid are selected as decomplexer in the step (5), and oxalic acid, sodium carbonate, ammonia water, ammonium carbonate and carbon dioxide are selected as precipitants.
Preferably, hydrochloric acid with the concentration of 1-6M is selected as a decomplexing agent in the step (5), and oxalic acid is selected as a precipitating agent.
Preferably, the roasting temperature in the step (6) is 700-900 ℃ and the roasting time is 1-2 h.
The invention has the beneficial effects that:
1. the scandium in the crude scandium oxide is purified by adopting a multistage extraction impurity removal method, and impurities such as iron, magnesium, lithium, zinc, aluminum, manganese, nickel and the like are deeply removed, so that a high-purity scandium oxide product is prepared.
2. Simple flow, low cost, small scandium loss rate and excellent product quality.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which mainly comprises the steps of acid dissolution, primary extraction for removing iron and zinc, secondary extraction for removing calcium, magnesium, aluminum and manganese, precipitation scandium by a precipitation method and the like, and for the purpose of describing the invention in detail, the specific embodiments of each part of the invention are respectively exemplified:
1. acid dissolution of crude scandium oxide
The crude scandium oxide employed in this example was recovered from scandium-containing waste liquid produced in the chloride process titanium dioxide process, and contained 76.44% of Sc 2 O 3 The main impurities are Fe (III) and Mg, li, zn, al, mn, ni.
Example 1
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) Weighing coarse scandium oxide with certain mass, adding 12M hydrochloric acid according to a liquid-solid ratio of 20:1 into a beaker, sealing by adopting a preservative film, and preventing the hydrochloric acid from volatilizing.
(2) Heating and dissolving for 30min at 90 ℃, and the scandium dissolution rate can reach 97.72%.
Example 2
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) Weighing coarse scandium oxide with certain mass, adding 8M hydrochloric acid according to a liquid-solid ratio of 15:1 into a beaker, and reacting under a closed condition to prevent volatilization of the hydrochloric acid.
(2) Heating and dissolving for 25min at 85 ℃, and the scandium dissolution rate can reach 92.77%.
Example 3
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) Weighing coarse scandium oxide with certain mass, adding 6M hydrochloric acid according to a liquid-solid ratio of 15:1 into a beaker, sealing by adopting a preservative film, and preventing the hydrochloric acid from volatilizing.
(2) The scandium dissolution rate can reach 86.76% when the scandium is heated for 20min under the condition that the heating temperature is 80 ℃.
2. Extraction of scandium-containing chloridized solution to remove iron and zinc
Example 1
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) 12M hydrochloric acid is added into scandium-containing chloridized solution obtained by acid dissolution, and the acidity is adjusted to 4M.
(2) Extracting impurities of iron and zinc from scandium-containing solution with adjusted acidity by using N235, acidifying an organic phase by using 1M hydrochloric acid in advance, wherein the volume fraction of N235 is 15%, and the balance is sulfonated kerosene.
(3) Under the condition of O/A=1:1, the extraction rate of ferric iron and zinc is 99.91 percent and 99.94 percent by 6-stage countercurrent extraction, and the scandium extraction rate is less than 0.15 percent.
Example 2
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) 6M hydrochloric acid is added into scandium-containing chloridized solution obtained by acid dissolution, and the acidity is adjusted to 2M.
(2) Extracting impurities of iron and zinc from scandium-containing solution with adjusted acidity by using N235, acidifying an organic phase by using 1M hydrochloric acid in advance, wherein the volume fraction of N235 is 5%, and the balance is sulfonated kerosene.
(3) Under the condition of O/A=5:1, the extraction rate of ferric iron and zinc is 99.90 percent and 99.95 percent by 4-stage countercurrent extraction, and the scandium extraction rate is less than 0.13 percent.
Example 3
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) 8M hydrochloric acid is added into scandium-containing chloridizing solution obtained by acid dissolution, and the acidity is adjusted to 3M.
(2) Extracting impurities of iron and zinc from scandium-containing solution with adjusted acidity by using N235, acidifying an organic phase by using 1M hydrochloric acid in advance, wherein the volume fraction of the N235 is 10%, and the balance is sulfonated kerosene.
(3) Under the condition of O/A=3:1, the extraction rate of ferric iron and zinc is 99.91 percent and 99.96 percent by 5-stage countercurrent extraction, and the scandium extraction rate is less than 0.14 percent.
3. Extraction and removal of calcium, magnesium, aluminum and manganese from a primary purification liquid
Example 1
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) EDTA (ethylenediamine tetraacetic acid) is added to the first-stage purification solution to complex scandium, and the addition amount is 1.0 times the amount which can theoretically complex all Sc (III).
(2) To the scandium complexed solution was added sodium hydroxide solids to adjust the pH to ph=5.0. Complexing for 24h under stirring, and filtering to obtain filtrate.
(3) The scandium-containing solution with the pH adjusted is used for extracting impurities of calcium, magnesium, aluminum and manganese by using P204. The volume fraction of P204 is 5%, the volume fraction of TBP is 5%, and the balance is sulfonated kerosene.
(4) Under the condition of O/A=5:1, the extraction rate of calcium, magnesium, aluminum and manganese is 99.97%, 99.90%, 99.99%, 99.95% and scandium extraction rate is less than 0.08% respectively at equilibrium pH=4.90 through 3-stage countercurrent extraction.
Example 2
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) And adding lactic acid to complex scandium into the first-stage purifying liquid, wherein the adding amount is 0.9 times of the theoretical complex Sc (III).
(2) To the scandium complexed solution was added sodium carbonate solids to adjust the pH to ph=3.2. Complexing for 24h under stirring, and filtering to obtain filtrate.
(3) The scandium-containing solution with the pH adjusted was extracted with P507 for impurities of calcium, magnesium, aluminum and manganese. The volume fraction of P507 is 10%, the volume fraction of isooctanol is 5%, and the rest is sulfonated kerosene.
(4) Under the condition of O/A=3:1, the extraction rate of calcium, magnesium, aluminum and manganese is 99.92%, 99.82%, 99.95%, 99.89% and the scandium extraction rate is less than 0.4% respectively at the equilibrium pH=4.51 through 4-stage countercurrent extraction.
Example 3
The invention provides a method for preparing high-purity scandium oxide from crude scandium oxide, which comprises the following steps of:
(1) And adding DCTA to complex scandium into the first-stage purifying liquid, wherein the adding amount is 0.95 times of the theoretical complex Sc (III).
(2) To the scandium complexed solution was added sodium bicarbonate solids to adjust the pH to ph=4.2. Complexing for 24h under stirring, and filtering to obtain filtrate.
(3) The scandium-containing solution with the pH adjusted is used for extracting impurities of calcium, magnesium, aluminum and manganese by using P204. The volume fraction of P204 is 10%, the volume fraction of sec-octanol is 10%, and the rest is sulfonated kerosene.
(4) Under the condition of O/A=1:1, the extraction rate of calcium, magnesium, aluminum and manganese is 99.91%, 99.82%, 99.96%, 99.88% and scandium is less than 0.29% respectively at equilibrium pH=4.86 through 5-stage countercurrent extraction.
4. Preparation of high-purity scandium oxide by precipitating scandium with oxalic acid
Example 1
The method for preparing high-purity scandium oxide from crude scandium oxide provided by the invention removes lithium nickel through oxalic acid precipitation scandium, and the preparation method comprises the following steps:
(1) 6M hydrochloric acid is added into the second raffinate to decomplex, and the addition amount is 1.0 times of the theoretical amount.
(2) Adding 1.0 times of dihydrate oxalic acid which is needed by the theoretical complexing Sc (III) into the decomplexed solution, stirring and precipitating for 2 hours to obtain scandium oxalate precipitate, and removing impurities lithium and nickel.
(3) Washing scandium oxalate precipitate with ultrapure water, removing sodium salt, and roasting at 900 ℃ for 1h to obtain scandium oxide solid. The purity of scandium oxide is more than 99.99%, and the removal rate of lithium and nickel is 99.96% and 99.92% respectively.
Example 2
The method for preparing high-purity scandium oxide from crude scandium oxide provided by the invention removes lithium nickel through oxalic acid precipitation scandium, and the preparation method comprises the following steps:
(1) 1M hydrochloric acid is added into the second raffinate to decomplex, and the addition amount is 1.1 times of the theoretical amount.
(2) Adding sodium oxalate which is 0.9 times of the amount required by theoretical complexing Sc (III) into the decomplexed solution, stirring and precipitating for 2 hours to obtain scandium oxalate precipitate, and removing impurities lithium and nickel.
(3) Washing scandium oxalate precipitate with ultrapure water, removing sodium salt, and roasting at 800 ℃ for 1.5h to obtain scandium oxide solid. The purity of scandium oxide is more than 99.99%, and the removal rate of lithium and nickel is 99.94% and 99.90% respectively.
Example 3
The method for preparing high-purity scandium oxide from crude scandium oxide provided by the invention removes lithium nickel through oxalic acid precipitation scandium, and the preparation method comprises the following steps:
(1) 3M hydrochloric acid is added into the second raffinate to decomplex, and the addition amount is 1.0 times of the theoretical amount.
(2) Adding 1.1 times of dihydrate oxalic acid which is needed by the theoretical complexing Sc (III) into the decomplexed solution, stirring and precipitating for 2 hours to obtain scandium oxalate precipitate, and removing impurities lithium and nickel.
(3) Washing scandium oxalate precipitate with ultrapure water, removing sodium salt, and roasting at 700 ℃ for 2 hours to obtain scandium oxide solid. The purity of scandium oxide is more than 99.99%, and the removal rate of lithium and nickel is 99.95% and 99.91% respectively.
The above examples are merely illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, as various modifications and variations may be suggested to one skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A process for preparing a high purity scandia product from crude scandia, comprising the steps of:
(1) Acid soluble crude scandium: dissolving crude scandium oxide by adopting hydrochloric acid to obtain scandium-containing chloridized solution;
(2) And (3) extracting and removing impurities: adding inorganic acid to regulate acidity of scandium-containing chloridizing solution, and extracting impurities ferric iron and zinc ions by adopting an amine extractant to obtain a first-stage purifying solution after primary impurity removal;
(3) Complexing: adding a complexing agent into the first section of purified liquid after the impurity removal in the step (2) to complex scandium;
(4) Two-stage extraction and impurity removal: adding an alkaline reagent into the scandium-containing solution after complexation in the step (3), adjusting the pH value of the solution, and then adopting a phosphate acidic extractant to further extract calcium, magnesium, aluminum and manganese impurities in the solution;
(5) Decomplexing and precipitating scandium: adding a decomplexing agent into the purified liquid after the impurity removal in the step (4) to decomplexate, and then adding a precipitating agent to precipitate scandium;
(6) Roasting: and filtering, washing and roasting scandium-containing precipitate to obtain refined high-purity scandium oxide.
2. The method according to claim 1, characterized in that the coarse scandium oxide is a solid powder or granules with a scandium oxide mass fraction of 30-99%.
3. The method of claim 1, wherein the step (1) is performed by dissolving the crude scandium oxide solids using hydrochloric acid heating.
4. The method according to claim 1, wherein the inorganic acid used for adjusting the acidity in the step (2) is concentrated hydrochloric acid of 2 to 12M, and the target acidity is adjusted to 1 to 6M.
5. The process according to claim 1, wherein the extractant used in step (2) is tri (octyl-decyl) alkyl tertiary amine by multistage countercurrent extraction.
6. The method according to claim 1, wherein the complexing agent used in the step (3) is one or more of ethylenediamine tetraacetic acid, nitrilotriacetic acid, hydroxyethyl ethylenediamine tetraacetic acid, diethyl triamine pentaacetic acid, trans-1, 2-cyclohexanediamine tetraacetic acid and lactic acid, and the addition amount is 0.8-1.0 times of the theoretical amount required for complexing scandium (iii).
7. The method according to claim 1, wherein the alkaline agent for adjusting the pH in the step (4) is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, and ammonia water, and the pH is adjusted to 2 to 7.
8. The method of claim 1, wherein the acidic extractant used in the step (4) is P204 or P507, the modifier used in the extraction is one or more of TBP, sec-octanol and isooctanol, and the extraction mode is multistage countercurrent extraction.
9. The method according to claim 1, wherein one or more of hydrochloric acid, sulfuric acid and nitric acid are selected as decomplexer in the step (5), and oxalic acid, sodium carbonate, ammonia water, ammonium carbonate and carbon dioxide are selected as precipitants.
10. The method according to claim 1, wherein the firing temperature in the step (6) is 700 to 900 ℃ and the firing time is 1 to 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311774675.7A CN117800380A (en) | 2023-12-21 | 2023-12-21 | Method for preparing high-purity scandium oxide product from crude scandium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311774675.7A CN117800380A (en) | 2023-12-21 | 2023-12-21 | Method for preparing high-purity scandium oxide product from crude scandium oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117800380A true CN117800380A (en) | 2024-04-02 |
Family
ID=90429039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311774675.7A Pending CN117800380A (en) | 2023-12-21 | 2023-12-21 | Method for preparing high-purity scandium oxide product from crude scandium oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117800380A (en) |
-
2023
- 2023-12-21 CN CN202311774675.7A patent/CN117800380A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11459636B2 (en) | Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore | |
| EP3489372B1 (en) | Method for process laterite-nickel ore | |
| CN111020188B (en) | Extracting agent and preparation method and application thereof | |
| US4008076A (en) | Method for processing manganese nodules and recovering the values contained therein | |
| CN110093506A (en) | Valuable metal high efficiency extraction and its minimizing processing method in germanic zinc leaching residue | |
| CN109593977B (en) | Method for removing iron ions in neodymium, praseodymium, dysprosium and iron-containing solution | |
| CN105274352B (en) | A kind of method that copper cobalt manganese is separated in the manganese cobalt calcium zinc mixture from copper carbonate | |
| CN110983044B (en) | Method for recycling scandium and vanadium from titanium white wastewater produced by chlorination process | |
| CN117800380A (en) | Method for preparing high-purity scandium oxide product from crude scandium oxide | |
| CN113479937B (en) | Method for preparing spheroidal iron oxide | |
| CN115927884A (en) | Defluorination method for rare earth ore leaching solution | |
| CN112746185B (en) | Method for recovering indium from indium-containing acidic solution | |
| Senapati et al. | Purification of nickel sulphate solutions containing iron, copper, cobalt, zinc and manganese | |
| CN110117721B (en) | Method for extracting valuable metals from sulfuric acid residue by phosphoric acid leaching-extraction | |
| CN113106255B (en) | Method for separating and recycling cobalt, zirconium and tantalum from cobalt-zirconium-tantalum target cutting material | |
| CN114318019B (en) | Method for separating rare earth and aluminum from ionic rare earth mine leachate | |
| KR102390682B1 (en) | Selective recovery method of vanadium and cesium from waste sulfuric acid vanadium catalyst, and high-quality vanadium aqueous solution and cesium alum produced thereby | |
| CN114480860B (en) | Method for selectively leaching rare earth elements from red mud | |
| CN114835165B (en) | Method for directly producing tungsten oxide powder by adopting sodium tungstate solution | |
| CN113584327B (en) | Method for purifying scandium oxide | |
| CN116083723A (en) | Method for separating and recovering rare earth and iron in neodymium iron boron waste | |
| CN117604240A (en) | Method for recovering rare earth, zirconium and ferric phosphate by decomposing xenotime through high-temperature roasting of concentrated sulfuric acid | |
| CN114369731A (en) | Method for reducing molybdenum back-extraction triphase substances | |
| CN117758081A (en) | Method for extracting scandium from titanium white waste acid and ferric hydroxide slag in cooperation | |
| CN117758072A (en) | Method for recycling scandium from scandium-containing solid waste generated by extracting titanium by chlorination process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |