CN1699609A - Process for preparing aluminium-scandium intermediate alloy from scandium-containing mineral by one-step method - Google Patents
Process for preparing aluminium-scandium intermediate alloy from scandium-containing mineral by one-step method Download PDFInfo
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- CN1699609A CN1699609A CNA200510010813XA CN200510010813A CN1699609A CN 1699609 A CN1699609 A CN 1699609A CN A200510010813X A CNA200510010813X A CN A200510010813XA CN 200510010813 A CN200510010813 A CN 200510010813A CN 1699609 A CN1699609 A CN 1699609A
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- chloride solution
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- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 149
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 70
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 52
- 239000011707 mineral Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000000956 alloy Substances 0.000 title claims description 68
- 229910045601 alloy Inorganic materials 0.000 title claims description 66
- -1 aluminium-scandium Chemical compound 0.000 title claims description 8
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims abstract description 82
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 19
- 230000005484 gravity Effects 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims description 58
- LUKDNTKUBVKBMZ-UHFFFAOYSA-N aluminum scandium Chemical compound [Al].[Sc] LUKDNTKUBVKBMZ-UHFFFAOYSA-N 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 239000012141 concentrate Substances 0.000 claims description 34
- 238000000926 separation method Methods 0.000 claims description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 20
- 239000006184 cosolvent Substances 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910018057 ScCl3 Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007885 magnetic separation Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 7
- 229910018134 Al-Mg Inorganic materials 0.000 abstract description 6
- 229910018467 Al—Mg Inorganic materials 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 229910001646 scandium mineral Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 35
- 229910000838 Al alloy Inorganic materials 0.000 description 23
- 238000011160 research Methods 0.000 description 16
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000542 Sc alloy Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- WTKQDILJIUYBGG-UHFFFAOYSA-N aluminum;magnesium;oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Sc+3] WTKQDILJIUYBGG-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001608 iron mineral Inorganic materials 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001773 titanium mineral Inorganic materials 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AHCSHBOAPHEPDO-UHFFFAOYSA-N diethyl octyl phosphate Chemical compound CCCCCCCCOP(=O)(OCC)OCC AHCSHBOAPHEPDO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to a technology of producing Al-Sc interalloy from scandium-containing mineral, belonging to the field of new material and its application. Based on the property of scandium-containing material and technological mineralogy, and according to the difference of characteristics between scandium- containing mineral and rocky mineral, a combined ore dressing process of gravity, magnetic and electric ore dressing is adopted to select fine Sc mineral, and then leaching, extracting and purifying are employed with hydrochloric acid plus assistant solvent, as a result, highly pure scandium chloride solution is obtained, which is used to prepare anhydrous scandium chloride salt. Finally, thermo-reduction of Al or Al-Mg is adopted for the reduction of scandium chloride solution to produce Al-Sc interalloy. The present process simplifies the preparation technology of Al-Sc interalloy considerably. There is no intermediate product process from the selection of scandium mineral to the preparation of Al-Sc interalloy. The technology has the advantages of low production cost, simple process, little environment pollution, high yield and stable quality.
Description
The technical field; the invention relates to a process method for preparing an aluminum-scandium master alloy from scandium-containing minerals, and belongs to the technical field of new materials and application.
Background art: scandium, like other rare earth elements, is a family of elements that can participate in the modification engineering of metal-based composites in the 21 st century as a "hope" in the case of well-established applications of traditional metal materials. At present, the application field of scandium relates to a plurality of high-tech fields such as alloy materials, electrothermal materials, laser materials, catalysts, glass additives, superconductors, medicine, chemical engineering, light sources, nuclear energy shielding and the like. The most demanding of the major fields of use of scandium products today is the use in aluminium-scandium alloys, where the annual demand for scandium is 1000 tons and is growing at a rate of 15% per year. The main reasons are: scandium is the most effective alloy element for optimizing the performance of aluminum alloy, and the aluminum alloy containing scandium has high strength, good plasticity, excellent welding performance, corrosion resistance and the like, and is a new generation of aluminum alloy excellent structural material in the fields of aerospace, ships, traffic, nuclear energy and the like, so scandium becomes a micro-alloying addition element of a novel aluminum alloy which is concerned by the international material community.
The earliest and most intensive countries for the study of scandium-containing aluminum alloys reported to be the former soviet union and the current russia, and they conducted a great deal of fundamental theoretical research and applied research work on the research of scandium-containing aluminum alloys. Four series of 14-grade industrial scandium-containing aluminum alloy systems have been developed, and all the developed scandium-containing aluminum alloys are obviously improved in strength, plasticity, welding performance, corrosion resistance and damage resistance compared with the scandium-free aluminum alloy systems. As for aluminum alloy, Russia is always in the leading position in the world, the research power is strong, the results are remarkable, and a complete industrial system from the production of raw scandium to the application of scandium-containing series products is formed. At present, research work for applying scandium-containing aluminum alloy materials to light automobile structural materials is being carried out in cooperation with various manufacturers. In addition, research work on aluminum alloys containing not only scandium has been carried out in countries such as the united states, japan, germany, and canada, and has achieved a great deal of results.
In China, the research on scandium-containing aluminum alloy starts late, and some researches are carried out in recent years, so that some progress is made. But still rely on imported aluminium-scandium master alloys to produce aluminium-scandium alloys. At present, the domestic market does not have the supply of aluminum-scandium master alloy, so that the research and application of scandium-containing aluminum alloy are greatly limited, and the development of the aluminum-scandium master alloy production process has very important significance for promoting the application and development of scandium-containing aluminum alloy in China and converting scandium resource advantages in China into economic benefits and technical advantages.
The melting point of scandium is much higher than that of aluminum, the melting point of scandium metal is as high as 1541 ℃, and the melting point of aluminum is only 660 ℃, so when preparing scandium-containing aluminum alloy, scandium must be added in the form of Al-Sc, Mg-Sc or Al-Mg-Sc intermediate alloy, therefore, the scandium intermediate alloy is prepared and contains enough time for temperature, and is cast into an iron mold or a water-cooling copper mold after being fully stirred, so that the scandium intermediate alloy can be prepared. The doping principle is simple, but the melting points of scandium and aluminum are greatly different (Al: 660 ℃, Sc: 1541 ℃), and an aluminum melt needs to be heated to a higher temperature, so that an intermediate alloy product with stable components and uniform distribution is difficult to prepare, and a large amount of scandium burning loss is difficult to avoid.
Metallothermic reduction: the metallothermic reduction method mainly includes a scandium oxide-aluminum magnesium thermal reduction method, a scandium fluoride vacuum aluminothermic reduction method and a scandium chloride-aluminum magnesium thermal reduction method.
(1) The scandium oxide-aluminum magnesium thermal reduction method is characterized in that powdery scandium oxide is used as a raw material, is mixed with active aluminum powder, is immersed in molten aluminum liquid after being prefabricated into small balls, the aluminum liquid is used as a reducing agent, the aluminum powder is used as a dispersing agent, scandium is reduced into metal scandium at high temperature, and the metal scandium enters the aluminum liquid to form an intermediate alloy.
(2) The scandium fluoride vacuum aluminothermic reduction method is a method in which scandium fluoride is used as a raw material, active aluminum powder is used as a reducing agent, and reduction reaction is performed under vacuum.
(3) The scandium chloride-aluminum magnesium thermal reduction method utilizes high-purity Sc2O3Is taken as a raw material and is dissolved and converted into ScCl-containing material by hydrochloric acid3The solution of (A) is evaporated, dehydrated in vacuum and heated at high temperature to become ScCl3The molten salt is put into molten aluminum-magnesium alloy liquid at the high temperature of 900 ℃, and then Sc-Cl is added3The metal magnesium is reduced into metal scandium, and the metal scandium is captured by aluminum to generate Al-Mg-Sc master alloy. The method is characterized in that ScCl is adopted3Has very high water absorbabilityStrong, and the difficulty of preparing anhydrous scandium chloride is large.
Molten salt electrolysis: the molten salt electrolysis method is carried out in an electrolytic cell, and the adopted molten salt system is ScCl3-NaCl-KCl、NaF-ScF3-Sc2O3、LiF-ScF3-Sc2O3、Na3AlF6-LiF-Sc2O3) The graphite electrode is an anode, the argon is used for protection, and the electrolysis temperature is 800-1000 ℃. Scandium is reduced to scandium at the anode. However, under the condition of high-temperature molten salt electrolysis, the corrosion of fluorine salt is serious, an electrolytic cell and an electrolytic material are easy to corrode and lose efficacy, in addition, molten aluminum may participate in electrode reaction under the condition of high-temperature molten salt electrolysis, and a cathode region and an anode region cannot be well isolated, so that the process has low current efficiency and large power consumption, and the problems need to be further researched and solved.
The extraction of scandium oxide and scandium metal needs to be carried out by the process flows of ore dressing, scandium concentrate leaching, extraction, back extraction, oxalic acid precipitation filtration, high-temperature ashing, metallurgy and the like, and the process flow is complex and has high production cost; in the doping method, the metallothermic reduction method, and the molten salt electrolysis method, scandium trioxide or scandium metal is generally dissolved with hydrochloric acid or the like, or scandium metal is added to a molten aluminum metal to prepare an aluminum-scandium master alloy. Therefore, the existing aluminum scandium preparation process needs a complex aluminum scandium intermediate alloy preparation process, so that the process is complex, the scandium yield is not high, the quality is unstable, and the environmental pollution is easily caused. The technology for directly preparing the aluminum-scandium master alloy from the scandium-containing ore in one step by adopting a set of complete process flow without preparing the scandium oxide or metal scandium in advance is not reported in documents.
The invention is provided; the invention aims to overcome the defects of the prior art and provide a process for preparing an aluminum-scandium master alloy from scandium-containing minerals by a one-step method, which has the advantages of no intermediate product, low production cost, high scandium yield and stable quality.
The technical scheme of the invention is as follows: the process for preparing the aluminum-scandium intermediate alloy from the scandium-containing minerals by the one-step method comprises the steps of directly preparing the aluminum-scandium intermediate alloy from the scandium-containing minerals, finding out the physical property difference between the scandium-containing minerals and gangue minerals from the research of the properties of the scandium-containing minerals and the process mineralogy, and separating scandium concentrate from the scandium-containing minerals by adopting a combined mineral separation process of gravity separation, magnetic separation and electric separation, wherein the scandium-containing minerals can be scandium carrier minerals such as ilmenite, zircon, spodumene, vanadium-titanium magnetite, bauxite, wolframite and the like; then, hydrochloric acid and a cosolvent are adopted to leach and extract scandium concentrate, a high-purity scandium chloride solution is obtained through purification, and then the high-purity scandium chloride solution is used for preparing anhydrous scandium chloride molten salt; and finally, reducing the scandium chloride molten salt by adopting an aluminum or aluminum-magnesium thermal reduction method to obtain the aluminum-scandium intermediate alloy.
The method comprises the steps of leaching and extracting scandium concentrate, wherein hydrochloric acid with the concentration of 20-25% and cosolvent ammonium fluoride are added according to the amount of 40-50 g/t at the temperature of 80-100 ℃, so that the scandium concentrate is subjected to leaching reaction, and solid-liquid separation is carried out; and extracting, separating and enriching scandium at normal temperature by adopting tributyl phosphate (TBP) or diethyloctyl phosphate (P204) to obtain a scandium chloride solution, and purifying by using a back extraction method to obtain the high-purity scandium chloride solution. Scandium metal is easily dissolved in acid, particularly hydrochloric acid, and a common compound scandium oxide occurring in nature is insoluble in dilute acid, but can be dissolved in high temperature and concentrated acid; the scandium separation and enrichment adopts an organic solvent extraction method, because the extraction method is more effective than a precipitation method and an ion exchange method under most conditions, and can be adopted at all stages of scandium extraction, the scandium separation and enrichment method has the characteristics of simple method, easiness in mastering, rapidness, good enrichment and separation effects, large processing capacity and the like.
The process for preparing the anhydrous scandium chloride molten salt comprises the steps of evaporating a scandium chloride solution, dehydrating in vacuum, and heating to 360-400 ℃ to obtain anhydrous ScCl3Melting a salt; the scandium chloride molten salt is required to be dehydrated completely so as to improve the actual yield, the quality and the crystal form integrity degree of scandium in the aluminum-scandium intermediate alloy process.
The process for preparing the aluminum-scandium intermediate alloy by aluminothermic or aluminomagnesiothermic reduction of the anhydrous scandium chloride molten salt comprises the step of carrying out ScCl treatment at the high temperature of 900-1000 DEG C3Molten salt is put into molten aluminum or aluminum-magnesium alloy liquid to lead Sc-Cl3Is reduced into scandium metal by magnesium metal and is captured by aluminum to obtain Al-Mg-a Sc master alloy. The reduction reaction formula is as follows:
(1) and (2) obtaining:
when the anhydrous scandium chloride molten salt is reduced by aluminothermic or aluminomagnesiothermic process to prepare the aluminum-scandium intermediate alloy, according to thermodynamic calculation of reduction reaction, under different temperatures, Gibbs free energy and equilibrium constant of reduction reaction of metals Na, Ca, Mg and Al and the anhydrous scandium chloride are obtained, wherein a relation curve calculation result of the equilibrium constant and the temperature shows that the metals Na, Ca and Mg can reduce scandium chloride, and because the prices of Na and Ca are high, the performances of aluminum alloy are adversely affected, and Mg is a main component of a plurality of aluminum alloys, Mg is used as a reducing agent to prepare the aluminum-scandium intermediate alloy. Al cannot reduce scandium chloride to metallic scandium, but can form a stable intermetallic compound with Sc.
The aluminum-scandium master alloy is prepared by a counter doping method, a metallothermic reduction method and a molten salt electrolysis method, and is generally prepared by dissolving scandium trioxide or metal scandium by hydrochloric acid and the like. However, the extraction of the scandium oxide and the metal scandium is obtained by leaching scandium-containing minerals with hydrochloric acid, extracting and purifying and smelting. It can be seen that the extraction of the scandium trioxide and the metal scandium and the preparation of the aluminum-scandium master alloy are necessary ways for the scandium chloride solution to appear. The invention adopts hydrochloric acid to leach scandium concentrate enriched by mineral dressing, obtains high-purity scandium chloride solution after extraction and purification, simultaneously prepares anhydrous scandium chloride molten salt, and then prepares the aluminum-scandium intermediate alloy by an aluminum or aluminum-magnesium thermal reduction method. The process greatly simplifies the process of preparing the aluminum-scandium intermediate alloy, and has no intermediate product process from the mineral dressing of scandium-containing minerals to the preparation of the aluminum-scandium intermediate alloy, so that the process is low in cost, simple in process, low in environmental pollution, high in scandium yield and stable in quality. The Sc 2% and Mg 15% aluminum-scandium master alloy obtained by the invention reaches the YS/T282-2000 aluminum-scandium master alloy ingot standard, and the actual yield of scandium is more than or equal to 90%.
Description of the drawings:
the attached drawing is a process flow chart of the invention.
The specific implementation mode is as follows: the invention is further illustrated by the following figures and examples.
Example 1: the silt at the tail of the Yangtze river Sanxia reservoir (Chongqing section) is a material which mainly comprises non-metallic minerals, is high in silicon and calcium and magnesium, contains certain iron and titanium minerals, contains trace rare earth yttrium and ytterbium and a rare dispersion element scandium, and contains 25.8g/t of yttrium, 2.06g/t of ytterbium and 6.60g/t of scandium.
The specific process for preparing the aluminum-scandium master alloy from the tail silt of the Yangtze river Sanxia reservoir by the one-step method comprises the following steps: firstly, from the research of the Yangtze river silt property and the process mineralogy, finding out the physical property difference of scandium-containing minerals and gangue minerals, and separating out scandium concentrate by adopting a combined mineral separation process of gravity separation, magnetic separation and electric separation; then, hydrochloric acid and a cosolvent (ammonium fluoride) are adopted to leach and extract the scandium concentrate, a high-purityscandium chloride solution is obtained through purification, and then the high-purity scandium chloride solution is used for preparing anhydrous scandium chloride molten salt; and finally, preparing the aluminum-scandium intermediate alloy by adopting a scandium chloride molten salt aluminum-magnesium thermal reduction method.
The technological steps of the leaching and the extraction of the scandium concentrate are that hydrochloric acid with the concentration of 25 percent and cosolvent ammonium fluoride are added according to the amount of 40g/t at the temperature of 95 ℃, so that the scandium concentrate generates leaching reaction, after solid-liquid separation, scandium is extracted, separated and enriched by adopting tributyl phosphate (TBP) organic solvent at normal temperature, scandium chloride solution is obtained, and then the high-purity scandium chloride solution is obtained after purification by a back extraction method.
The process for preparing the anhydrous scandium chloride molten salt comprises the steps of evaporating a high-purity scandium chloride solution, completely dehydrating in vacuum, and heating to 360 ℃ to obtain anhydrous ScCl3And (3) melting salt.
Preparation of aluminum-scandium intermediate alloy by aluminum-magnesium thermal reduction of anhydrous scandium chloride molten saltThe gold processing step is to mix ScCl at 950 ℃ high temperature3Molten salt is put into molten Al-Mg alloy liquid to make Sc-Cl3Reducing the metal magnesium into metal scandium and trapping the metal scandium by aluminum to obtain the Al-Mg-Sc master alloy. The reduction reaction formula is as follows:
example 2: the rare earth ore is mainly ilmenite and contains 18g/t of scandium.
The specific process for preparing the aluminum-scandium master alloy from the rare earth ore by the one-step method comprises the following steps: firstly, based on the research of the properties of the rare earth ore and the process mineralogy, finding out the physical property difference of scandium-containing minerals and gangue minerals, and separating out scandium concentrate by adopting a combined beneficiation flow of gravity separation, magnetic separation and electric separation; then, hydrochloric acid and a cosolvent (ammonium fluoride) are adopted to leach and extract the scandium concentrate, a high-purity scandium chloride solution is obtained through purification, and then the high-purity scandium chloride solution is used for preparing anhydrous scandium chloride molten salt; and finally, preparing the aluminum-scandium intermediate alloy by adopting a scandium chloride molten salt aluminothermic reduction method.
The technological steps of the leaching and the extraction of the scandium concentrate are that hydrochloric acid with the concentration of 20 percent and cosolvent ammonium fluoride are added according to the amount of 45g/t at the temperature of 90 ℃, so that the scandium concentrate generates leaching reaction, after solid-liquid separation, scandium is extracted, separated and enriched by adopting an organic solvent of dioctyl phosphate (P204) at normal temperature, scandium chloride solution is obtained, and then the high-purity scandium chloride solution is obtained after purification by a back extraction method.
The process for preparing the anhydrous scandium chloride molten salt comprises the steps of evaporating a scandium chloride solution, completely dehydrating in vacuum, and then heating to 380 ℃ to obtain anhydrous ScCl3And (3) melting salt.
The process for preparing the Al-Sc intermediate alloy by aluminothermic reduction of the anhydrous scandium chloride molten salt comprises the step of carrying out ScCl treatment at the high temperature of 900 DEG C3Molten salt is put into molten aluminum alloy liquid to enable Sc-Cl3Is reduced into scandium metal by magnesium metal and is collected by aluminum, and Al-Sc master alloy is obtained. The reduction reaction formula is as follows:
example 3: some is mainly bauxite, contains certain iron and titanium minerals and contains scandium 104 g/t.
The specific process for preparing the aluminum-scandium master alloy from the ore by the one-step method comprises the following steps: firstly, from the research of the mineral property and the process mineralogy, finding out the physical property difference of scandium-containing minerals and gangue minerals, and separating out scandium concentrate by adopting a combined mineral separation process of gravity separation, magnetic separation and electric separation; then, hydrochloric acid and a cosolvent (ammonium fluoride) are adopted to leach and extract the scandium concentrate, a high-purity scandium chloride solution is obtained through purification, and then the high-purity scandium chloride solution is used for preparing anhydrous scandium chloride molten salt; and finally, preparing the aluminum-scandium intermediate alloy by adopting a scandium chloride molten salt aluminum-magnesium thermal reduction method.
The technological steps of the leaching and the extraction of the scandium concentrate are that hydrochloric acid with the concentration of 23 percent and cosolvent ammonium fluoride are added according to the amount of 42g/t at the temperature of 80 ℃, so that the scandium concentrate generates leaching reaction, after solid-liquid separation, scandium is extracted, separated and enriched by adopting tributyl phosphate (TBP) organic solvent at normal temperature, scandium chloride solution is obtained, and then the high-purity scandium chloride solution is obtained after purification by a back extraction method.
The process for preparing the anhydrous scandium chloride molten salt comprises the steps of evaporating a scandium chloride solution, completely dehydrating in vacuum, and then heating to 400 ℃ to obtain anhydrous ScCl3And (3) melting salt.
The process for preparing the Al-Sc intermediate alloy by using the Al-Mg thermal reduction of the anhydrous scandium chloride molten salt comprises the step of carrying out ScCl treatment at the high temperature of 1000 DEG C3Molten salt is put into molten aluminum alloy liquid to enable Sc-Cl3Reducing the metal magnesium into metal scandium and trapping the metal scandium by aluminum to obtain the Al-Mg-Sc master alloy. The reduction reaction formula is as follows:
example 4: some of them mainly contain Tildite and contain 38g/t of scandium.
The specific process for preparing the aluminum-scandium master alloy from the ore by the one-step method comprises the following steps: firstly, from the research of the mineral property and process mineralogy, finding out the physical property difference of scandium-containing minerals and gangue minerals, and separating out scandium concentrate by adopting a combined mineral separation process of gravity separation, magnetic separation and electric separation; then, hydrochloric acid and a cosolvent (ammonium fluoride) are adopted to leach and extract the scandium concentrate, a high-purity scandium chloride solution is obtained through purification, and then the high-purity scandium chloride solution is used for preparing anhydrous scandium chloridemolten salt; and finally, preparing the aluminum-scandium intermediate alloy by adopting a scandium chloride molten salt aluminum-magnesium thermal reduction method.
The technological steps of the leaching and the extraction of the scandium concentrate are that hydrochloric acid with the concentration of 24 percent and cosolvent ammonium fluoride are added according to the amount of 50g/t at the temperature of 98 ℃, so that the scandium concentrate generates leaching reaction, after solid-liquid separation, scandium is extracted, separated and enriched by adopting an organic solvent of dioctyl phosphate (P204) at normal temperature, scandium chloride solution is obtained, and then the high-purity scandium chloride solution is obtained after purification by a back extraction method.
The process for preparing the anhydrous scandium chloride molten salt comprises the steps of evaporating a scandium chloride solution, completely dehydrating in vacuum, and heating to 375 ℃ to obtain anhydrous ScCl3And (3) melting salt.
The process for preparing the Al-Sc intermediate alloy by using the Al-Mg thermal reduction of the anhydrous scandium chloride molten salt comprises the step of carrying out ScCl treatment at the high temperature of 980 DEG C3Molten salt is put into molten aluminum alloy liquid to enable Sc-Cl3Reducing the metal magnesium into metal scandium and trapping the metal scandium by aluminum to obtain the Al-Mg-Sc master alloy. The reduction reaction formula is as follows:
example 5: certain iron zircon ore is taken as the main component and contains 26g/t of scandium.
The specific process for preparing the aluminum-scandium master alloy from the ore by the one-step method comprises the following steps:firstly, based on the research of the mineral property and process mineralogy, finding out the difference between the physical properties of a scandium-containing mineral and a gangue mineral, and separating out scandium concentrate by adopting a combined mineral separation process of gravity separation, magnetic separation and electric separation; then, hydrochloric acid and a cosolvent (ammonium fluoride) are adopted to leach and extract the scandium concentrate, a high-purity scandium chloride solution is obtained through purification, and then the high-purity scandium chloride solution is used for preparing anhydrous scandium chloride molten salt; and finally, preparing the aluminum-scandium intermediate alloy by adopting a scandium chloride molten salt aluminum-magnesium thermal reduction method.
The technological steps of the leaching and the extraction of the scandium concentrate are that hydrochloric acid with the concentration of 21 percent and cosolvent ammonium fluoride are added according to the amount of 48g/t at the temperature of 100 ℃, so that the scandium concentrate generates leaching reaction, after solid-liquid separation, scandium is extracted, separated and enriched by adopting a dioctyl phosphate organic solvent at normal temperature, scandium chloride solution is obtained, and then the high-purity scandium chloride solution is obtained after purification by a back extraction method.
The process for preparing the anhydrous scandium chloride molten salt comprises the steps of evaporating a scandium chloride solution, completely dehydrating in vacuum, and then heating to 370 ℃ to obtain anhydrous ScCl3And (3) melting salt.
The process for preparing the Al-Sc intermediate alloy by using the Al-Mg thermal reduction of the anhydrous scandium chloride molten salt comprises the step of carrying out ScCl treatment at the high temperature of 960 DEG C3Molten salt is put into molten aluminum alloy liquid to enable Sc-Cl3Reducing the metal magnesium into metal scandium and trapping the metal scandium by aluminum to obtain the Al-Mg-Sc master alloy. The reduction reaction formula is as follows:
example 6: some vanadium titano-magnetite ore is taken as the main material and contains 13g/t scandium.
The specific process for preparing the aluminum-scandium master alloy from the ore by the one-step method comprises the following steps: firstly, from the research of the mineral property and process mineralogy, finding out the physical property difference of scandium-containing minerals and gangue minerals, and separating out scandium concentrate by adopting a combined mineral separation process of gravity separation, magnetic separation and electric separation; then, hydrochloric acid and a cosolvent (ammonium fluoride) are adopted to leach and extract the scandium concentrate, a high-purity scandium chloride solution is obtained through purification, and then the high-purity scandium chloride solution is used for preparing anhydrous scandium chloride molten salt; and finally, preparing the aluminum-scandium intermediate alloy by adopting a scandium chloride molten salt aluminum-magnesium thermal reduction method.
The technological steps of the leaching and the extraction of the scandium concentrate are that hydrochloric acid with the concentration of 24 percent and cosolvent ammonium fluoride are added according to the amount of 46g/t at the temperature of 96 ℃, so that the scandium concentrate generates leaching reaction, after solid-liquid separation, scandium is extracted, separated and enriched by adopting tributyl phosphate organic solvent at normal temperature, scandium chloride solution is obtained, and then the high-purity scandium chloride solution is obtained after purification by a back extraction method.
The process for preparing anhydrous scandium chloride molten salt includes evaporating scandium chloride solution, vacuum dewatering, heating to 385 deg.CTo obtain anhydrous ScCl3And (3) melting salt.
The process for preparing the Al-Sc intermediate alloy by using the Al-Mg thermal reduction of the anhydrous scandium chloride molten salt comprises the step of carrying out ScCl treatment at the high temperature of 970 DEG C3Molten salt is put into molten aluminum alloy liquid to enable Sc-Cl3Reducing the metal magnesium into metal scandium and trapping the metal scandium by aluminum to obtain the Al-Mg-Sc master alloy. The reduction reaction formula is as follows: 。
Claims (6)
1. a process for preparing an aluminum-scandium master alloy from scandium-containing minerals by a one-step method is characterized in that the scandium-containing minerals are used for directly preparing the aluminum-scandium master alloy.
2. The process for preparing the aluminum-scandium master alloy from the scandium-containing minerals by the one-step method according to claim 1, wherein scandium concentrate is separated from the scandium-containing minerals by a combined beneficiation flow of gravity separation, magnetic separation and electric separation, then hydrochloric acid and a cosolvent are adopted to leach and extract the scandium concentrate, a high-purity scandium chloride solution is obtained through purification, and then the high-purity scandium chloride solution is used for preparing the anhydrous scandium chloride molten salt; and finally, reducing the scandium chloride molten salt by adopting an aluminum or aluminum-magnesium thermal reduction method to obtain the aluminum-scandium intermediate alloy.
3. The process of claim 1 or 2, wherein the scandium-containing mineral is a scandium-containing carrier mineral selected from the group consisting of ilmenite, zircon, titanpsidium, vanadium titanomagnetite, bauxite, wolframite, and the like.
4. The process for preparing an aluminum-scandium master alloy from scandium-containing minerals by the one-step method according to claim 2, wherein the leaching and extraction process steps of scandium concentrate are as follows: adding hydrochloric acid with the concentration of 20-25% and cosolvent ammonium fluoride with the concentration of 40-50 g/t at the temperature of 80-100 ℃, enabling scandium concentrate to generate leaching reaction, carrying out solid-liquid separation, then adopting tributyl phosphate or dioctyl phosphate organic solvent, carrying out extraction separation and scandium enrichment at normal temperature, obtaining scandium chloride solution, and purifying to obtain high-purity scandium chloride solution.
5. The process for preparing the aluminum-scandium master alloy from the scandium-containing mineral by the one-step method according to claim 2, wherein the process for preparing the anhydrous scandium chloride molten salt comprises the following steps: and (3) evaporating and vacuum dehydrating the scandium chloride solution, and then heating to 360-400 ℃ to obtain anhydrous ScCl3 molten salt.
6. The process for preparing the aluminum-scandium master alloy from the scandium-containing mineral by the one-step method according to claim 2, wherein the process for preparing the aluminum-scandium master alloy by reducing the anhydrous scandium chloride molten salt by aluminothermic or aluminomagnesiothermic reduction comprises the following steps: at the high temperature of 900-1000 ℃, ScCl is added3Molten salt is put into molten aluminum or aluminum-magnesium alloy liquid to lead Sc-Cl3Reducing the metal magnesium into metal scandium and trapping the metal scandium by aluminum to obtain the Al-Mg-Sc master alloy.
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