CN111961872A - Method for extracting valuable elements in calcium-thermal vacuum reduction rare earth slag - Google Patents
Method for extracting valuable elements in calcium-thermal vacuum reduction rare earth slag Download PDFInfo
- Publication number
- CN111961872A CN111961872A CN202010813244.7A CN202010813244A CN111961872A CN 111961872 A CN111961872 A CN 111961872A CN 202010813244 A CN202010813244 A CN 202010813244A CN 111961872 A CN111961872 A CN 111961872A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- vacuum
- calcium
- slag
- valuable elements
- 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
- 239000002893 slag Substances 0.000 title claims abstract description 64
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 59
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000011575 calcium Substances 0.000 claims abstract description 61
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 51
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 43
- 239000011737 fluorine Substances 0.000 claims abstract description 43
- 238000002386 leaching Methods 0.000 claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 26
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 238000003916 acid precipitation Methods 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 7
- -1 rare earth fluoride Chemical class 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 40
- 239000000463 material Substances 0.000 description 30
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 30
- 229910052721 tungsten Inorganic materials 0.000 description 30
- 239000010937 tungsten Substances 0.000 description 30
- 238000003825 pressing Methods 0.000 description 29
- 238000001816 cooling Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 229910052688 Gadolinium Inorganic materials 0.000 description 13
- 229910052692 Dysprosium Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052689 Holmium Inorganic materials 0.000 description 10
- 229910052771 Terbium Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 10
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 10
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 229910052691 Erbium Inorganic materials 0.000 description 8
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 8
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 5
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 5
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 5
- 229940075613 gadolinium oxide Drugs 0.000 description 5
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 5
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 5
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910003451 terbium oxide Inorganic materials 0.000 description 5
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 description 2
- 229910001279 Dy alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 2
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 2
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
-
- 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
-
- 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
-
- 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
- C01F17/253—Halides
- C01F17/265—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for extracting valuable elements from calcium-thermal vacuum reduction rare-earth residues, which comprises the steps of uniformly mixing the calcium-thermal vacuum reduction rare-earth residues with lithium salt to obtain a mixture; and sequentially carrying out first-stage vacuum replacement and second-stage vacuum distillation on the obtained mixture to obtain the high-purity lithium fluoride. The invention adopts a vacuum replacement-vacuum distillation method to directly replace fluorine in the calcium thermal reduction rare earth slag with lithium salt to prepare lithium fluoride, and the distillation slag is subjected to leaching acid decomposition-extraction separation process to prepare rare earth fluoride or oxide, wherein the purity of the lithium fluoride is not lower than 99.9 percent, and the purity of the rare earth oxide is not lower than 99.5 percent, thereby realizing resource recovery of fluorine and rare earth elements in the calcium thermal reduction rare earth slag.
Description
Technical Field
The invention belongs to the technical field of rare earth residue resource recovery, and relates to a method for extracting valuable elements in calcium-thermal vacuum reduction rare earth residues, in particular to a method for extracting rare earth and fluorine in calcium-thermal vacuum reduction rare earth residues.
Background
The production of high melting point rare earth metal and low boiling point rare earth metal mainly adopts vacuum thermal reduction process. The low boiling point rare earth metals (such as Sm, Eu, Yb and Tm) are generally prepared by a vacuum lanthanum thermal reduction-distillation method, the generated slag consists of lanthanum oxide, a small amount of lanthanum metal, the prepared metal and oxides thereof, and the lanthanum oxide and the oxides of the prepared metal can be obtained by utilizing the existing separation process after the slag is dissolved in acid, so that the rare earth in the slag can be completely recovered. When producing high melting point rare earth metals (such as Gd, Tb, Dy, Ho, Er, Y, Lu metals, Tb-Dy alloys and the like), metallic calcium is generally adopted as a reducing agent, rare earth fluoride is adopted as a raw material, and the main component of the generated calcium thermal reduction slag is CaF2And 5-7% of rare earth (calculated as REO) remains.
The calcium thermal reduction slag is decomposed by using a leaching acid and extracted and separated process at presentLeaching and recovering rare earth accounting for 65.0 percent of the total amount of the rare earth in the reducing slag, wherein the residue still contains 2 to 3 percent of the rare earth, and the main reason is that the residue contains 34 percent of the rare earth in the slag and REF3Form exists, and REF3If the rare earth is to be recovered, other leaching agents are required to be selected, but most of calcium is dissolved out, even all of calcium is dissolved out, so that the recovery cost is greatly increased and is irretrievable; the leaching solution contains a large amount of calcium and high contents of iron, aluminum and silicon, and rare earth solution obtained after extraction and impurity removal can be used for preparing rare earth fluoride or rare earth oxide. Therefore, the recovery rate of the qualified rare earth prepared by recovering the rare earth from the calcium thermal reduction furnace slag is only 65.0 percent, and the fluorine in the slag is not comprehensively utilized. In order to further improve the comprehensive utilization rate of rare earth and fluorine, the development of an economic, simple-flow and environment-friendly 'green' metallurgical process is urgent.
Disclosure of Invention
Aiming at the defects of the existing technology for extracting valuable elements in the calcium-thermal vacuum reduction rare earth slag, the invention aims to provide a method for extracting valuable elements in the calcium-thermal vacuum reduction rare earth slag, which can effectively improve the recovery rate of the valuable elements and reduce the energy consumption and the production cost.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for extracting valuable elements from calcium-thermal vacuum reduction rare-earth residues comprises uniformly mixing calcium-thermal vacuum reduction rare-earth residues with lithium salt to obtain a mixture; and sequentially carrying out first-stage vacuum replacement and second-stage vacuum distillation on the obtained mixture to obtain the high-purity lithium fluoride.
The invention firstly adopts vacuum replacement to directly replace fluorine in the calcium thermal reduction rare earth slag by lithium salt to convert the fluorine into lithium fluoride, then vacuum distillation is carried out to evaporate the lithium fluoride to obtain high-purity lithium fluoride and residual distillation slag containing calcium oxide and rare earth oxide, and the distillation slag is further subjected to leaching acid decomposition-extraction separation process to prepare rare earth fluoride or oxide, thereby realizing resource recovery of fluorine and rare earth elements in the calcium thermal reduction rare earth slag, and the main process principle is as follows:
3Li2CO3+2REF3→6LiF+RE2O3+3CO2
Li2CO3+CaF2→2LiF+CaO+CO2
preferably, the addition amount of the lithium salt is 1.2-1.6 times of the theoretical calculated molar amount of fluorine in the calcium thermal vacuum reduction rare earth slag.
Preferably, the lithium salt is lithium carbonate.
Preferably, the mixture is firstly pressed, and the pressure is 5-10 Mpa.
Preferably, the conditions of the one-stage vacuum replacement are as follows: the temperature is 450-650 ℃, the vacuum degree is 10-15 Pa, and the time is 1-3 h.
Preferably, the conditions of the two-stage vacuum distillation are as follows: the temperature is 750-950 ℃, the vacuum degree is 30-40 Pa, and the time is 1-3 h.
Preferably, the distillation residue remained after the two-stage vacuum distillation is subjected to leaching acid decomposition, extraction separation, precipitation and firing processes in sequence to obtain the rare earth oxide.
Preferably, the distillation slag is subjected to counter-current leaching by adopting 3.0-6.0 mol/L HCl, leaching solution is extracted and separated by a P507-HCl system to obtain rare earth solution, and then the rare earth solution is precipitated by oxalic acid and then is calcined to prepare rare earth oxide.
The invention has the beneficial effects that:
(1) the invention adopts a vacuum replacement-vacuum distillation method to directly replace fluorine in the calcareous thermally reduced rare earth slag with lithium salt to prepare lithium fluoride, and the distilled slag is subjected to leaching acid decomposition-extraction separation process to prepare rare earth fluoride or oxide, wherein the purity of the lithium fluoride is not lower than 99.9 percent, and the purity of the rare earth oxide is not lower than 99.5 percent.
(2) The invention can obviously improve the yield of lithium, fluorine and rare earth, and the yield is not lower than 97.5 percent, 99.5 percent and 98.0 percent respectively.
(3) The raw materials of the invention contain high-value rare earth elements (such as Gd, Tb, Dy, Ho, Er, Lu metal, Tb-Dy alloy and the like), and the recovery rate of the rare earth elements can be improved from 65.00 percent to more than 98.00 percent by the invention.
(4) The inventionThe raw material contains solid waste CaF2The invention can prepare lithium fluoride with higher value than lithium carbonate, and fully utilize fluorine, thereby reducing pollution.
(5) The method has the advantages of low raw material cost, short process flow, simple equipment, strong operability, no secondary pollution and easy industrial scale production.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
FIGS. 2 to 4 show the results of detection of the lithium fluoride product obtained in example 3;
FIG. 5 shows the measurement results of the gadolinium oxide product obtained in example 1;
FIG. 6 shows the results of detecting terbium oxide product obtained in example 2;
FIG. 7 shows the results of measuring dysprosium oxide products obtained in example 3;
fig. 8 is a result of measurement of the holmium oxide product obtained in example 4;
fig. 9 shows the results of the detection of the erbium oxide product obtained in example 5.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be further described with reference to specific embodiments.
Example 1
Adding calcium thermal reduction gadolinium slag containing 6.51% of gadolinium, 48.51% of calcium and 44.91% of fluorine (calculated according to mass percentage) into a reactor, uniformly mixing the calcium thermal reduction gadolinium slag with lithium carbonate, wherein the addition amount of the lithium carbonate is 1.2 times of the theoretical calculated molar amount of the fluorine content in the calcium thermal vacuum reduction rare earth slag, putting the mixture into a material pressing mold for pressing, and controlling the pressure during material pressing to be 6Mpa to obtain a cake-shaped material; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 10 Pa; electrifying, heating to 450 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 35Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.94%; and taking the gadolinium slag out of the tungsten crucible, leaching the gadolinium slag by using 5.0mol/L HCl in a counter current manner, carrying out Ca/Gd separation on the leaching solution by using a P507-HCl system to obtain a gadolinium chloride solution, and preparing gadolinium oxide by oxalic acid precipitation and ignition, wherein the purity of the gadolinium oxide is 99.99% by analysis. The yields of lithium, fluorine and gadolinium obtained were calculated to be 98.61%, 99.58% and 98.59%, respectively.
Example 2
Adding calcium thermal reduction terbium slag containing 6.13 percent of terbium, 47.85 percent of calcium and 46.03 percent of fluorine (calculated by mass percentage) into a reactor, uniformly mixing with lithium carbonate, wherein the addition amount of the lithium carbonate is 1.2 times of the theoretical calculated molar amount of the fluorine content in the calcium thermal vacuum reduction rare earth slag, putting into a material pressing mold, and pressing, wherein the pressure during material pressing is controlled at 6 Mpa; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 10 Pa; electrifying, heating to 500 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 35Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.92%; then taking out the terbium slag in the tungsten crucible, carrying out countercurrent leaching by using 5.0mol/L HCl, carrying out Ca/Tb separation on leaching solution by using a P507-HCl system to obtain terbium chloride solution, and preparing terbium oxide by oxalic acid precipitation and ignition, wherein the purity of the terbium oxide is analyzed to be 99.99%. The yields of lithium, fluorine and terbium obtained by calculation were respectively 98.6%, 99.6% and 98.5%.
Example 3
Adding 5.82% of dysprosium, 48.68% of calcium and 45.41% of fluorine (by mass percent) calcium thermal reduction dysprosium slag and lithium salt into a reactor, uniformly mixing, wherein the addition amount of the lithium salt is 1.2 times of the theoretical calculated molar amount of the fluorine content in the calcium thermal vacuum reduction rare earth slag, putting into a material pressing mold, and pressing, wherein the pressure during material pressing is controlled at 6 Mpa; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 10 Pa; electrifying, heating to 550 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 35Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.95%; then taking the dysprosium slag out of the tungsten crucible, leaching the dysprosium slag by using 5.0mol/L HCl in a countercurrent way, carrying out Ca/Dy separation on the leaching solution by using a P507-HCl system to obtain a dysprosium chloride solution, and preparing dysprosium oxide by oxalic acid precipitation and ignition, wherein the purity of the dysprosium oxide is 99.6% by analysis. The yields of lithium, fluorine and dysprosium were calculated to be 98.56%, 99.59% and 98.64%, respectively.
Example 4
Adding 5.54% of holmium, 48.70% of calcium and 45.71% of fluorine (by mass percent) into a reactor, uniformly mixing the holmium through calcium thermal reduction and lithium salt, wherein the addition amount of the lithium salt is 1.2 times of the theoretical calculated molar amount of the fluorine content in the rare earth slag through calcium thermal vacuum reduction, putting the mixture into a material pressing mold, and pressing under the condition that the pressure is controlled at 6 MPa; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 10 Pa; electrifying, heating to 600 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 35Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.95%; and then taking out holmium slag in the tungsten crucible, carrying out countercurrent leaching by using 5.0mol/L HCl, carrying out Ca/Ho separation on leaching solution by using a P507-HCl system to obtain holmium chloride solution, and preparing holmium oxide by oxalic acid precipitation and ignition, wherein the analyzed purity of the holmium oxide is 99.9%. The calculated yields of lithium, fluorine and holmium are respectively 98.62%, 99.65% and 98.25%.
Example 5
Adding calcium thermal reduction erbium slag containing 6.25% of erbium, 47.96% of calcium and 45.60% of fluorine (calculated by mass percentage) into a reactor, uniformly mixing with lithium salt, wherein the addition amount of the lithium salt is 1.2 times of the theoretical calculated molar amount of the fluorine content in the calcium thermal vacuum reduction rare earth slag, putting into a material pressing mold, and pressing, wherein the pressure intensity during material pressing is controlled at 6 Mpa; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 10 Pa; electrifying, heating to 650 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 35Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.95%; and taking out erbium residues in the tungsten crucible, leaching the erbium residues in a countercurrent manner by using 5.0mol/L HCl, separating Ca/Er in leaching solution by using a P507-HCl system to obtain erbium chloride solution, and preparing erbium oxide by oxalic acid precipitation and ignition, wherein the purity of the erbium oxide is 99.99% by analysis. The calculated yields of lithium, fluorine and erbium were 98.62%, 99.65% and 98.25%, respectively.
Example 6
Adding calcium thermal reduction gadolinium slag containing 6.51% of gadolinium, 48.51% of calcium and 44.91% of fluorine (calculated by mass percentage) into a reactor, uniformly mixing with lithium salt, wherein the addition amount of the lithium salt is 1.4 times of the theoretical calculated molar amount of the fluorine content in the calcium thermal vacuum reduction rare earth slag, putting into a material pressing mold for pressing, and controlling the pressure during material pressing to be 8 Mpa; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 12 Pa; electrifying, heating to 450 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 40Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.94%; and taking the gadolinium slag out of the tungsten crucible, leaching the gadolinium slag by using 5.0mol/L HCl in a counter current manner, carrying out Ca/Gd separation on the leaching solution by using a P507-HCl system to obtain a gadolinium chloride solution, and preparing gadolinium oxide by oxalic acid precipitation and ignition, wherein the purity of the gadolinium oxide is 99.99% by analysis. The yields of lithium, fluorine and gadolinium obtained were calculated to be 97.65%, 99.62% and 98.61%, respectively.
Example 7
Adding calcium thermal reduction terbium slag containing 6.13 percent of terbium, 47.85 percent of calcium and 46.03 percent of fluorine (calculated by mass percentage) into a reactor, uniformly mixing with lithium salt, wherein the addition amount of the lithium salt is 1.4 times of the theoretical calculated molar amount of the fluorine content in the calcium thermal vacuum reduction rare earth slag, putting into a material pressing mold, and pressing, wherein the pressure during material pressing is controlled at 8 Mpa; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 12 Pa; electrifying, heating to 500 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 40Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.92%; then taking out the terbium slag in the tungsten crucible, carrying out countercurrent leaching by using 5.0mol/L HCl, carrying out Ca/Tb separation on leaching solution by using a P507-HCl system to obtain terbium chloride solution, and preparing terbium oxide by oxalic acid precipitation and ignition, wherein the purity of the terbium oxide is analyzed to be 99.99%. The yields of lithium, fluorine and terbium were calculated to be 97.61%, 99.63% and 98.57%, respectively.
Example 8
Adding 5.82% of dysprosium, 48.68% of calcium and 45.41% of fluorine (by mass percent) calcium thermal reduction dysprosium slag and lithium salt into a reactor, uniformly mixing, wherein the addition amount of the lithium salt is 1.4 times of the theoretical calculated molar amount of the fluorine content in the calcium thermal vacuum reduction rare earth slag, putting into a material pressing mold, and pressing, wherein the pressure during material pressing is controlled at 8 Mpa; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 12 Pa; electrifying, heating to 550 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 40Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.95%; then taking the dysprosium slag out of the tungsten crucible, leaching the dysprosium slag by using 5.0mol/L HCl in a countercurrent way, carrying out Ca/Dy separation on the leaching solution by using a P507-HCl system to obtain a dysprosium chloride solution, and preparing dysprosium oxide by oxalic acid precipitation and ignition, wherein the purity of the dysprosium oxide is 99.6% by analysis. The yields of lithium, fluorine and dysprosium were calculated to be 97.57%, 99.67% and 98.51%, respectively.
Example 9
Adding 5.54% of holmium, 48.70% of calcium and 45.71% of fluorine (by mass percent) into a reactor, uniformly mixing the holmium through calcium thermal reduction and lithium salt, wherein the addition amount of the lithium salt is 1.4 times of the theoretical calculated molar amount of the fluorine content in the rare earth slag through calcium thermal vacuum reduction, putting the mixture into a material pressing mold, and pressing under the condition that the pressure is controlled at 8Mpa during material pressing; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 12 Pa; electrifying, heating to 600 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 40Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.95%; and then taking out holmium slag in the tungsten crucible, carrying out countercurrent leaching by using 5.0mol/L HCl, carrying out Ca/Ho separation on leaching solution by using a P507-HCl system to obtain holmium chloride solution, and preparing holmium oxide by oxalic acid precipitation and ignition, wherein the analyzed purity of the holmium oxide is 99.9%. The calculated yields of lithium, fluorine and holmium are respectively 97.68%, 99.60% and 98.35%.
Example 10
Adding calcium thermal reduction erbium slag containing 6.25% of erbium, 47.96% of calcium and 45.60% of fluorine (calculated by mass percentage) into a reactor, uniformly mixing with lithium salt, wherein the addition amount of the lithium salt is 1.4 times of the theoretical calculated molar amount of the fluorine content in the calcium thermal vacuum reduction rare earth slag, putting into a material pressing mold, and pressing, wherein the pressure intensity during material pressing is controlled at 8 Mpa; putting the cake-shaped material into a tungsten crucible, then putting the tungsten crucible into a vacuum carbon tube furnace, vacuumizing the furnace, and controlling the vacuum degree to be 12 Pa; electrifying, heating to 650 ℃, controlling the vacuum degree to 15Pa, and keeping the temperature for 2 h; then heating to 800 ℃, controlling the vacuum degree to 40Pa, and keeping the temperature for 2 h; and after cooling for 2 hours, closing the large vacuum butterfly valve and the power supply of the vacuum gauge, closing other vacuum butterfly valves, finally filling Ar to-0.06 Mpa, cooling for 4 hours, and discharging. After the system is cooled in air, taking out a product in a nickel-grade Hardgrove collector, and analyzing that the purity of lithium fluoride is 99.95%; and taking out erbium residues in the tungsten crucible, leaching the erbium residues in a countercurrent manner by using 5.0mol/L HCl, separating Ca/Er in leaching solution by using a P507-HCl system to obtain erbium chloride solution, and preparing erbium oxide by oxalic acid precipitation and ignition, wherein the purity of the erbium oxide is 99.99% by analysis. The calculated yields of lithium, fluorine and erbium were 97.68%, 99.75% and 98.45%, respectively.
Claims (8)
1. A method for extracting valuable elements in calcium-thermal vacuum reduction rare earth slag is characterized by comprising the following steps: uniformly mixing the calcium-thermal vacuum reduction rare earth slag and the lithium salt to obtain a mixture; and sequentially carrying out first-stage vacuum replacement and second-stage vacuum distillation on the obtained mixture to obtain the high-purity lithium fluoride.
2. The method for extracting valuable elements from the hot calcium vacuum reduction rare earth slag according to claim 1, wherein the method comprises the following steps: the addition amount of the lithium salt is 1.2-1.6 times of the theoretical calculated molar amount of fluorine in the thermal vacuum reduction rare earth slag of calcium.
3. The method for extracting valuable elements from the hot calcium vacuum reduction rare earth slag according to claim 2, wherein the method comprises the following steps: the lithium salt is lithium carbonate.
4. The method for extracting valuable elements from the hot calcium vacuum reduction rare earth slag according to claim 1, wherein the method comprises the following steps: the mixture is pressed at first, and the pressure is 5-10 MPa.
5. The method for extracting valuable elements from the hot calcium vacuum reduction rare earth slag according to claim 1, wherein the method comprises the following steps: the conditions of the first-stage vacuum replacement are as follows: the temperature is 450-650 ℃, the vacuum degree is 10-15 Pa, and the time is 1-3 h.
6. The method for extracting valuable elements from the hot calcium vacuum reduction rare earth slag according to claim 1, wherein the method comprises the following steps: the conditions of the two-stage vacuum distillation are as follows: the temperature is 750-950 ℃, the vacuum degree is 30-40 Pa, and the time is 1-3 h.
7. The method for extracting valuable elements from the hot calcium vacuum reduction rare earth residues as claimed in any one of claims 1 to 6, wherein the method comprises the following steps: and (3) after the two-stage vacuum distillation, the distillation residues are remained, and the rare earth oxide is obtained by sequentially carrying out leaching acid decomposition, extraction separation, precipitation and firing processes.
8. The method for extracting valuable elements from the hot calcium vacuum reduction rare earth slag according to claim 7, wherein the method comprises the following steps: the distillation residues are subjected to counter-current leaching by adopting 3.0-6.0 mol/L HCl, leaching solution is subjected to extraction separation by a P507-HCl system to obtain rare earth solution, and then the rare earth solution is subjected to oxalic acid precipitation and then is burned to prepare rare earth oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010813244.7A CN111961872A (en) | 2020-08-13 | 2020-08-13 | Method for extracting valuable elements in calcium-thermal vacuum reduction rare earth slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010813244.7A CN111961872A (en) | 2020-08-13 | 2020-08-13 | Method for extracting valuable elements in calcium-thermal vacuum reduction rare earth slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111961872A true CN111961872A (en) | 2020-11-20 |
Family
ID=73365440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010813244.7A Pending CN111961872A (en) | 2020-08-13 | 2020-08-13 | Method for extracting valuable elements in calcium-thermal vacuum reduction rare earth slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111961872A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116287735A (en) * | 2022-09-09 | 2023-06-23 | 江苏金石稀土有限公司 | Recovery and Utilization of Rare Earth and Fluorine in Terbium Waste Slag Produced by Vacuum Calcitherm Reduction |
| CN116497241A (en) * | 2023-07-03 | 2023-07-28 | 赣州晨光稀土新材料有限公司 | A kind of recovery method of terbium element in terbium calcium slag |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519020A (en) * | 2020-05-08 | 2020-08-11 | 赣州有色冶金研究所 | Method for recovering valuable elements from rare earth electrolytic molten salt slag |
-
2020
- 2020-08-13 CN CN202010813244.7A patent/CN111961872A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519020A (en) * | 2020-05-08 | 2020-08-11 | 赣州有色冶金研究所 | Method for recovering valuable elements from rare earth electrolytic molten salt slag |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116287735A (en) * | 2022-09-09 | 2023-06-23 | 江苏金石稀土有限公司 | Recovery and Utilization of Rare Earth and Fluorine in Terbium Waste Slag Produced by Vacuum Calcitherm Reduction |
| CN116287735B (en) * | 2022-09-09 | 2025-06-20 | 江苏金石稀土有限公司 | Method for recovering rare earth and fluorine from waste residue of terbium produced by vacuum calcium thermal reduction method |
| CN116497241A (en) * | 2023-07-03 | 2023-07-28 | 赣州晨光稀土新材料有限公司 | A kind of recovery method of terbium element in terbium calcium slag |
| CN116497241B (en) * | 2023-07-03 | 2023-09-19 | 赣州晨光稀土新材料有限公司 | A method for recovering terbium element in terbium-calcium slag |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111519020B (en) | Method for recovering valuable elements from rare earth electrolytic molten salt slag | |
| CN101812599B (en) | Method for preparing metal magnesium by using dolomite as raw material | |
| CN111286653B (en) | A kind of method for producing magnesium-lithium alloy by vacuum aluminothermic reduction | |
| CN114132951B (en) | Method for extracting lithium from waste lithium battery black powder by pressure roasting and fluorine fixing | |
| US20220307108A1 (en) | Method for producing magnesium-lithium alloy by gaseous co-condensation method | |
| CN102644093A (en) | Method for producing metal aluminium by high-alumina fly ash chlorination electrolysis | |
| CN111961872A (en) | Method for extracting valuable elements in calcium-thermal vacuum reduction rare earth slag | |
| CN102643985A (en) | Method for extracting valuable metals from high-iron bauxite with step-by-step acid leaching | |
| US20220307107A1 (en) | Method for Preparing High-purity Metal Lithium by Vacuum Thermal Reduction Method | |
| CN105039724B (en) | Smelting furnace soot treatment method | |
| CN107739840A (en) | A kind of method of efficient-decomposition recovering rare earth electrolysis fused salt waste residue middle rare earth | |
| CN111187924A (en) | Device and method for continuously refining lithium from lithium-containing material | |
| Wulandari et al. | Magnesium: current and alternative production routes | |
| CN113149052B (en) | A kind of method for treating fluorine-containing waste electrolyte | |
| Chen et al. | Review of efficient recycling and resource utilization for rare earth molten salt electrolytic slag | |
| Yang et al. | REEs recovery from molten salt electrolytic slag: Challenges and opportunities for environmentally friendly techniques | |
| CN107523700A (en) | A kind of method that vacuum-thermal reduction William stone ore deposit prepares magnesium metal and byproduct | |
| CN111534701B (en) | Method for efficiently recovering valuable elements from rare earth molten salt electrolytic slag | |
| CN107805717A (en) | A kind of system and method that aluminium-scandium alloy is prepared using red mud | |
| CN105567973A (en) | Method for preparing ferro-nickel alloy and ferrotungsten-molybdenum alloy from waste material containing tungsten, molybdenum and nickel | |
| CN114538495A (en) | Method for extracting high-purity scandium oxide | |
| CN109207738B (en) | Treatment method of waste refractory material of aluminum electrolytic cell | |
| CN108516569B (en) | Method for preparing lithium sulfate solution by roasting lepidolite | |
| CN114990364B (en) | Method for recovering phosphorus and rare earth from rare earth-containing phosphorite | |
| Prentice et al. | Magsonic™ carbothermal technology compared with the electrolytic and Pidgeon Processes |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201120 |