CN110616335A - Recovery device for recovering rare earth metal from rare earth metal slag and processing method - Google Patents
Recovery device for recovering rare earth metal from rare earth metal slag and processing method Download PDFInfo
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- CN110616335A CN110616335A CN201910956773.XA CN201910956773A CN110616335A CN 110616335 A CN110616335 A CN 110616335A CN 201910956773 A CN201910956773 A CN 201910956773A CN 110616335 A CN110616335 A CN 110616335A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 144
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 138
- 239000002893 slag Substances 0.000 title claims abstract description 65
- 238000011084 recovery Methods 0.000 title claims abstract description 19
- 238000003672 processing method Methods 0.000 title claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 89
- 239000002994 raw material Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 66
- 238000010298 pulverizing process Methods 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 53
- 230000008569 process Effects 0.000 claims abstract description 40
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims description 29
- 238000005868 electrolysis reaction Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 239000010937 tungsten Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims description 17
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 17
- 238000004064 recycling Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003801 milling Methods 0.000 claims description 15
- 230000007704 transition Effects 0.000 claims description 15
- 229910052772 Samarium Inorganic materials 0.000 claims description 13
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 11
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 11
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 11
- -1 rare earth fluoride Chemical class 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000005192 partition Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035939 shock Effects 0.000 claims description 3
- 241000237983 Trochidae Species 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 19
- 238000004821 distillation Methods 0.000 abstract description 9
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 19
- 238000000498 ball milling Methods 0.000 description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 4
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001954 samarium oxide Inorganic materials 0.000 description 3
- 229940075630 samarium oxide Drugs 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- RKLPWYXSIBFAJB-UHFFFAOYSA-N [Nd].[Pr] Chemical compound [Nd].[Pr] RKLPWYXSIBFAJB-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- ONLCZUHLGCEKRZ-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[La+3].[Ce+3] ONLCZUHLGCEKRZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KBLRIGLPGMRISA-UHFFFAOYSA-N neodymium(3+) oxygen(2-) praseodymium(3+) Chemical compound [O-2].[Pr+3].[Nd+3].[O-2].[O-2] KBLRIGLPGMRISA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a recovery device and a processing method for recovering rare earth metal from rare earth metal slag, wherein the recovery device comprises a raw material pulverization device, a calcination device and an electrolytic bath device, the processing method is to pulverize and calcine rare earth generated in the process of preparing high-purity rare earth by a reduction-distillation method into rare earth oxide powder, or to crush rare earth metal slag into powder by a direct crushing method, and then electrolyze the powder to obtain the rare earth metal2And a small amount of CO, has small environmental pollution, belongs to a green and environment-friendly process, and is suitable for large-scale production.
Description
Technical Field
The invention mainly relates to the technical field of rare earth purification, in particular to a recovery device and a processing method for recovering rare earth metal from rare earth metal slag.
Background
At present, the existing preparation method of high-purity rare earth metal mainly comprises a molten salt electrolysis method and a metal thermal reduction method, wherein the molten salt electrolysis method mainly prepares light rare earth metal or alloy such as lanthanum, cerium, praseodymium, neodymium, lanthanum cerium, praseodymium neodymium and the like; the metallothermic reduction method is subdivided into a calthermic reduction method and a lanthanum thermic reduction method (reduction-distillation method), wherein the calthermic reduction method is mainly used for preparing high-melting-point and high-boiling-point medium-heavy rare earth metals such as dysprosium, yttrium and scandium; while metals with larger vapor pressure such as samarium, europium, ytterbium, thulium and the like are prepared by thermal reduction of lanthanum or cerium or lanthanum and cerium.
The process of preparing high purity RE metal through thermal lanthanum reduction includes mixing metal lanthanum scraps and RE oxide in certain proportion, briquetting, and reducing in a vacuum carbon tube furnace to prepare RE metal. Taking the example of preparing metal samarium by lanthanum thermal reduction, the reaction equation is as follows: la + Sm2O3=Sm+La2O3In addition, the lanthanum slag is directly subjected to a wet process flow, namely lanthanum oxide and samarium oxide products are obtained through multi-stage extraction separation. However, the multi-stage extraction separation method has the disadvantages of complicated steps, large amount of acid and alkali liquor required in the process, great difficulty in treating three wastes, high cost, difficulty in further separation and treatment of the extracted products which are all mixed rare earth metal oxides, and low industrial utilization rate. At present, pure lanthanum oxide, cerium oxide, lanthanum cerium oxide, praseodymium oxide, neodymium oxide and praseodymium neodymium oxide are used as raw materials, a molten salt electrolysis method is adopted to prepare rare earth metals such as lanthanum, cerium, lanthanum cerium and the like, however, the method is difficult to adopt by using mixed rare earth oxides as raw materials, mainly because the rare earth oxides contain more metal elements and also contain different oxides such as samarium, europium, ytterbium and the like, and the oxides such as samarium, europium, ytterbium and the like are variable-valence rare earth metals, and because the electronic structures of + 2-valence ions of the oxides are kept or close to a half-full or full-full state, the stable electrolysis is difficult to be kept to be in a required rare earth metal state; on the other hand, the rare earth is required to be prepared into rare earth oxide before electrolysis, namely, the ball milling and oxidation processes are required, but the steps are complex, poor in continuity, poor in effect and safety, batch production cannot be realized in the preparation process, the labor cost input is large, the period is long, and the method is difficult to carry out in industryAnd (5) popularization and application.
In summary, there is no effective method for recovering rare earth metal slag generated during the preparation of high-purity rare earth by reduction-distillation.
Disclosure of Invention
The invention mainly provides a recovery device and a processing method for recovering rare earth metal from rare earth metal slag, which are used for solving the technical problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a recovery device for recovering rare earth metals from rare earth metal slag comprises a raw material pulverizing device, a calcining device and an electrolytic cell device, wherein supporting legs are welded at four top corners of the bottom of the raw material pulverizing device one by one, a supporting platform frame is welded at the bottoms of a plurality of supporting legs, a first airtight conveying device is connected to the bottom of the raw material pulverizing device in intervals of the supporting legs, the bottom of the first airtight conveying device is fixed on the top surface of the supporting platform frame through bolts, one end, far away from the raw material pulverizing device, of the first airtight conveying device is connected with an airtight transition pipeline, and the airtight transition pipeline is vertically downwards connected with the outer surface of the top of one end of the calcining device through bolts along the edge of the supporting platform frame;
the bottom outer wall of the calcining device is fixedly provided with a discharge bin through bolts, one side of the discharge bin is connected with a second airtight conveying device, the second airtight conveying device is far away from one end of the discharge bin is a slope and upwards extends to the top of the electrolytic cell device is connected with a protective top cover, and the bottom of the protective top cover is fixedly connected with a top shell of the electrolytic cell device through bolts.
Preferably, the inside of raw materials powdering device is the level and is provided with the broken roller set of skewed tooth, the one end of the broken roller set of skewed tooth runs through the lateral wall of raw materials powdering device extends to the external connection of raw materials powdering device has meshing gear train, just drive gear in the meshing gear train is kept away from the one end of raw materials powdering device is connected with first driving motor.
Preferably, the lower extreme of broken roller set of skewed tooth is equipped with ball-milling reducing mechanism, ball-milling reducing mechanism's inside is equipped with the spheroid of milling, be equipped with a plurality of hemisphere type lugs on the spheroidal outer wall of milling one by one, just the spheroidal horizontal center department of milling runs through and is equipped with the axis of rotation, the axis of rotation is close to first driving motor's one end runs through the lateral wall of raw materials powdering device extends to the external connection of raw materials powdering device has second driving motor.
Preferably, the raw material pulverizing device is welded with a fixing frame at one side close to the first driving motor and the second driving motor, the fixing frame is sequentially provided with two partition plates from top to bottom, and the first driving motor and the second driving motor are respectively fixed on the two partition plates from top to bottom through bolts.
Preferably, the raw materials powdering device is close to one side of calcining device runs through and is equipped with spray set, spray set is close to raw materials powdering device opening part passes through the bolt fastening, just spray set extends to through the pipe and keeps away from one side of mount is connected with the booster pump, the booster pump passes through the bolt fastening in the top of supporting platform frame is surperficial.
Preferably, a calcining silo is arranged in the calcining device, the bottom of the calcining silo is connected with the discharging bin, a stirring device is arranged in the calcining silo, one end, close to the supporting platform frame, of the stirring device sequentially penetrates through the calcining silo and the shell of the calcining device through a rotating shaft and extends to the bottom of the supporting platform frame, a third driving motor is connected to the bottom of the stirring device, and the bottom of the third driving motor is in contact with the ground through a plurality of shock pads.
Preferably, a plurality of power supply line pipe groups are arranged on the outer wall of the calcining device one by one from one end close to the closed transition pipeline to one end far away from the closed transition pipeline, the power supply line pipe groups penetrate through the shell of the calcining device and extend to the top of the calcining silo, and a nickel-chromium alloy heat conduction device is connected with the inner wall of the calcining device in a welded and fixed mode.
Preferably, the one end top of electrolysis trough device is connected with electrolyte feeding ooff valve, the electrolysis trough device is kept away from electrolyte feeding ooff valve's one end lateral wall below is connected with electrolyte and discharges the ooff valve, just the top of electrolysis trough device articulates there is airtight cell lid, airtight cell lid runs through one by one and is equipped with a plurality of exhaust holes.
Preferably, a graphite heat insulation layer is arranged on the inner wall of the electrolytic cell device, graphite anodes are arranged on two sides of the graphite heat insulation layer one by one, tungsten rod cathodes are arranged between the graphite anodes one by one, the tungsten rod cathodes and the graphite anodes are vertically arranged, a tungsten crucible is vertically arranged below the tungsten rod cathodes, and the bottom of the tungsten crucible is connected with the upper surface of the bottom of the graphite heat insulation layer.
The invention also provides a recycling processing method for recycling rare earth metal from rare earth metal slag, which is sequentially carried out according to the following steps:
s1, powder making process
Taking rare earth metal slag generated in the process of preparing high-purity rare earth by a distillation-thermal reduction method as a raw material, adding water into the rare earth metal slag for pulverization, calcining the rare earth metal slag into rare earth oxide powder at the high temperature of 800-1200 ℃, or directly crushing the raw material into 100-mesh-processed 300-mesh powder to obtain A;
the rare earth metal slag is one or a mixture of more of lanthanum, cerium, praseodymium, neodymium, samarium, europium or ytterbium;
the rare earth metal slag powder in the step is carried out by two modes: 1. adding water into the rare earth metal slag to pulverize the rare earth metal slag, and calcining the pulverized rare earth metal slag to prepare powder; 2. the rare earth metal slag is directly crushed into powder;
s2. molten salt electrolysis process
Electrolyzing the A in a fluoride molten salt electrolyte system to prepare rare earth metal; the fluoride in the fluoride molten salt electrolyte system is binary fluoride consisting of rare earth fluoride and lithium fluoride or multi-element fluoride consisting of rare earth fluoride, lithium fluoride and alkali metal fluoride;
the invention adopts fluoride system to melt salt electricityIn the decomposing technology, because the raw materials are not single rare earth metals (namely oxides of pure lanthanum, cerium, lanthanum-cerium, praseodymium, neodymium, praseodymium-neodymium and the like) and also contain various oxides of different samarium, europium, ytterbium and the like, the oxides of samarium, europium, ytterbium and the like are variable valence rare earth metals, and for the variable valence rare earth metals of samarium, europium and ytterbium, the electronic structure of +2 valence ions of the variable valence rare earth metals is kept or is close to a half-filled or full-filled state, namely Sm is kept or is close to a half-filled or full-filled state2+Ion (4f6), Tm2+Ion (4f6) and Yb2+Ions (4f7) are not only in +3 valence but also in +2 valence states, so that in the actual electrolysis process, the ions are not completely discharged at the cathode to become low-valence ions and then are oxidized to high-valence states, the cyclic oxidation-reduction reaction of the +3 valence and the +2 valence occurs, and the electrolysis current is consumed. Therefore, in production practice, the variable-valence rare earth metals can not be obtained basically by adopting the traditional molten salt electrolysis method, but the fluoride system molten salt electrolysis technology can better solve the problem, so that the variable-valence rare earth metals such as samarium, europium, ytterbium and the like can be better electrolyzed to form metal blocks with higher purity.
Compared with the prior art, the invention has the beneficial effects that:
the method comprises the steps of finely pulverizing or crushing rare earth metal slag by a raw material pulverizing device to form powder, conveying the powder into a calcining device in a dust-free closed manner by a first closed conveying device, calcining the rare earth metal slag powder into rare earth oxide powder by the calcining device, introducing the rare earth oxide powder into a second closed conveying device from a discharge bin at the bottom of the calcining device in a dust-free closed manner, conveying the powder into an electrolytic tank device, carrying out an electrolysis process in the electrolytic tank device, and preparing rare earth metal by using a fluoride electrolyte system as an electrolysis condition; the device is easy to disassemble and maintain, good in production continuity, short in preparation period, labor cost-saving, simple in whole process, easy to control, low in cost, good in continuity, stable in product components, low in energy consumption and convenient for resource recovery, and can recover mixed rare earth metal oxide into rare earth metal, and only CO is generated in the process2And a small amount of CO, has small environmental pollution, belongs to a green and environment-friendly process, and is suitable for large-scale production.
The present invention will be explained in detail below with reference to the drawings and specific embodiments.
Drawings
FIG. 1 is a flow chart of a process of the present invention;
FIG. 2 is a schematic view of the overall structure of the recycling apparatus of the present invention;
FIG. 3 is a sectional view showing the internal structure of the raw material pulverizing apparatus according to the present invention;
FIG. 4 is a sectional view showing the internal structure of the calcining apparatus of the present invention;
FIG. 5 is a sectional view showing the internal structure of the electrolytic cell apparatus of the present invention;
fig. 6 is an enlarged view of region a in fig. 1.
Description of the drawings: 1. a raw material pulverizing device; 1a, supporting legs; 11. an arc-shaped baffle plate; 11a, a through port; 12. a helical tooth crushing roller set; 12a, a meshing gear set; 121. a first drive motor; 13. a ball milling and crushing device; 13a, grinding the sphere; 13a-1, a hemispherical bump; 13a-2, a rotating shaft; 13b, a fixing piece; 131. a second drive motor; 14. a spraying device; 141. a booster pump; 15. a fixed mount; 15a, a partition plate; 16. a support platform frame; 17. a first closed conveying device; 17a, sealing a transition pipeline; 171. a first conveying motor; 2. a calcination device; 2a, calcining the silo; 21. a discharging bin; 21a, a discharge valve door plate; 21b, a connecting rod; 21c, a multi-fold movable rod; 21d, controlling the motor; 22. a power supply line tube group; 22a, a nickel-chromium alloy heat conducting device; 22b, a nickel-chromium alloy heat conducting rod; 23. an exhaust pipe; 24. a base; 25. a second closed conveying device; 25a, a support working frame; 25b, a protective top cover; 251. a second conveying motor; 26. a stirring device; 26a, stirring blades; 261. a third drive motor; 3. an electrolytic cell means; 31. an electrolyte feed on-off valve; 32. an electrolyte discharge switching valve; 33. a closed tank cover; 331. an exhaust hole; 34. a tungsten rod cathode; 35. a tungsten crucible; 36. a graphite anode; 37. graphite insulating layer.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described more fully hereinafter with reference to the accompanying drawings, in which the devices described in the following examples are known, unless otherwise specified, and in which methods and connections, if not otherwise specified, are known.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may be present, and when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present, as the terms "vertical", "horizontal", "left", "right" and the like are used herein for descriptive purposes only.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the knowledge of the terms used herein in the specification of the present invention is for the purpose of describing particular embodiments and is not intended to limit the present invention, and the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1 recovery device and processing method for recovering rare earth metal from rare earth metal slag
Referring to FIG. 2, this example is a recovery apparatus for recovering rare earth metals from rare earth metal slag, which comprises a raw material pulverizing apparatus 1, a calcining apparatus 2, and an electrolytic bath apparatus 3.
Raw material pulverizing device 1
Supporting legs 1a are welded at four top corners of the bottom of the raw material pulverizing device 1 one by one, supporting platform frames 16 are welded at the bottoms of a plurality of supporting legs 1a, and the bottom of the raw material pulverizing device 1 is positioned in the interval of a plurality of supporting legs 1a and is connected with a first closed conveying device 17, the bottom of the first capsule transferring device 17 is fixed to the top end surface of the supporting platform frame 16 by bolts, one end of the first closed conveying device 17 far away from the raw material pulverizing device 1 is connected with a closed transition pipeline 17a, a first conveying motor 171 is arranged outside one end of the first closed conveying device 17 close to the closed transition pipeline 17a, the first conveying motor 171 drives the conveying belt in the first closed conveying device 17 to convey, the closed transition pipeline 17a is vertically downwards connected with the outer surface of the top of one end of the calcining device 2 along the edge of the supporting platform frame 16 through bolts; there is a feed bin 21 through the bolt fastening on calcining device 2's the bottom outer wall, one side that goes out feed bin 21 is connected with second closed conveyor 25, second closed conveyor 25 keeps away from the one end that goes out feed bin 21 is the slope upwards to extend to electrolysis trough device 3's top is connected with protection overhead guard 25b, the bottom of second closed conveyor 25 slope conveying section has support work frame 25a through the bolt fastening, support work frame 25 a's bottom and ground contact, protection overhead guard 25 b's bottom pass through the bolt with electrolysis trough device 3's top casing fixed connection.
Specifically, please refer to fig. 3 and 6, the top of the raw material pulverizing device 1 is provided with an opening, the raw material pulverizing device 1 extends to the inside along the opening and is provided with an arc baffle 11, two ends of the arc baffle 11 are fixedly connected with the side walls of the two ends of the raw material pulverizing device 1 through bolts, and the center of the arc bottom of the arc baffle 11 is provided with a through opening 11a, the middle section in the raw material pulverizing device 1 is horizontally provided with a skewed tooth crushing roller group 12, the passing opening 11a is positioned right above the inclined tooth crushing roller group 12, one end of the inclined tooth crushing roller group 12 penetrates through the side wall of the raw material pulverizing device 1 and extends to the outside of the raw material pulverizing device 1 to be connected with a meshing gear group 12a, and one end of the driving gear in the meshing gear group 12a far away from the raw material pulverizing device 1 is connected with a first driving motor 121. In this embodiment, pour into through the top opening part with the rare earth metal sediment from raw materials atomizing device 1, through arc baffle 11's arrangement in drawing in, concentrate the rare earth metal sediment along the cambered surface to in passing through mouth 11a falls into broken roller set 12 of skewed tooth, and broken roller set 12 of skewed tooth is through the meshing of the meshing gear train 12a of external connection, it rotates to drive gear by first driving motor 121, make two rotor rolls on the broken roller set 12 of skewed tooth carry out opposite direction's rotation that rolls, and utilize the skewed tooth of a plurality of crisscross installations on two rotor rolls to roll crushing work, carry out preliminary broken pulverization with the rare earth metal sediment.
Specifically, referring to fig. 1 and 3 again, a ball mill crushing device 13 is disposed at the lower end of the skewed tooth crushing roller set 12, a milling sphere 13a is disposed inside the ball mill crushing device 13, a plurality of hemispherical protrusions 13a-1 are disposed on the outer wall of the milling sphere 13a one by one, a rotating shaft 13a-2 penetrates through the horizontal center of the milling sphere 13a, and one end of the rotating shaft 13a-2, which is close to the first driving motor 121, penetrates through the side wall of the raw material pulverizing device 1 and extends to the outside of the raw material pulverizing device 1 to be connected with a second driving motor 131. In this embodiment, a plurality of mountings 13b through the welded on the outer wall of ball-milling reducing mechanism 13 pass through the bolt fastening on the inner wall of raw materials powdering device 1, and the feedstock opening that ball-milling reducing mechanism 13's top set up is located the broken roller set 12 of skewed tooth under perpendicular, make the tombarthite metal sediment after preliminary crushing fall into ball-milling reducing mechanism 13, connect axis of rotation 13a-2 by outside second driving motor 131 and drive ball 13a of milling and grind the rotation in ball-milling reducing mechanism 13, a plurality of hemisphere type lugs 13a-1 that set up on ball 13a surface of milling simultaneously have played the meticulous effect of milling, carry out more detailed crushing formation powder to tombarthite metal sediment.
Specifically, please refer to fig. 2 and 6 again, a fixing frame 15 is welded on one side of the raw material pulverizing apparatus 1 close to the first driving motor 121 and the second driving motor 131, two partition plates 15a are sequentially arranged on the fixing frame 15 from top to bottom, and the first driving motor 121 and the second driving motor 131 are fixed on the two partition plates 15a from top to bottom through bolts respectively. In this embodiment, the fixing position and the fixing manner of the first driving motor 121 and the second driving motor 131 are realized by the installation of the fixing frame 15, so that the power transmission by the driving belt is reduced due to the position relationship, and the maximum power supply condition is provided for the helical tooth crushing roller set 12 and the ball mill crushing device 13 in the raw material pulverizing device 1.
Specifically, please refer to fig. 2 again, one side of the raw material pulverizing device 1 close to the calcining device 2 is provided with a spraying device 14 in a penetrating manner, the spraying device 14 is close to the opening of the raw material pulverizing device 1 and is fixed by bolts, the spraying device 14 extends to one side far away from the fixed frame 15 through a conduit and is connected with a booster pump 141, the booster pump 141 is externally connected with a water source, and the booster pump 141 is fixed on the top surface of the supporting platform frame 16 by bolts. In the embodiment, the water flow is pressurized and conveyed to the spraying device 14 through the booster pump 141, the rare earth metal slag entering the raw material pulverizing device 1 is sprayed, the spraying speed and the water quantity are controlled according to actual requirements, the process not only accelerates the pulverizing speed of the rare earth metal slag, so that the rare earth metal slag can be quickly oxidized, the later grinding and ball milling are convenient to reach the particle size of 100-plus-one 300 meshes, but also has the dust suppression effect, and the loss of the rare earth metal in the pulverizing process is reduced; meanwhile, the process can lead the rare earth metal slag to be quickly changed into oxide in the subsequent calcining process, thereby preparing for the later electrolysis process.
(II) calcining device 2
Referring to fig. 2 and 4, a calcining silo 2a is arranged inside the calcining device 2, the bottom of the calcining silo 2a is connected with the discharging bin 21, a stirring device 26 is arranged inside the calcining silo 2a, one end of the stirring device 26, which is close to the supporting platform frame 16, sequentially penetrates through the calcining silo 2a and the shell of the calcining device 2 through a rotating shaft and extends to the bottom of the supporting platform frame 16, and is connected with a third driving motor 261, and the bottom of the third driving motor 261 is in contact with the ground through a plurality of shock pads, so that noise and vibration in the stirring process are reduced. In the embodiment, two bases 24 fixed at the bottom of two ends of the calcining device 2 are contacted with the ground to form a support, and then the support is formed by a discharge valve plate 21a fitted on the bottom shell of the calcining silo 2a, the discharge valve plate 21a is made of high temperature resistant metal material, two ends of the bottom of the discharge valve plate 21a are symmetrically welded with connecting rods 21b, the bottoms of the two connecting rods 21b are rotatably connected with multi-fold movable rods 21c through ball bearings, one ends of the two multi-fold movable rods 21c far away from the two connecting rods 21b are connected with a control motor 21d, the two multi-fold movable rods 21c and the two connecting rods 21b are driven to generate displacement through the rotation of the two control motors 21d, so that the discharge valve plate 21a moves out in the bottom shell of the calcining silo 2a, and calcined powder containing rare earth oxide enters a horizontal conveying section installed in the discharge silo 21, meanwhile, in the calcining process, a rotating shaft in the stirring device 26 is driven by an external third driving motor 261, a plurality of stirring blades 26a arranged on the rotating shaft inside the calcining silo 2a are used for stirring the rare earth-containing powder, the stirring blades 26a are L-shaped, and the horizontal end part of the stirring blades is a tip end, so that the stirring disorder can be increased, rare earth metal can be punctured, the stirring blades penetrate into the material in the horizontal direction, the horizontal deep stirring is realized, the rapid and uniform heating of the material is ensured, the calcining speed and the oxidizing speed of the material are accelerated, and the heat gas during calcining is discharged into the atmosphere through an exhaust pipe 23.
Specifically, referring to fig. 2 and 4 again, power supply line pipe groups 22 are arranged on the outer wall of the calcining device 2 one by one from the end close to the sealed transition pipeline 17a to the end far from the sealed transition pipeline 17a, a plurality of power supply line pipe groups 22 extend to the top of the calcining silo 2a through the casing of the calcining device 2, and are connected with a nickel-chromium alloy heat conducting device 22a, and the nickel-chromium alloy heat conducting device 22a is welded and fixed with the inner wall of the calcining device 2. In this embodiment, the nickel-chromium alloy heat conducting device 22a inside the calcining device 2 is heated by the resistance principle through the protective power supply of the plurality of power supply line pipe groups 22, and then the heat is conducted into the calcining silo 2a through the nickel-chromium alloy heat conducting rod 22b, so that a heat source is provided for the calcining process of the rare earth metal.
(III) electrolytic tank device 3
Referring to the attached drawings 2 and 5, an electrolyte feeding switch valve 31 is connected to the top of one end of the electrolytic cell device 3, an electrolyte discharging switch valve 32 is connected to the lower portion of the side wall of one end of the electrolytic cell device 3 far away from the electrolyte feeding switch valve 31, a closed cell cover 33 is hinged to the top of the electrolytic cell device 3, a plurality of exhaust holes 331 are formed in the closed cell cover 33 in a penetrating mode one by one, a graphite heat insulation layer 37 is arranged on the inner wall of the electrolytic cell device 3, graphite anodes 36 are arranged on two sides of the graphite heat insulation layer 37 one by one, tungsten rod cathodes 34 are arranged among the graphite anodes 36 one by one, and a plurality of tungsten rod cathodes 34 are arranged between the graphiteThe graphite anodes 36 are vertically arranged, a tungsten crucible 35 is vertically arranged below the tungsten rod cathodes 34, and the bottom of the tungsten crucible 35 is connected with the upper surface of the bottom of the graphite heat insulation layer 37. In this embodiment, the second conveying motor 251 disposed on the side of the protective top cover 25b on the top of the electrolytic cell device 3 close to the electrolyte feeding switch valve 31 drives the slope section to convey, so as to send the rare earth oxide powder into the electrolytic cell device 3, and utilize the electrolyte feeding switch valve 31 to send the fluoride molten salt electrolyte liquid into the electrolytic cell device 3, and then tightly cover and seal the closed cell cover 33, so that the inside of the electrolytic cell device 3 forms a closed space, after continuously sending a certain amount of rare earth oxide powder, the set direct current is sent into the electrolytic cell device 3, each graphite anode 36 fixed on the two side walls of the electrolytic cell device 3 is used as an anode, each tungsten rod cathode 34 is used as a cathode, the top of a plurality of tungsten rod cathodes 34 is connected with the support plate, the two ends of the support plate are fixed on the two side walls of the electrolytic cell device 3 in a penetrating manner, during electrolysis, under the action of DC electric field, the positive ion Re in fluoride molten salt electrolyte3+Migrate to the cathode and the anion Cl-Or O-Then it moves to the anode and after the cations migrate to the cathode surface, it is mainly Re3+The electron is abstracted to rare earth metal atoms on the cathode, and the process is represented by Re3++3e → Re, after the anion has moved to the anode surface, e.g. Cl-The ions lose electrons at the anode and combine to form chlorine which is exhausted through a plurality of exhaust holes 331, while at the anode the oxygen ions lose electrons and are oxidized to CO2Or CO, CO2Or CO is discharged through a plurality of exhaust holes 331, rare earth ions on the cathode obtain electrons, the electrons are reduced into metal, the metal is collected in the tungsten crucible 35 below, and finally the original fluoride molten salt electrolyte liquid can be discharged by utilizing the electrolyte discharge switch valve 32, so that the regular replacement and supplement of the fluoride molten salt electrolyte liquid are facilitated.
This example also provides a method for recovering rare earth metals from rare earth metal slag using the recovery apparatus described in this example (in the step of processing method S1, the 1 st crushing mode uses the apparatus provided in this example, and the 2 nd crushing mode: crushing the raw material directly into powder, and the method does not use the apparatus of this example), and the specific flow chart can be referred to in FIG. 1, which is carried out in the following order:
s1, powder making process
Taking rare earth metal slag generated in the process of preparing high-purity rare earth by a distillation-thermal reduction method as a raw material, adding water into the rare earth metal slag for pulverization, calcining the pulverized rare earth metal slag into rare earth oxide powder at the high temperature of 800-1200 ℃ for 10-12h, or directly crushing the pulverized rare earth oxide powder into 100-mesh 300-mesh powder to obtain A;
the rare earth metal is one or a mixture of more of lanthanum, cerium, praseodymium, neodymium, samarium, europium or ytterbium;
s2. molten salt electrolysis process
Electrolyzing the A in a fluoride molten salt electrolyte system to prepare rare earth metal; the fluoride in the fluoride molten salt electrolyte system is binary fluoride composed of rare earth fluoride and lithium fluoride or multi-element fluoride composed of rare earth fluoride, lithium fluoride and alkali metal fluoride.
The preparation of the raw material into powder in the step S1 is performed in two ways:
1. the pulverization-calcination procedure was as follows: carrying out coarse crushing (artificial crushing) on rare earth metal slag generated in the process of preparing high-purity rare earth by a reduction-distillation method, then putting the crushed slag into a raw material pulverizing device 1, sequentially carrying out water spraying, grinding and ball milling to pulverize the crushed slag to obtain powder containing rare earth, then sending the powder containing rare earth into a calcining device 2, and calcining the powder containing rare earth; in the step, the rare earth metal slag is firstly added with water so as to pulverize the massive materials to be beneficial to later-stage grinding and ball milling, simultaneously, the rare earth metal particles in the materials are quickly oxidized and then calcined, the calcination can ensure that the rare earth metal-containing powder is quickly and thoroughly oxidized, the pulverization-calcination effect is better than that of direct crushing (ball milling by a ball mill), the energy consumption is low, the production cost is low, and the rare earth oxide materials suitable for next-stage electrolysis can be obtained.
2. The direct crushing process is as follows: the rare earth metal slag is crushed into powder by a ball mill or a crusher under the conditions that the ball-material ratio is 120:1, the rotating speed is 400 rpm, the ball milling time is 25 min and the intermittence time is 5 min.
Example 2 recovery processing method for recovering rare earth metals from rare earth metal slag
Rare earth metal slag (components shown in the table) generated in the process of preparing samarium metal by a reduction-distillation method is put into a raw material pulverizing device 1, water is added for pulverization, and the powder is calcined for 10 hours at 1000 ℃ in a calcining device 2 to obtain 100-mesh and 300-mesh powder mainly containing lanthanum oxide and samarium oxide; the powder is electrolyzed in an electrolytic cell apparatus 3. Electrolyte proportions were lanthanum fluoride: lithium fluoride: calcium fluoride = 5: 1: 0.3 (weight ratio), the electrolytic current intensity is 3800A, and the cathode current density is 9A/cm2The current density of the anode is 1.5A/cm2Electrolyzing at 1000 +/-50 deg.c for 24 hr to obtain 105kg of lanthanum metal.
(mass%)
Example 3A recovery processing method for recovering rare earth metals from rare earth metal slag
Rare earth metal slag (components shown in the table) generated in the process of preparing samarium metal by a reduction-distillation method is put into a raw material pulverizing device 1, added with water for pulverization, and then put into a calcining device 2 for calcining for 11 hours at 1000 ℃ to obtain 100-mesh and 300-mesh powder mainly containing lanthanum oxide and samarium oxide; the powder is electrolyzed in an electrolytic cell apparatus 3. Electrolyte proportions were lanthanum fluoride: lithium fluoride: barium fluoride = 4: 1: 0.2 (weight ratio), the electrolytic current intensity is 3600A, and the cathode current density is 9A/cm2The current density of the anode is 1.5A/cm2Electrolyzing at 1000 +/-50 deg.c for 24 hr to obtain 97kg of metal lanthanum.
(mass%)
Example 4A recovery processing method for recovering rare earth metals from rare earth metal slag
Putting rare earth metal slag (components shown in the table) generated in the process of preparing the metal ytterbium by a reduction-distillation method into a raw material pulverizing device 1, adding water for pulverization, and then putting the raw material pulverizing device into a calcining device 2 for calcining for 12 hours at 1200 ℃ to obtain 100-mesh 300-mesh powder mainly containing lanthanum oxide and ytterbium oxide; the powder is electrolyzed in an electrolytic cell apparatus 3. Electrolyte proportions were lanthanum fluoride: lithium fluoride = 5: 1 (weight ratio), the electrolytic current intensity is 3500A, and the cathode current density is 8.5A/cm2The current density of the anode is 1.5A/cm2And electrolyzing for 24 hours at the electrolysis temperature of 1000 +/-50 ℃ to obtain 112kg of metal lanthanum.
(mass%)
Example 5A recovery processing method for recovering rare earth metals from rare earth metal slag
Putting rare earth metal slag (the components are shown in the table) generated in the process of preparing europium metal by a reduction-distillation method into a raw material pulverizing device 1, adding water for pulverization, and then calcining for 10 hours at 800 ℃ in a calcining device 2 to obtain 100-mesh 300-mesh powder mainly containing lanthanum oxide and europium oxide; the powder is electrolyzed in an electrolytic cell apparatus 3. Electrolyte proportions were lanthanum fluoride: lithium fluoride = 5.5: 1 (weight ratio), the electrolytic current intensity is 5400A, and the cathode current density is 8.2A/cm2The current density of the anode is 1.3A/cm2Electrolyzing at 1000 +/-50 deg.c for 24 hr to obtain metallic lanthanum in 193 kg.
(mass%)
The working process is as follows:
the specific process of rare earth metal recovery of rare earth metal slag in the apparatus provided in embodiment 1 of the present invention is as follows:
firstly, rare earth metal waste slag generated in the process of preparing high-purity rare earth by a reduction-distillation method is put into a raw material pulverizing device 1, the rare earth metal slag is concentrated into a through hole 11a along an arc surface and falls into a skewed tooth crushing roller group 12 through furling and sorting of an arc baffle plate 11, the skewed tooth crushing roller group 12 is meshed through a meshing gear group 12a connected with the outside, a driving gear is driven by a first driving motor 121 to rotate, two rotating rollers on the skewed tooth crushing roller group 12 are driven to rotate in opposite directions, a plurality of skewed teeth arranged on the two rotating rollers in a staggered mode are used for rolling and crushing, the rare earth metal slag is subjected to primary crushing and pulverizing, in the process, a spraying device 14 can spray fine water mist, on one hand, dust can be suppressed, on the other hand, oxidation and pulverizing of the rare earth metal slag can be accelerated, and certainly, in the process of spraying the fine water mist, the water spraying speed is matched with the feeding and crushing speed, so that the rare earth metal slag can not drip a large amount of water, and the resource waste is avoided. Then the primarily crushed rare earth metal slag falls into a ball milling and crushing device 13, an external second driving motor 131 is connected with a rotating shaft 13a-2 to drive a milling sphere 13a to mill and rotate in the ball milling and crushing device 13, meanwhile, a plurality of hemispherical bumps 13a-1 arranged on the outer surface of the milling sphere 13a have a fine milling effect, the rare earth metal slag is more finely crushed to form rare earth-containing powder, the rare earth-containing powder is conveyed to a closed transition pipeline 17a by a first closed conveying device 17 to enter a calcining silo 2a in the calcining device 2, the rare earth-containing powder is subjected to protective power supply by a plurality of power supply pipeline groups 22, a nickel-chromium alloy heat conduction device 22a in the calcining device 2 is subjected to resistance principle heating, and heat is conducted to the calcining silo 2a by a nickel-chromium alloy heat conduction rod 22b to be subjected to rare earth-containing powder calcining work, in the calcining process, a rotating shaft in the stirring device 26 is used for driving through an external third driving motor 261, a plurality of stirring blades 26a arranged on the rotating shaft inside the calcining silo 2a are used for stirring the powder containing the rare earth, the heating uniformity is kept, the calcining speed is accelerated, the heat gas during calcining is discharged into the atmosphere through an exhaust pipe 23, the pulverized rare earth metal powder is rapidly and thoroughly oxidized into the rare earth metal powder, after the calcining is finished, the powder containing the rare earth oxide is moved by a discharge valve plate 21a at the bottom of the calcining silo 2a through two connecting rods 21b, two multi-fold movable rods 21c and two control motors 21d, so that the calcined powder containing the rare earth oxide enters a horizontal conveying section arranged in a discharge bin 21, and then the horizontal conveying section and a slope section are driven by a second conveying motor 251, the powder containing rare earth oxide is sent into an electrolytic bath device 3 for corresponding electrolysis, and finally, corresponding rare earth metal is prepared.
The invention has been described above with reference to the accompanying drawings, it is obvious that the invention is not limited to the specific implementation in the above-described manner, and it is within the scope of the invention to adopt such insubstantial modifications of the inventive concept and solution, or to apply the inventive concept and solution directly to other applications without such modifications.
Claims (10)
1. The utility model provides a retrieve recovery unit of rare earth metal in follow rare earth metal sediment, includes raw materials powdering device (1), calcining device (2), electrolysis trough device (3), its characterized in that, four apex angle departments in bottom of raw materials powdering device (1) weld one by one and have supporting leg (1 a), a plurality of the bottom welding of supporting leg (1 a) has supporting platform frame (16), just the bottom of raw materials powdering device (1) is located a plurality of the interval in-connection of supporting leg (1 a) has first airtight conveyor (17), the bottom of first airtight conveyor (17) is through bolted fixation in the top of supporting platform frame (16) is surperficial, first airtight conveyor (17) are kept away from the one end of raw materials powdering device (1) is connected with airtight transition pipeline (17 a), airtight transition pipeline (17 a) are followed the border of supporting platform frame (16) perpendicularly downwards with the one end of calcining device (2) The outer surface of the top part is fixedly connected through a bolt;
the bottom outer wall of the calcining device (2) is fixedly provided with a discharge bin (21) through bolts, one side of the discharge bin (21) is connected with a second airtight conveying device (25), the second airtight conveying device (25) is kept away from one end of the discharge bin (21) is slope and upwards extends to the top of the electrolytic tank device (3) is connected with a protective top cover (25 b), and the bottom of the protective top cover (25 b) is fixedly connected with the top shell of the electrolytic tank device (3) through bolts.
2. The recycling device for recycling rare earth metals from rare earth metal slag according to claim 1, characterized in that the inside of the raw material pulverizing device (1) is horizontally provided with a skewed tooth crushing roller set (12), one end of the skewed tooth crushing roller set (12) extends through the side wall of the raw material pulverizing device (1) to the outside of the raw material pulverizing device (1) to be connected with a meshing gear set (12 a), and one end of a driving gear in the meshing gear set (12 a) far away from the raw material pulverizing device (1) is connected with a first driving motor (121).
3. The recovery device for recovering rare earth metals from rare earth metal slag according to claim 2, wherein a ball mill crushing device (13) is arranged at the lower end of the skewed tooth crushing roller set (12), a milling sphere (13 a) is arranged inside the ball mill crushing device (13), a plurality of hemispherical convex blocks (13 a-1) are arranged on the outer wall of the milling sphere (13 a) one by one, a rotating shaft (13 a-2) penetrates through the horizontal center of the milling sphere (13 a), and one end of the rotating shaft (13 a-2) close to the first driving motor (121) penetrates through the side wall of the raw material pulverizing device (1) and extends to the outside of the raw material pulverizing device (1) to be connected with a second driving motor (131).
4. The recycling apparatus for recycling rare earth metals from rare earth metal slag according to claim 2, wherein a fixed frame (15) is welded on one side of the raw material pulverizing apparatus (1) close to the first driving motor (121) and the second driving motor (131), two partition plates (15 a) are sequentially arranged on the fixed frame (15) from top to bottom, and the first driving motor (121) and the second driving motor (131) are respectively fixed on the two partition plates (15 a) from top to bottom through bolts.
5. The recycling apparatus for recycling rare earth metals from rare earth metal slag according to claim 4, wherein a spraying device (14) is penetratingly disposed at one side of the raw material pulverizing device (1) close to the calcining device (2), the spraying device (14) is fixed by bolts at the position close to the opening of the raw material pulverizing device (1), and the spraying device (14) is connected with a booster pump (141) by a pipe extending to the side far away from the fixing frame (15), and the booster pump (141) is fixed on the top surface of the supporting platform frame (16) by bolts.
6. The recycling device for recycling rare earth metals from rare earth metal slag according to claim 1, wherein a calcination silo (2 a) is arranged inside the calcination device (2), the bottom of the calcination silo (2 a) is connected with the discharge bin (21), a stirring device (26) is arranged inside the calcination silo (2 a), one end of the stirring device (26) close to the supporting platform frame (16) sequentially penetrates through the shells of the calcination silo (2 a) and the calcination device (2) through a rotating shaft and extends to the bottom of the supporting platform frame (16) to be connected with a third driving motor (261), and the bottom of the third driving motor (261) is in contact with the ground through a plurality of shock pads.
7. The recycling device for recycling rare earth metals from rare earth metal slag according to claim 6, wherein a plurality of power supply line pipe groups (22) are arranged on the outer wall of the calcining device (2) one by one from the end close to the closed transition pipeline (17 a) to the end far away from the closed transition pipeline (17 a), each of the plurality of power supply line pipe groups (22) penetrates through the shell of the calcining device (2) and extends to the top of the calcining silo (2 a) to be connected with a nickel-chromium alloy heat conducting device (22 a), and the nickel-chromium alloy heat conducting device (22 a) is welded and fixed with the inner wall of the calcining device (2).
8. The recycling device for recycling rare earth metals from rare earth metal slag according to claim 1, characterized in that an electrolyte feeding switch valve (31) is connected to the top of one end of the electrolytic cell device (3), an electrolyte discharging switch valve (32) is connected to the lower portion of the side wall of one end of the electrolytic cell device (3) far away from the electrolyte feeding switch valve (31), a closed cell cover (33) is hinged to the top of the electrolytic cell device (3), and a plurality of exhaust holes (331) are arranged through the closed cell cover (33) one by one.
9. The recycling device for recycling rare earth metals from rare earth metal slag according to claim 8, wherein a graphite heat insulating layer (37) is provided on the inner wall of the electrolytic cell device (3), graphite anodes (36) are provided one by one on both sides of the graphite heat insulating layer (37), tungsten rod cathodes (34) are provided one by one between the graphite anodes (36), the tungsten rod cathodes (34) and the graphite anodes (36) are vertically provided, a tungsten crucible (35) is provided under the tungsten rod cathodes (34), and the bottom of the tungsten crucible (35) is connected with the upper surface of the bottom of the graphite heat insulating layer (37).
10. A recovery processing method for recovering rare earth metals from rare earth metal slag is characterized by sequentially carrying out the following steps:
s1, powder making process
Taking rare earth metal slag generated in the process of preparing high-purity rare earth by a distillation-thermal reduction method as a raw material, adding water into the rare earth metal slag for pulverization, calcining the rare earth metal slag into rare earth oxide powder at the high temperature of 800-1200 ℃, or directly crushing the raw material into powder with the particle size of below 100-300 meshes to obtain A;
the rare earth metal slag is one or a mixture of more of lanthanum, cerium, praseodymium, neodymium, samarium, europium or ytterbium;
s2. molten salt electrolysis process
Electrolyzing the A in a fluoride molten salt electrolyte system to prepare rare earth metal; the fluoride in the fluoride molten salt electrolyte system is binary fluoride composed of rare earth fluoride and lithium fluoride or multi-element fluoride composed of rare earth fluoride, lithium fluoride and alkali metal fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910956773.XA CN110616335A (en) | 2019-10-10 | 2019-10-10 | Recovery device for recovering rare earth metal from rare earth metal slag and processing method |
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| CN112538640A (en) * | 2020-12-21 | 2021-03-23 | 桂林智工科技有限责任公司 | Rare earth metal and alloy electrolytic reduction intelligent production line |
| CN113846238A (en) * | 2021-09-22 | 2021-12-28 | 连云港市兆昱新材料实业有限公司 | Recovery device and recovery method for recovering rare earth metal from rare earth metal slag |
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| CN112538640A (en) * | 2020-12-21 | 2021-03-23 | 桂林智工科技有限责任公司 | Rare earth metal and alloy electrolytic reduction intelligent production line |
| CN113846238A (en) * | 2021-09-22 | 2021-12-28 | 连云港市兆昱新材料实业有限公司 | Recovery device and recovery method for recovering rare earth metal from rare earth metal slag |
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