CN105441987A - Rare earth fused-salt electrolysis cell for producing rare earth metals and alloys by using liquid cathode - Google Patents
Rare earth fused-salt electrolysis cell for producing rare earth metals and alloys by using liquid cathode Download PDFInfo
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- CN105441987A CN105441987A CN201510959552.XA CN201510959552A CN105441987A CN 105441987 A CN105441987 A CN 105441987A CN 201510959552 A CN201510959552 A CN 201510959552A CN 105441987 A CN105441987 A CN 105441987A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
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- 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
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- 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
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
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Abstract
The invention discloses a rare earth fused-salt electrolysis cell for producing rare earth metals and alloys by using a liquid cathode. The rare earth fused-salt electrolysis cell mainly comprises an electrolysis cell body, an anode and the liquid cathode; the anode and the cathode are provided with horizontal planes parallel to and facing each other; the anode is vertically inserted in the electrolysis cell body; the liquid cathode is a liquid metal electrolyzed at the bottom; a tungsten plate is inlaid in the internal bottom of the electrolysis cell body; a molybdenum plate or a niobium plate can be taken as a cathode bottom plate or a rare earth metal catcher for an electrolytic product separated out on the cathode. The rare earth fused-salt electrolysis cell for producing rare earth metals and alloys by using the liquid cathode has the advantages of high current efficiency, low radiant heat losses, high anode utilization rate, long electrolysis cell service life and low investment of the electrolysis cell body; the single plant capacity can reach above 100 KA, the energy consumption per unit product is greatly reduced, and produced products are stable in quality, low in production cost and relatively closed.
Description
Technical field
The present invention relates to a kind of rare earth molten salt electrolytic producing rare earth metal and alloy, specifically a kind of molectron be made up of cell body, rectangular-shaped anode, liquid cathode, the especially rare earth molten salt electrolytic of more than 30KA.
Background technology
Present stage, about the method for producing rare earth metal and alloy, be mainly fluoride smelt salt rare earth oxide electrolytic process, its electrolyzer adopted mainly contains following several structure:
The clear 61-253391 of Japanese Patent, metallic substance such as cell lining pressure tungsten, molybdenum etc. is made, and because the material such as tungsten, molybdenum is oxidizable in high temperature environments, this electrolyzer is the closed cell of filling with inert gas protection;
The clear 62-146291 of Japanese Patent, cell lining is iron or stainless material, and when producing single rare earth metal, metal product is vulnerable to pollute;
Chinese patent CN85100748A, cell lining is overall graphite, and liner outside is made up of graphite linings, irony overcoat and thermal insulation layer, because liner is that overall graphite is made, so the scale of this electrolyzer is subject to the restriction of graphite size;
Chinese patent application No.98194785.8, cell lining is built by laying bricks or stones by the graphite block with emboss pit, and outside is carbonaceous or the knotting of carbonaceous compound layer, flame-proof thermal insulation material, structured metal layer and thermal insulation layer.This electrolyzer can be built by laying bricks or stones according to scale, less expensive, but electrolyzer power line is even not respectively, makes raw material easily be deposited in the edge of cell body, and blow-on ionogen consumption is large, and then affects the unit consumption of current efficiency and graphite anode.
Chinese patent CN103290434A, cell lining is built by laying bricks or stones by the graphite block with emboss pit, and outside is carbonaceous or the knotting of carbonaceous compound layer, flame-proof thermal insulation material, structured metal layer and thermal insulation layer.The sidewall of cell body is mutually connected by the arc surface of two or more to surround closed form, and cell body is non-hermetic type, and this electrolyzer can be built by laying bricks or stones according to scale, but be greater than 20KA electrolyzer and build difficulty by laying bricks or stones, and work-ing life is short.
Chinese patent ZL201420648564.1, cell lining is built by laying bricks or stones by with graphite block, and outside is carbonaceous or the knotting of carbonaceous compound layer, flame-proof thermal insulation material, structured metal layer and thermal insulation layer.Cell body is non-hermetic type, and this electrolyzer can be built by laying bricks or stones according to scale, and be applicable to more than 30KA electrolyzer, but built certain difficulty by laying bricks or stones, work-ing life has much room for improvement.
Summary of the invention
The object of this invention is to provide the fused-salt bath that a kind of liquid cathode produces rare earth metal and alloy, its current efficiency is high, bath voltage is low, radiation heat loss is little, anode utilization ratio is high, blow-on ionogen consumption is little, electrolyzer uncovered realize semiclosed, graphite unit consumption is low, long service life, can expand single device capacity, significantly reduce energy consumption of unit product, and constant product quality, the production cost of production are low.
Another object of the present invention is to provide a kind of fused-salt bath producing rare earth metal and alloy, and it can solve, and rare earth molten salt electrolytic maximizes, energy-conservation structural limitation problem.
The present invention is achieved through the following technical solutions for achieving the above object:
A kind of liquid cathode produces the rare earth molten salt electrolytic of rare earth metal and alloy, it is characterized in that, mainly comprise electrolytic cell body, anode and liquid cathode, described anode, negative electrode have be parallel to each other, opposed facing horizontal plane, described anode is vertically inserted in electrolytic cell body, described liquid cathode is the liquid metal that bottom electrical solves, the inner bottom part damascene tungsten plate of described electrolytic cell body, molybdenum plate or niobium plate not only can be used as negative electrode base plate but also can be used as the rare earth metal adaptor that electrolysate separates out on negative electrode.
Preferably; also comprise the cover plate of cell body; described electrolytic cell body is built by laying bricks or stones from inside to outside by inner bag, water-cooling system, refractory insulating layer, metal-coating and stiffening web and is formed; described inner bag is that high-temperature-resistant steel is as 310s or No. 314 steel; described inner bag outside weldings water-cooling system; water-cooling system can make the rare earth molten salt of melting form crust protective layer, to prevent fused salt corrosion inner bag at inner bag surface crust.Other production process or bathing is can be used for after water coolant heating in water-cooling system.Described negative electrode base plate is arranged on bottom inner bag, described electrolytic cell body sidepiece, sealed bottom, and top is open type.
Preferably, described water-cooling system is made up of cooling water tank or the external high-pressure hydraulic pump of snakelike water-cooled tube, switch-valve, rate of flow meter, tensimeter.
Preferably, described cooling water tank is steel or copper material water tank, and described snakelike water-cooled tube is weldless steel tube.
Preferably, described anode and electrolyzer inner bag on crust protective layer between be spaced apart 3-5cm, described anode become two row or multiple row arrangement, anode interval 3-5cm is arranged in parallel.
Preferably, described anode is made up of graphite anode, conducting plates and conducting rod, is arranged on liftable cathode lifting device
Preferably, described anode is 20-600mm at the depth of penetration of electrolyzer, and the pole span between negative electrode, anode is 20-200mm, and electrolytic solution fluoride smelt salt composition range of choice is: 75-98%REF
3, 2-25%LiF, electrolysis temperature is 700-1300 DEG C, and cathode current density is 0.5-1.5A/cm
2, anodic current density is 0.3-2A/cm
2.
Preferably, the high temperaturesteel inner bag that described liquid cathode lays niobium plate, tungsten plate or molybdenum plate by bottom is connected with negative electrode conducting copper; Negative electrode conducting copper is connected with the negative pole of rectifying device.
Preferably, be placed in the rectangular parallelepiped anode of electrolyzer noncontact cell body, be connected the positive pole of rectifying installation by conducting plates with liftable special anode conduction rack.
The present invention is used in the production of more than 30KA capacity fluoride system rare earth molten salt.
According to fused-salt bath of the present invention, current efficiency is high, cathode and anode spacing is stable, blow-on ionogen consumption is little, graphite unit consumption is low, electrolyzer long service life and single device capacity can be expanded, single device capacity can reach more than 100KA, significantly reduce radiation heat loss and energy consumption of unit product, constant product quality, the production cost of production are low, cell body is semiclosed.
According to fused-salt bath of the present invention, rare earth molten salt electrolytic maximization, energy-conservation structural limitation problem can be solved.
Accompanying drawing explanation
Fig. 1 is the vertical view that liquid cathode of the present invention produces the rare earth molten salt electrolytic of rare earth metal and alloy;
Fig. 2 is the front view that liquid cathode of the present invention produces the rare earth molten salt electrolytic of rare earth metal and alloy.
Embodiment
Produce the fused-salt bath of rare earth metal and alloy according to liquid cathode of the present invention, comprise electrolytic cell body, negative electrode base plate 8, liquid cathode 9, anode 6, cover plate etc.Cell body is assembled from inside to outside by the protective layer 5 that crusts, high temperaturesteel inner bag 4, water-cooling system 3, refractory insulating layer 2, metal outer steel sleeve 1, and electrolyzer bottom surface and five, side close, and electrolyzer upper surface is opening; The rare earth molten-salt electrolysis matter 7 that crust protective layer 5 is melting is formed, liquid cathode 9 and the external rectifying installation negative pole of negative electrode base plate 8 at inner bag 4 surface crust after being cooled by water-cooling system 3, and being negative electrode is again metal container containing.Anode 6 is rectangular parallelepiped, and anode 6 and liquid cathode 9 plane-parallel, vertical plane is arranged.Anode 6 is two or more rows, and liquid cathode 9 is an entirety.Fluoride smelt salt composition range of choice is: 75-98%REF
3, 2-25%LiF.Pass into direct current, electrolysis temperature is 700-1300 DEG C, and liquid cathode 9 current density is 0.5-1.5A/cm
2, anode 6 current density is 0.3-2A/cm
2, depth of penetration is at 20-200mm, and pole span is 20-200mm.Electrolysate rare earth metal is separated out on negative electrode 9.
According to rare earth molten salt electrolytic of the present invention, adopt negative electrode, anode horizontal parallel, the vertical upper plug type structure of anode, cathodic overvoltage and fused salt resistance can be reduced, reduce uncovered area, thus realize keeping electrolyzer energy balance when reducing energy input, meet the temperature condition needed for electrolysis.
According to rare earth molten salt electrolytic of the present invention, comprise electrolytic cell body, negative electrode, anode assemblies, cover plate, electrolytic cell body is built by laying bricks or stones from inside to outside by high temperaturesteel, water-cooling system, refractory insulating layer, metal-coating and stiffening web and is formed, it is characterized in that: electrolyzer inner bag is made up of high temperaturesteel and crust fused salt, base plate paving niobium plate, tungsten plate or molybdenum plate, and cell body sidepiece, sealed bottom, top is open type; Negative electrode and positive electrode is plane-parallel, and vertical plane is arranged, negative electrode is liquid metal product, and anode is two row or multiple row.
Described electrolyzer inner bag welds the cavity that the 5 face seal upper surfaces that surround open wide and the fused salt the being attached to cavity internal surface layer that crusts by high temperature resistant steel plate and forms.
Described water-cooling system is made up of cooling water tank or the external high-pressure hydraulic pump of water-cooled tube, switch-valve, rate of flow meter, tensimeter.
Described anode assemblies is made up of graphite anode, conducting plates and conducting rod, and it is arranged on can on the cathode lifting device of oscilaltion, and cathode lifting device is connected with the positive pole of rectifying installation.Negative electrode, anode adopt the vertical down inserting type of plane-parallel anode to arrange, its depth of penetration continuously adjustabe within the scope of 20-600mm, the pole span between cathode and anode changes within the scope of 20-200mm.
The fused-salt bath of described production rare earth metal and alloy, the cathode current density of its work is 0.5-1.5A/cm
2, anodic current density is 0.3-2A/cm
2, electrolysis temperature is 700-1300 DEG C.
The present invention is used in the production of more than 30KA capacity fluoride system rare earth molten salt.
Claims (9)
1. the rare earth molten salt electrolytic of a liquid cathode production rare earth metal and alloy, it is characterized in that, mainly comprise electrolytic cell body, anode and liquid cathode, described anode, negative electrode have be parallel to each other, opposed facing horizontal plane, described anode is vertically inserted in electrolytic cell body, described liquid cathode is the liquid metal that bottom electrical solves, the inner bottom part damascene tungsten plate of described electrolytic cell body, molybdenum plate or niobium plate not only can be used as negative electrode base plate but also can be used as the rare earth metal adaptor that electrolysate separates out on negative electrode.
2. a kind of liquid cathode according to claim 1 produces the rare earth molten salt electrolytic of rare earth metal and alloy, it is characterized in that, also comprise the cover plate of cell body, described electrolytic cell body is by inner bag, water-cooling system, refractory insulating layer, metal-coating and stiffening web are built by laying bricks or stones from inside to outside and are formed, described inner bag is that high-temperature-resistant steel is as 310s or No. 314 steel, described inner bag outside weldings water-cooling system, water-cooling system can make the rare earth molten salt of melting form crust protective layer at inner bag surface crust, described negative electrode base plate is arranged on bottom inner bag, described electrolytic cell body sidepiece, sealed bottom, top is open type.
3. a kind of liquid cathode according to claim 2 produces the rare earth molten salt electrolytic of rare earth metal and alloy, it is characterized in that, described water-cooling system is made up of cooling water tank or the external high-pressure hydraulic pump of snakelike water-cooled tube, switch-valve, rate of flow meter, tensimeter.
4. a kind of liquid cathode according to claim 3 produces the rare earth molten salt electrolytic of rare earth metal and alloy, and it is characterized in that, described cooling water tank is steel or copper material water tank, and described snakelike water-cooled tube is weldless steel tube.
5. a kind of liquid cathode according to claim 2 produces the rare earth molten salt electrolytic of rare earth metal and alloy; it is characterized in that; described anode and electrolyzer inner bag on crust protective layer between be spaced apart 3-5cm, described anode become two row or multiple row arrangement, anode interval 3-5cm is arranged in parallel.
6. a kind of liquid cathode according to claim 2 produces the rare earth molten salt electrolytic of rare earth metal and alloy, it is characterized in that, the degree of depth that described anode inserts in a cell is 20-600mm, pole span between negative electrode, anode is 20-200mm, and electrolytic solution fluoride smelt salt composition range of choice is: 75-98%REF
3, 2-25%LiF, electrolysis temperature is 700-1300 DEG C, and liquid cathode current density is 0.5-1.5A/cm
2, anodic current density is 0.3-2A/cm
2.
7. a kind of liquid cathode according to claim 2 produces the rare earth molten salt electrolytic of rare earth metal and alloy, it is characterized in that, the high temperaturesteel inner bag that described liquid cathode lays niobium plate, tungsten plate or molybdenum plate by bottom is connected with negative electrode conducting copper; Described negative electrode conducting copper is connected with the negative pole of electrolyzer rectifying device.
8. a kind of liquid cathode according to claim 1 produces the rare earth molten salt electrolytic of rare earth metal and alloy, it is characterized in that, is placed in the anode of electrolyzer, be connected the positive pole of rectifying device by conducting plates with liftable special anode conduction rack.
9. a kind of liquid cathode according to the arbitrary claim of claim 1-8 produces the purposes of the rare earth molten salt electrolytic of rare earth metal and alloy, is applied in the production of more than 30KA capacity fluoride system rare earth molten salt.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510959552.XA CN105441987A (en) | 2015-12-21 | 2015-12-21 | Rare earth fused-salt electrolysis cell for producing rare earth metals and alloys by using liquid cathode |
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| CN201510959552.XA CN105441987A (en) | 2015-12-21 | 2015-12-21 | Rare earth fused-salt electrolysis cell for producing rare earth metals and alloys by using liquid cathode |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435648A (en) * | 2016-10-13 | 2017-02-22 | 北京科技大学 | Method for preparing molybdenum through high temperature electrolysis fusion of molybdenum concentrate |
| CN109797408A (en) * | 2019-04-01 | 2019-05-24 | 江西金世纪新材料股份有限公司 | A kind of electrolytic furnace |
| CN113802150A (en) * | 2021-03-01 | 2021-12-17 | 包头瑞鑫稀土金属材料股份有限公司 | Water-cooled anode current conducting plate device of large-scale rare earth molten salt electrolytic cell |
| CN114214670A (en) * | 2022-01-13 | 2022-03-22 | 内蒙古科技大学 | Integrated rare earth metal electrolysis process and rare earth electrolysis device |
| CN115074781A (en) * | 2022-06-21 | 2022-09-20 | 东北大学 | Bottom cathode rare earth electrolytic cell |
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| CN103540961A (en) * | 2012-07-09 | 2014-01-29 | 有研稀土新材料股份有限公司 | Electrolytic bath and method for electrolyzing light rare earth metals or alloys |
| CN104805471A (en) * | 2015-05-13 | 2015-07-29 | 江西理工大学 | Method and device for preparing rare-earth metal through lower cathode electrolysis and in-situ ingot casting synchronization |
| CN205241811U (en) * | 2015-12-21 | 2016-05-18 | 江西稀有金属钨业控股集团有限公司 | Tombarthite fused salt electrolysis groove of liquid negative pole production rare earth metal and alloy |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435648A (en) * | 2016-10-13 | 2017-02-22 | 北京科技大学 | Method for preparing molybdenum through high temperature electrolysis fusion of molybdenum concentrate |
| CN109797408A (en) * | 2019-04-01 | 2019-05-24 | 江西金世纪新材料股份有限公司 | A kind of electrolytic furnace |
| CN113802150A (en) * | 2021-03-01 | 2021-12-17 | 包头瑞鑫稀土金属材料股份有限公司 | Water-cooled anode current conducting plate device of large-scale rare earth molten salt electrolytic cell |
| CN114214670A (en) * | 2022-01-13 | 2022-03-22 | 内蒙古科技大学 | Integrated rare earth metal electrolysis process and rare earth electrolysis device |
| CN115074781A (en) * | 2022-06-21 | 2022-09-20 | 东北大学 | Bottom cathode rare earth electrolytic cell |
| CN115074781B (en) * | 2022-06-21 | 2024-03-15 | 东北大学 | Bottom cathode rare earth electrolytic tank |
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