CN114634199B - Method for preparing ultra-high purity scandium oxide at low cost - Google Patents
Method for preparing ultra-high purity scandium oxide at low cost Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000605 extraction Methods 0.000 claims abstract description 82
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 35
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012074 organic phase Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000011550 stock solution Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 14
- -1 nitrate ions Chemical class 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 14
- 238000001556 precipitation Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000542 Sc alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- LUKDNTKUBVKBMZ-UHFFFAOYSA-N aluminum scandium Chemical compound [Al].[Sc] LUKDNTKUBVKBMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SNAMIIGIIUQQSP-UHFFFAOYSA-N bis(6-methylheptyl) hydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(=O)OCCCCCC(C)C SNAMIIGIIUQQSP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/212—Scandium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing ultra-high purity scandium oxide with low cost. The method comprises the following steps: adjusting the acidity of the extraction stock solution to be 6-9 mol/L, adjusting the concentration of nitrate ions in the extraction stock solution to be less than or equal to 2mol/L, adjusting the concentration of sulfate ions in the extraction stock solution to be less than 3mol/L, and extracting to obtain a loaded organic phase and raffinate, wherein the extraction stock solution is scandium-containing solution taking chloride ions as a main system, and the concentration of chloride ions is more than or equal to 0.5mol/L; the extractant in the extracted organic phase adopts phosphate extractant; washing and back-extracting the loaded organic phase sequentially to obtain back-extracting solution, wherein the acidity of the washing solution is more than or equal to 6mol/L, and the acidity of the back-extracting solution is less than 6mol/L; and precipitating and calcining the strip liquor to obtain scandium oxide. The scandium oxide prepared by the method is easy to realize the back extraction process, does not need strong alkali precipitation back extraction, does not cause a large amount of organic impurities, does not cause loss, and has the advantages of low cost, low requirements on equipment, simple process, high safety and high extraction rate.
Description
Technical Field
The invention relates to the technical field of scandium oxide preparation, in particular to a method for preparing ultra-high purity scandium oxide with low cost.
Background
Scandium is an important rare earth element, is the best aluminum alloy grain refiner, and has unique properties, so that scandium materials represented by aluminum scandium alloy have irreplaceable effects in the fields of aerospace, aviation, national defense, new energy, new generation information technology and the like, and scandium is listed as a key mineral resource in the United states, japan, australia and other countries. Currently, 4N scandium oxide in the international market is expensive, up to $4600 per kilogram. With the popularization of 5G, high-power communication modules and base stations expand, and high-frequency high-power devices and modules gradually go on the stage of application; in addition, scandium is widely applied to ohmic contact electrodes, schottky contact electrodes, phase change storage media and the Internet of third-generation semiconductor power electronic chips, so that the demand for high-purity scandium is increasing.
At present, the preparation of the ultra-high purity scandium oxide is generally carried out by adopting extractants such as P350, TBP and the like or corresponding extraction resin thereof, and other extractants such as P204, P507, cyanex272 and the like are also adopted. The scandium oxide prepared by the extractant in the prior art has a series of problems of high cost, low safety, high equipment requirement, complex process, difficult back extraction and the like. Specifically, for example:
1) The main problems of the preparation of high-purity scandium oxide by using P350 are that the cost of the P350 is high, and the P350 extractant has a great danger in the preparation process and the process is complex.
2) In the process of preparing high-purity scandium oxide by adopting TBP, higher acidity is required, and mineral acid is easy to volatilize under the condition of higher acidity. In addition, the solubility of TBP in the solution is higher, the corrosion capacity of TBP extractant to the extraction tank is higher, and the requirements on the material of the extraction tank are higher, thus the preparation cost is increased in an intangible way. In practical applications, TBPs are used less often.
3) When other extractant such as P204 or P507 is adopted to prepare high-purity scandium oxide, the back extraction is difficult, the back extraction by alkali is needed, the phase separation is difficult, and the secondary introduction of impurities is extremely easy. When the Cyanex272 is loaded with scandium, the method is easy to realize in the back extraction process, but has no selective characteristic, other impurities in extracted scandium cannot be removed, and the method can be used for preliminary enrichment of scandium, but cannot be used for preparing high-purity scandium oxide.
Disclosure of Invention
Based on the above problems, it is an object of the present invention to provide a low cost method for preparing ultra-high purity scandium oxide; the method has low cost, easy back extraction, no need of back extraction by precipitation of strong alkali, no occurrence of a large amount of organic impurities, and little loss in the preparation process; can solve a series of problems of high cost, low safety, high equipment requirement, complex process, difficult back extraction and the like existing in the existing scandium oxide preparation methods.
The above object of the present invention is achieved by the following technical solutions:
according to one aspect of the invention, the invention provides a method for preparing ultra-high purity scandium oxide at low cost, comprising the following steps:
adjusting the acidity of the extraction stock solution to be 6-9 mol/L, adjusting the concentration of nitrate ions in the extraction stock solution to be less than or equal to 2mol/L, adjusting the concentration of sulfate ions in the extraction stock solution to be less than 3mol/L, and extracting to obtain a loaded organic phase and raffinate; wherein the extraction stock solution is scandium-containing solution taking chloride ions as a main system, and the concentration of the chloride ions is more than or equal to 0.5mol/L; the extractant in the extracted organic phase adopts phosphate extractant;
Washing and back-extracting the loaded organic phase in sequence to obtain back-extraction liquid; wherein the acidity of the washing liquid is more than or equal to 6mol/L, and the acidity of the back extraction liquid is less than 6mol/L;
And (3) precipitating and calcining the strip liquor to obtain scandium oxide.
Optionally, the diluent is one or more of sulfonated kerosene, toluene, n-hexane, n-octanol, sec-octanol and isooctyl alcohol in the extracted organic phase, and the concentration of the phosphate extractant is 5-80%.
Optionally, in the step of extracting, the O/A ratio is 5:1-1:10, the reaction time is 10 s-30 min, and the reaction temperature is 5-100 ℃. Preferably, in the step of extraction, the reaction time is 2-15 min and the reaction temperature is 15-60 ℃ when the ratio of O/A is 3:1-1:5.
Optionally, the washing liquid is hydrochloric acid. Optionally, in the step of washing, the reaction time is 10 s-30 min and the reaction temperature is 5-100 ℃ when the ratio of O/A is 1:1-10:1. Preferably, in the step of back extraction, the reaction time is as follows: the reaction temperature is 5-100 ℃ within 10 s-30 min.
Optionally, the back extraction liquid is hydrochloric acid. Optionally, in the step of washing, the reaction time is 2-15 min and the reaction temperature is 15-60 ℃ when the ratio of O/A is 1:1-5:1. Preferably, in the back extraction step, the O/A ratio is 1:1-5:1, the reaction time is 2-15 min, and the reaction temperature is 15-60 ℃.
Preferably, in the step of precipitating, oxalic acid or ammonium bicarbonate is used.
Preferably, the extractant in the extracted organic phase is one or more compound extractants in neutral phosphorus extractant.
The beneficial effects are that: according to the method for preparing the ultra-high purity scandium oxide with low cost, acidity in extraction, washing and back extraction processes is optimized, the concentration of each ion in the extraction stock solution is regulated and controlled, and the extraction agent is selected, so that scandium extraction capacity and selectivity are improved; the back extraction is easier, and the back extraction by precipitation of strong alkali is not needed; the method can not introduce a large amount of organic impurities and can not cause the problem of cost increase caused by loss due to the introduction of a large amount of organic impurities; the technical problems of the two parts are avoided by subtracting the impurity removal and precipitation back extraction parts, and the process flow is simplified; solves a series of problems of high cost, low safety, high equipment requirement, complex process, difficult back extraction and the like of the traditional scandium oxide preparation method.
Drawings
FIG. 1 is a schematic flow chart of a process for producing ultra-high purity scandium oxide at low cost;
FIG. 2 is a graph showing the results of an H-spectrum nuclear magnetic test of a neutral phosphorus extractant employed in the examples;
FIG. 3 is the results of an infrared spectrum test of a neutral phosphorus extractant used in the examples.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
FIG. 1 schematically shows a flow of a method for preparing ultra-high purity scandium oxide at low cost according to the present invention, which comprises the steps of S10 adjusting an extraction stock solution, and extracting, as shown in FIG. 1; step S20, carrying out improved line washing and back extraction on the loaded organic phase; and step S30, precipitating and calcining the strip liquor. The invention provides a method for preparing ultra-high purity scandium oxide with low cost in an embodiment, which comprises the following steps:
1) Extraction water phase adjustment:
And regulating and controlling the concentration of each ion in the scandium-containing extraction stock solution. Wherein the water phase takes chloride ions as a main system, the concentration of the chloride ions is more than or equal to 0.5mol/L, the preferable range is 3mol/L to 9mol/L, the acidity in scandium chloride solution is increased to more than 6mol/L, and the preferable value is 6.5mol/L to 9mol/L. The concentration of nitrate ions is regulated to be less than or equal to 2mol/L, otherwise, the subsequent extraction and purification behavior is greatly influenced, and the scandium extraction and purification degree can be improved in the range. When the sulfate ion concentration is controlled to 3mol/L or less, scandium ion precipitation is likely to occur when the scandium ion concentration is high, and scandium loss is caused, so that the scandium loss can be avoided in this range.
2) Purifying and extracting:
Purifying and extracting to obtain a loaded organic phase and raffinate. Wherein the O/A ratio is 5:1-1:10, and the preferable range is 3:1-1:5. Reaction time: 10s to 30min, preferably in the range of 2min to 15min. Reaction temperature: 5-100 deg.c, preferably 15-60 deg.c.
In the extraction organic, the extractant adopts phosphate extractant, and the diluent is preferably adopted to dilute the extractant to 5-80% of concentration, and the extraction phase separation time in the range is within 15 min; more preferably to 5% to 70%, and the extraction phase separation time is within about 10 minutes, for example, at a concentration of not more than 60%, and generally within about 5 minutes. Wherein, the diluent can be sulfonated kerosene, toluene, n-hexane, n-octanol, sec-octanol, isooctanol and the like.
The phosphate extractant can be one or more of 2-ethylhexyl phosphate (P507), diisooctyl phosphate (P204), di (2, 4-trimethylpentyl) phosphate (Cyanex 272), tributyl phosphate (TBP), dimethylheptyl (P350), trialkyl phosphine oxide (TRPO), trioctyl phosphite, trioctyl phosphate (TOP), dibutyl phosphate (C 8H19O4 P), dibutyl phosphate (C 12H27O3 P), ENFI04 and the like.
Preferably, the phosphate extractant is a compound extractant compounded by one or more neutral phosphorus extractants. Wherein the structural formula of the neutral phosphorus extractant can be (RO) 3PO,(RO)2RPO,(RO)R2PO,R3 PO, wherein R is a hydrocarbon group; further, tributyl phosphate (TBP), dimethylheptyl (P350), trialkylphosphine oxide (TRPO) and ENFI may be selected, or may be selected from several of them, for example, TBP is compounded with P350, tributyl phosphate (TBP) is compounded with trialkylphosphine oxide (TRPO), ENFI may be used as main extractant to compound TBP, P350 and TRPO, or may be used alone as extractant, wherein ENFI04 may be 5% -70%, diluent may be selected as sulfonated kerosene or n-hexane, and other extractant may be 0-30%. The main extractant ENFI is a neutral phosphorus extractant which has a straight chain or branched chain structure with a carbon molecular number of 12-24 and a relative molecular mass of 300-450, wherein the neutral phosphorus extractant has a P=O functional group explicitly; the H spectrum nuclear magnetic test result (BRUKER nuclear magnetic analysis result) of ENFI is shown in figure 1, the infrared spectrum test result is shown in figure 2, and from figure 1, it can be seen that the neutral phosphorus extractant has several space structure types of H element; all other characteristic functional groups except the p=o functional group can be seen from fig. 2.
3) Loaded organic wash:
The organic phase obtained by extraction is washed with a detergent. Wherein the O/A ratio is 1:1-10:1, and the preferable range is 1:1-5:1. Reaction time: 10s to 30min, preferably in the range of 2min to 15min. Reaction temperature: 5-100 deg.c, preferably 15-60 deg.c. The aqueous phase adopts hydrochloric acid solution, the acidity is more than or equal to 6mol/L, and scandium and Cl - mainly exist in the form of ScCl 4 - complex anions.
4) Carrying out organic back extraction:
And back-extracting the washed organic phase by adopting a back-extracting agent. Wherein, the ratio of O/A is 1:1-10:1, and the preferable value is 1:1-5:1. Reaction time: 10s to 30min, preferably in the range of 2min to 15min. Reaction temperature: 5-100 deg.c, preferably 15-60 deg.c. The aqueous phase adopts a low-concentration hydrochloric acid solution, the acidity is less than 6mol/L, and scandium ions are changed to exist form, so that the scandium ions can be reversely extracted from the loaded organic.
5) Precipitation and calcination:
Precipitating the back extraction liquid by oxalic acid or ammonium bicarbonate, drying and calcining to obtain scandium oxide.
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1:
The embodiment mainly explores the extraction rate of scandium and other 16 kinds of rare earth by the composite extractant under the condition of different acidity. Extraction conditions: ENFI 04% strength 30%, TBP strength 10%, O/A ratio 1:1, reaction time 5min, room temperature. The acidity of the water phase is regulated by adopting analytically pure hydrochloric acid and pure water, and the water phase is filtered by a filter membrane with the diameter of 0.45 mu m after extraction is finished and then is subjected to sample feeding test. The washing back extraction step is not carried out.
The results of the extraction test are shown in table 1 below. It can be seen that the extraction conditions have excellent separation effect on scandium and other rare earth elements, and the separation effect of scandium and other rare earth elements after washing is better in the loaded organic phase, wherein the other rare earth elements are yttrium and 15 lanthanide rare earth elements.
TABLE 1 extraction results of scandium and other rare earth elements by composite extractants at different acidity
Example 2:
The embodiment mainly explores the extraction and separation effects of the composite extractant compounded by the neutral phosphorus extractant on scandium and impurities Ca, co, fe, mg, mn, ni, ti, zr, cr (III), na and Si. The extraction test is carried out for 5min under the condition of room temperature at the acidity of hydrochloric acid of 7.2 mol/L. Washing is carried out by hydrochloric acid with the acidity of 7.2mol/L, and the reaction is carried out for 5min at room temperature. The back extraction is carried out by hydrochloric acid with the acidity of 3mol/L, and the reaction is carried out for 5min at room temperature. The organic phase ENFI had a concentration of 30% and TRPO 10% and the test O/A phase ratios were 1:1.
The test results are shown in table 2 below. Therefore, the composite extractant has better separation effect on the impurity elements under the current condition. Certain impurities such as Co, mn, na and the like can be eluted in the washing section, so that the deep purification of scandium is realized.
Table 2 extraction and separation results of the composite extractant on common element impurities
| Element(s) | Stock solution mg/L | Raffinate mg/L | Washing liquor mg/L | Stripping solution mg/L |
| Sc g/L | 13.9 | 4.36 | 1.13 | 8.52 |
| Ca | 211 | 203 | 2.68 | 1.91 |
| Co | 267 | 174 | 77.9 | 3.4 |
| Fe | 5.3 | 1.03 | 0.79 | 1.87 |
| Mg | 61.4 | 59.2 | 0.72 | 0.46 |
| Mn | 504 | 475 | 19.6 | 0.5 |
| Ni | 278 | 272 | 1.09 | 0.11 |
| Ti | 2.18 | 2.22 | 0.13 | 0.69 |
| Zr | 1.46 | 0.45 | 0.17 | 0.28 |
| Cr(III) | 39.8 | 39.7 | 0.46 | 0.17 |
| Na | 393 | 391 | 8.6 | 4.23 |
| Si | 5.7 | 7.03 | 0.41 | 0.78 |
Example 3
The embodiment mainly explores the extraction and separation conditions of scandium and impurities by the composite extractant and the preparation of ultra-high purity scandium oxide (the absolute purity of the ultra-high purity scandium oxide is more than 4N) under the condition of certain acidity. The extraction conditions are that the concentration of P350 is 20%, the concentration of TBP is 20%, the O/A ratio is 1:1, the countercurrent extraction is carried out at room temperature for 6 stages, and the single-stage reaction time is 10min. The acidity of the aqueous phase of the extraction stock solution is 7.0mol/L, the scandium extraction rate is more than 99%, and the extraction rate of other impurities is less than 4%; adopting 6.5mol/L hydrochloric acid solution to carry out countercurrent washing for 4 stages at an O/A ratio of 3:1, wherein the impurity elution rate is more than 99%, and the scandium elution loss rate is less than 1%; the process is carried out by using 3mol/L hydrochloric acid at the O/A ratio of 3:1 and the countercurrent stripping stage number of 10, the stripping temperature is 60 ℃, and the scandium stripping rate is 100%. Precipitating by adopting ammonium bicarbonate after low-pressure evaporation deacidification; oxidizing and calcining for 4 hours at 800 ℃ to obtain high-purity scandium oxide, wherein the absolute purity of a sample is more than 4N 5.
Example 4:
The embodiment mainly explores the behavior of extracting scandium with ENFI to 04 different concentrations in the composite extractant, and the diluent is sulfonated kerosene. The extraction conditions are that the O/A phase ratio is 1:1, and the reaction is carried out for 5min at room temperature. The acidity of the extraction stock solution is 7mol/L, and the scandium initial concentration is 14.5g/L.
The extraction results are shown in table 3 below. The test results show that: when the concentration of the extractant is high, the extraction phase separation of scandium is affected, and the extraction phase separation time is prolonged. And ENFI04 can effectively replace the concentration of P350 without affecting the extraction behavior of P350.
TABLE 3 extraction behavior of scandium by ENFI04 at different concentrations
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (5)
1. A method for preparing ultra-high purity scandium oxide at low cost, comprising:
Adjusting the acidity of the extraction stock solution to be 6-9 mol/L, adjusting the concentration of nitrate ions in the extraction stock solution to be less than or equal to 2mol/L, adjusting the concentration of sulfate ions in the extraction stock solution to be less than 3mol/L, and extracting to obtain a loaded organic phase and raffinate; wherein the extraction stock solution is scandium-containing solution taking chloride ions as a main system, and the concentration of the chloride ions is more than or equal to 0.5mol/L; the extractant in the extracted organic phase adopts phosphate extractant; during extraction, the O/A ratio is 3:1-1:5, the reaction time is 2-15 min, and the reaction temperature is 15-60 ℃;
washing and back-extracting the loaded organic phase in sequence to obtain back-extraction liquid; wherein the washing liquid and the back extraction liquid are hydrochloric acid, the acidity of the washing liquid is more than or equal to 6mol/L, and the acidity of the back extraction liquid is less than 6mol/L and not less than 3mol/L; during washing, the ratio of O/A is 1:1-10:1, the reaction time is 10 s-30 min, and the reaction temperature is 5-100 ℃; during back extraction, the reaction time is that the ratio of O/A is 1:1-10:1: 10 s-30 min, and the reaction temperature is 5-100 ℃;
And (3) precipitating and calcining the strip liquor to obtain scandium oxide.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
In the washing step, the O/A ratio is 1:1-5:1, the reaction time is 2-15 min, and the reaction temperature is 15-60 ℃;
in the back extraction step, the O/A ratio is 1:1-5:1, the reaction time is 2-15 min, and the reaction temperature is 15-60 ℃.
3. The method according to claim 2, wherein the step of precipitating is performed using oxalic acid or ammonium bicarbonate.
4. The method according to claim 1, wherein the organic phase is extracted by using one or more of sulfonated kerosene, toluene, n-hexane, n-octanol, sec-octanol and isooctanol as the diluent, and the concentration of the phosphate extractant is 5-80%.
5. The method of claim 1, wherein the extractant in the extracted organic phase is a complex extractant compounded from one or more neutral phosphorus extractants.
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