CN216304003U - Device for preparing metal by thermally reducing metal oxide with alkali metal - Google Patents
Device for preparing metal by thermally reducing metal oxide with alkali metal Download PDFInfo
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- CN216304003U CN216304003U CN202121046172.4U CN202121046172U CN216304003U CN 216304003 U CN216304003 U CN 216304003U CN 202121046172 U CN202121046172 U CN 202121046172U CN 216304003 U CN216304003 U CN 216304003U
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- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 64
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 38
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 97
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 37
- 230000009467 reduction Effects 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- -1 alkali metal salt Chemical class 0.000 claims description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 31
- 238000000034 method Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000007547 defect Effects 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000011946 reduction process Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910014810 CaCl2—CaF2 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020949 NaCl—CaCl2 Inorganic materials 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- GYIPQKRAWKCWHP-UHFFFAOYSA-N [V+5].[O-2].[Al+3].[O-2].[O-2].[O-2] Chemical compound [V+5].[O-2].[Al+3].[O-2].[O-2].[O-2] GYIPQKRAWKCWHP-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The utility model relates to the technical field of metal material preparation devices, and particularly discloses a device for preparing metal by thermally reducing metal oxide with alkali metal. The device for preparing metal by thermally reducing metal oxide with alkali metal comprises: a first vessel containing a molten first molten salt medium; a second vessel containing a molten second molten salt medium; the first electrode is an anode; the second electrode is a cathode; a first electrolysis power supply; the second container is arranged in the first container, the first electrode is inserted into the molten second molten salt medium stored in the second container, and the second electrode is inserted into the molten first molten salt medium stored in the first container; the first electrode and the second electrode are respectively and electrically connected with the anode and the cathode of an electrolysis power supply. The device of the utility model can promote the improvement of production efficiency and the reduction of energy consumption in the production process.
Description
Technical Field
The utility model relates to the technical field of metal material preparation devices, in particular to a device for preparing metal by thermally reducing metal oxide with alkali metal.
Background
Active metal M1By thermal reduction of another metalCompound M2X belongs to one of the high-temperature chemical preparation methods, and the total reaction expression is as follows:
M2X+M1＝M2+M1X (1)
wherein M is1Is an active metal, which acts as a reducing agent; m2X is a metal compound, wherein M2Is the metal to be produced, and X is a non-metallic element and may be oxygen, chlorine, fluorine, sulfur, carbon, nitrogen, or the like. Due to M1Thermodynamic stability ratio M of X2X is high, the standard reaction free energy change (. DELTA.G ℃) of the reaction (1) is always negative, and the reaction proceeds spontaneously. Moreover, reaction (1) is always an exothermic reaction and is therefore referred to as "metallothermic reduction". The metallothermic reduction method has been used industrially to produce certain high purity metals, e.g. magnesium separately thermally reducing TiCl4Or ZrCl4Production of titanium sponge or Zirconium metal (Trans. electrochem. Soc., 1940, 78, 35-47; "Zirconium" CRC Handbook of chem. Phys.4, 2007-2TaF7Sodium reduction produces metallic tantalum powder (us 3012877, 12.12.1961), aluminothermic reduction of a mixture of iron oxide and aluminum vanadium oxide produces ferrovanadium (Minerals eng., 2003, 16, 793-one 805).
The metallothermic reduction method requires the consumption of an excess of the active metal reducing agent M1So that the reaction (1) is carried out completely, and all the active metals themselves are expensive, thereby increasing the production cost of the thermal reduction method. From an economic point of view, the metallothermic reduction process is only suitable for producing metals that are more expensive than the metallic reducing agents. In addition, a large amount of reaction heat is released in the metallothermic reduction process, so that the reaction metal products are mutually sintered in situ to easily form spongy porous particles, and the superfine metal powder cannot be prepared.
In the metallothermic reduction method, alkali metal (Ma) and alkaline earth metal (Me) have been widely used as reducing agents in the metallothermic reduction method to prepare various metals, with the main disadvantages of: (1) the price of alkali metal and alkaline earth metal is high, so that the cost of the reduction process is high; (2) due to the chemical activity of alkali metals and alkaline earth metals, the direct use of these metal reducing agents causes operational risks, high safety management requirements and great difficulty; (3) the thermal reduction process releases a large amount of reaction heat, which is easy to cause the local sintering of reaction products, (4) because alkali metal and alkaline earth metal have strong volatility at high temperature, the chemical erosion to the furnace lining material is easy to occur; (5) the production process is complex; 6) the production period is long and the cost is high; (7) the process energy consumption is large; (8) the process is a batch production process, and is difficult to realize continuity or semi-continuity.
Alkali metals are more suitable for thermal reduction processes with lower reduction temperatures than alkaline earth metals, for example below 700 ℃. The biggest advantage of the low-temperature metal thermal reduction is that the method can greatly reduce the heat energy loss in the process, and simultaneously effectively reduce the partial sintering degree of the product, so that the structural performance of the product is more consistent.
Molten salts are widely used as reaction media in thermal reduction of alkali or alkaline earth metals. For example, U.S. patent No. 4992096, 12/2/1991 discloses a method for producing CaCl2The rare earth metal and the alloy thereof are prepared by the calcium thermal reduction of rare earth metal chloride in a molten salt medium. In CaCl2Preparation of rare earth metals and alloys by thermal reduction of rare earth metal oxides with calcium in NaCl molten salt medium (US4578242, 3/25/1986) in CaCl2Preparation of rare earth metals and their alloys by thermal reduction of rare earth metal fluorides with calcium in molten salt medium (US patent 5314526, 24/5/1994), MgCl2-NdCl3Magnesiothermic reduction of UO in molten salt medium2And other actinide metal oxides (US590337, 3/1/1994), in CaCl2-CaF2Thermal reduction of TiO by calcium in molten salt medium2Or ZrO2Preparation of metallic titanium or zirconium (US6117208, 9/12/2000), thermal reduction of Ta with sodium in alkali and alkaline-earth chlorides2O5And Nb2O5Metallic tantalum and niobium were prepared (CN1410209A, 4 months and 16 days 2003).
The main advantages of the molten salt medium are:
(i) the fused salt medium has good heat transfer performance, is easy to maintain the uniformity of the temperature of the medium, can effectively reduce the local sintering of a reduction product, and is beneficial to ensuring the consistency of the performance of the product;
(ii) alkali and alkaline earth metals have certain solubility in molten halide, and certain thermal reduction reaction byproducts (alkaline earth metal oxide MeO) have equivalent solubility in molten halide salt, so that the properties are favorable for direct contact of an alkali metal reducing agent and oxide MO, and the reaction speed is accelerated.
However, the above-mentioned metallothermic reduction process directly employs calcium or sodium in metallic form as a reducing agent. Therefore, the above-mentioned drawbacks (1), (2), (5), (6), (7) and (8) of the alkali metal and alkaline earth metal thermal reduction methods cannot be overcome despite the use of a molten salt medium.
Patent CN105274576B discloses a method for preparing metal by continuous reduction in molten salt medium, aiming at the defects existing in the prior art that oxide MO is thermally reduced by alkali metal in molten salt medium, so as to solve or overcome the following disadvantages:
(i) the alkali metal reducing agent in metallic form is replaced by a specially selected alkaline earth metal oxide MeO/alkali metal halide MaY mixture: the defects of complex operation and danger caused by the existing method of directly adding the alkali metal reducing agent are overcome; the problems of high safety management requirements and high difficulty in alkali metal treatment and operation are solved;
(ii) auxiliary electrolysis of alkaline earth metal oxide MeO-containing molten salt medium to generate and regenerate alkali metal reducing agent in situ: the problem that the prior alkali metal thermal reduction excessively uses an alkali metal reducing agent is solved; overcomes the defect that the existing batch production process of metal thermal reduction is difficult to realize continuity.
However, in the actual production process, the patent CN105274576B method is to carry out thermal reduction and auxiliary electrolysis reaction in conventional equipment; the conventional device has the defects of low production efficiency and high energy consumption for the method disclosed in the patent CN 105274576B.
SUMMERY OF THE UTILITY MODEL
The present invention aims to solve at least to some extent one of the technical problems indicated in the background.
The technical problem to be solved by the utility model is realized by the following technical scheme:
an apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal, comprising:
a first vessel containing a molten first molten salt medium;
a second vessel containing a molten second molten salt medium;
the first electrode is an anode;
the second electrode is a cathode;
a first electrolysis power supply;
the second container is arranged in the first container, and the first electrode is inserted into the molten second molten salt medium stored in the second container; the second electrode is a first container which functions as a cathode and is used for storing the molten first molten salt medium; the first electrode and the second electrode are electrically connected to the positive electrode and the negative electrode of the first electrolysis power supply, respectively.
As an example, the first container is a container made of a material having electron conduction, the inner wall of which is in contact with the first molten salt medium, serving as a second electrode, and serving as a cathode; the second container is a container made of a material with alkali metal ion conduction function; the material with the alkali metal ion conduction function is Ma+B-Al2O3。
The device for preparing metal by adopting the alkali metal thermal reduction metal oxide with the structure is characterized in that the second container is arranged in the first container, the first electrode is inserted into the molten second molten salt medium stored in the second container, and the second electrode is the molten first molten salt medium stored in the first container and used as a cathode; the first electrode and the second electrode are electrically connected to the positive electrode and the negative electrode of the first electrolysis power supply, respectively. The structure forms an 'inert anode, a second molten salt medium | alkali metal ion solid conductor | first molten salt medium, and an inert cathode' electrolysis device. The electrolysis device can overcome the defect that MaY-MeY is formed after electrolysis in the Chinese invention patent CN105274576B2The- (Ma) molten salt medium has the defect of ion/electron mixed conduction, greatly improves the current efficiency of electrolysis, can realize the high-efficiency preparation of the Ma reducing agent and finally promotes the productionThe production efficiency is improved and the energy consumption is reduced in the process. Y is halogen (Cl, F).
In addition, the inert anode, the second molten salt medium, the alkali metal ion solid conductor, the first molten salt medium and the inert cathode electrolysis device are adopted for electrolysis, so that oxygen and water vapor of an anode product and an alkali metal Ma of a cathode product are completely separated, the reverse reaction of the oxygen and the water vapor and an active metal Ma is avoided, the utilization rate of the alkali metal Ma in the process of thermally reducing Metal Oxide (MO) is improved, the production cost is reduced, and the process of thermally reducing MO by the (Ma) is enhanced.
As an example, the first molten salt medium is a mixture of alkali metal halides and alkaline earth metal halides.
As an example, the halide of the alkali metal is NaCl, KCl, LiCl, NaF, KF or LiF; the halide of the alkaline earth metal is CaCl2、SrCl2、BaCl2、CaF2、SrF2Or BaF2。
As an embodiment, the anode is an inert anode, and includes an electrode made of metal, alloy, electronic ceramic, metal ceramic, or graphite; the cathode is an electrode made of inert cathode material such as Mo or W.
As an embodiment, the second molten salt medium is a mixture of alkali metal salt and hydroxide of alkali metal.
As an example, the alkali metal salt is NaCl, KCl, LiCl, NaF, KF, LiF, Na2CO3、K2CO3Or K2CO3(ii) a The hydroxide of the alkali metal is NaOH, KOH or LiOH.
As an embodiment, the apparatus for preparing metal by thermally reducing metal oxide with alkali metal further comprises:
a third vessel containing a molten third molten salt medium;
a third electrode, said third electrode being an anode;
the second electrode is a cathode;
a second electrolysis power supply;
the third container is arranged in the first container, the third electrode is inserted into the molten third molten salt medium stored in the third container, and the second electrode is the first container and has the functions of serving as a cathode and storing the molten first molten salt medium; the third electrode and the second electrode are electrically connected with the anode and the cathode of the second electrolysis power supply respectively.
As an embodiment, the third container is composed of O2-A container made of ion conducting material.
As an example, the utility model provides a third container, the third container is arranged in the first container, the third electrode is inserted into the molten third molten salt medium stored in the third container, the second electrode is the first container and is used for storing the molten first molten salt medium while being used as a cathode; the third electrode and the second electrode are electrically connected with the anode and the cathode of the second electrolysis power supply respectively. The device further forms an inert anode with the first molten salt medium, and the third molten salt medium | O2-The ionic solid conductor, a first molten salt medium, an inert cathode electrolyzer, is subjected to an electrolysis reaction such that the anode and cathode electrolytes are coated with O2-Ion conductor container membrane completely separated by only O2-Ionic energy in the anode and cathode electrolytes and O2-Migration within the ion conductor membrane. It has larger solid-liquid contact area than the traditional solid-solid interface, and is beneficial to increasing O2-The ion transfer efficiency can greatly improve the current efficiency of the second electrolytic cell; also overcomes the defect of reverse reaction between anode oxygen and reducing molten salt medium in the patent CN105274576B, and solves the problem of MaY-MeY formation after electrolysis2The (Ma) reducing molten salt medium has the problem of ion/electron mixed conduction, contributing to efficiently reducing the concentration of (MeO) and increasing the concentration of (Ma); the regeneration efficiency of the alkali metal is improved, and the production efficiency of preparing metal by thermally reducing metal oxide with the alkali metal is further improved.
The inventor researches and discovers that the method of the patent CN105274576B has the defects that the speed of dissolving MeO in a molten salt medium is too slow near a reaction product, and the undissolved MeO increases the viscosity of surrounding molten salt; the reduction speed is reduced due to the increase of the viscosity of the molten salt, and the production efficiency is low; in addition, the uniformity of the molten salt performance is reduced due to the increase of the viscosity of the molten salt, particularly the heat transfer property of a molten salt medium is reduced, and the structural consistency of a product is easily reduced due to partial or excessive sintering of a metal product; and also causes an increase in energy consumption and production cost.
The device of the utility model further forms an inert anode and a third molten salt medium | O with the first molten salt medium2-The technical problem that the MeO in the vicinity of a reaction product is dissolved in the molten salt medium too slowly by the CN105274576B method and the viscosity of the surrounding molten salt is increased by the undissolved MeO is solved, so that the improvement of the production efficiency is promoted, and the technical problems of poor product consistency and high energy consumption are solved.
As an example, the third molten salt medium is a mixture of alkali metal oxide and alkali metal salt and alkali metal hydroxide.
As an example, the alkali metal oxide is Na2O、K2O or Li2O; the alkali metal salt is NaCl, KCl, LiCl, NaF, KF, LiF, Na2CO3、K2CO3Or K2CO3(ii) a The hydroxide of the alkali metal is NaOH, KOH or LiOH.
As an embodiment, the anode is an inert anode, and includes an electrode made of metal, alloy, electronic ceramic, metal ceramic, or graphite; the cathode is an inert cathode, and the inert cathode is an electrode made of metal, such as Mo or W.
Has the advantages that: the utility model provides a device with a brand-new structure for preparing metal by thermally reducing metal oxide with alkali metal. The device can overcome the defect that MaY-MeY is formed after electrolysis in the Chinese invention patent CN105274576B2The (Ma) molten salt medium has the defect of ion/electron mixed conduction, greatly improves the current efficiency of electrolysis and promotes the production efficiency in the production processThe improvement of the rate and the reduction of the energy consumption also overcome the defect that the anode oxygen and the reducing molten salt medium have reverse reaction in the patent CN 105274576B. The device can also overcome the problem that the method of the patent CN105274576B has too low speed of dissolving MeO in the molten salt medium near the reaction product, and the undissolved MeO increases the viscosity of the surrounding molten salt; thereby improving the reduction speed and the production efficiency and reducing the energy consumption and the production cost.
Drawings
FIG. 1 is a schematic view showing the structure of an apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal in example 1.
FIG. 2 is a schematic diagram of an apparatus for preparing metal by thermally reducing metal oxide with alkali metal in example 2.
In the figure, 1 is a first electrode, 2 is a second container, 3 is a second molten salt medium, 4 is the second electrode and the first container, 5 is the first molten salt medium, 6 is a third electrode, 7 is a third container, and 8 is a third molten salt medium.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
Example 1
As shown in fig. 1, the present embodiment provides an apparatus for preparing a metal by thermally reducing a metal oxide with an alkali metal, comprising:
a first vessel 4 in which is stored a molten first molten salt medium 5;
a second vessel 2, said second vessel 2 holding a molten second molten salt medium 3;
a first electrode 1, wherein the first electrode 1 is an anode;
a second electrode 4, which simultaneously serves as a cathode in the form of the first container 4;
a first electrolysis power supply;
the second container 2 is arranged in a first container 4, the first electrode 1 is inserted into the molten second molten salt medium 3 stored in the second container 2, and the second electrode 4 is used as the second electrode 4 as well as the molten first molten salt medium 5 in the form of the first container 4; the first electrode 1 and the second electrode 4 are electrically connected to the positive electrode and the negative electrode of the first electrolysis power supply, respectively.
The first electrode 1 is fixed by an electrode fixing bracket and then inserted into the second molten salt medium 3 stored in the second container 2. The second electrode 4 is a first vessel whose material is an electron conductor and whose inner wall is in direct contact with the molten first molten salt medium 5.
In particular, the second container 2 is made of Na+B-Al2O3A container made of the material.
Specifically, the first molten salt medium 5 is NaCl or NaCl and CaCl2A mixture of (a). The second molten salt medium 3 is NaOH or a mixture of NaOH and NaCl.
In the specific production process, the raw material of the first molten salt medium 5 is firstly put into the first container 4, and the raw material of the second molten salt medium 3 is put into the second container 2; heating to the molten salt electrolysis temperature, placing the second container 2 in the first container 4 after the first and second molten salt mediums are completely melted, inserting the first electrode 1 into the molten second molten salt medium 3 stored in the second container 2, and simultaneously storing the molten first molten salt medium 5 in the second electrode 4; the first electrode 1 and the second electrode 4 are respectively and electrically connected with the anode and the cathode of a first electrolysis power supply to form a device for preparing metal by thermally reducing metal oxide with alkali metal. Corresponding voltage is applied to carry out electrolysis. Then the prepared reducing molten salt medium NaCl-CaCl can be stored in the first container 42- (Na) adding the metal oxide MO to be thermally reduced to produce the metal M.
The device can overcome the defect that MaY-MeY is formed after electrolysis in the Chinese invention patent CN105274576B2The- (Ma) molten salt medium has the defect of ion/electron mixed conduction, so that the current efficiency of electrolysis is greatly improved, the Ma reducing agent can be efficiently prepared, and the improvement of the production efficiency and the reduction of energy consumption in the production process are finally promoted; in addition, the oxygen and the water vapor of the anode product can be completely separated from the alkali metal Ma of the cathode product, and the reverse reaction of the oxygen and the water vapor with the active metal Ma is avoided.
Example 2
As shown in fig. 2, the apparatus for preparing metal by thermally reducing metal oxide with alkali metal provided in this embodiment further includes, on the basis of embodiment 1:
a third vessel 7, said third vessel 7 holding a molten third molten salt medium 8;
a third electrode 6, wherein the third electrode 6 is an anode;
a first container 4, said first container 4 simultaneously serving as a cathode;
a second electrolysis power supply;
said third vessel 7 being placed in the first vessel 4, said third electrode 6 being inserted in a molten third molten salt medium 8 stored in the third vessel 7, said first vessel 4 being used to store the molten first molten salt medium 5 and also to act as a cathode; the third electrode 6 and the first container 4 are electrically connected to the anode and cathode of the second electrolysis power supply, respectively.
Specifically, the third container is composed of Y2O3Stabilized ZrO2Oxygen ion (O)2-) A container made of a conductive functional material. Specifically, the third molten salt medium 8 is Na2O and NaOH, or Na2O, NaOH and Na2CO3A mixture of (a).
In the specific production process, firstly, the molten third molten salt medium 8 is put into the third container 7, then the third container 7 is put into the first container 4, the third electrode 6 is inserted into the molten third molten salt medium 8 stored in the third container 7, and the first container 4 is used for storing the molten first molten salt medium 5; when the material of the first container 4 is an electron conductor, it again serves as a cathode for the first and second electrolytic cells. The third electrode 6 and the first container 4 are respectively connected with the anode and the cathode of the second electrolysis power supply to form the device for preparing metal by thermally reducing metal oxide with alkali metal. Corresponding voltage is applied to carry out electrolysis. Then the prepared reducing molten salt medium NaCl-CaCl can be stored in the first container 42- (Na) adding the metal oxide MO to be thermally reduced to produce the metal M. The apparatus also continuously reduces the generation of thermal reduction by-products (CaO)In NaCl-CaCl2Content in molten salt medium of- (Na) -CaO.
By adopting the device for preparing metal by thermally reducing metal oxide with alkali metal, the influence of electron conduction in the first molten salt medium on the electrolysis current efficiency is prevented by using the two diaphragms with different ion conduction, and the current efficiency of auxiliary electrolysis can be greatly improved; the defect of reverse reaction between anode oxygen and water vapor and a reducing molten salt medium in patent CN105274576B is overcome, and the method is beneficial to efficiently reducing the concentration of (MeO) and improving the concentration of (Ma); the regeneration efficiency of the alkali metal is improved, and the production efficiency of preparing metal by thermally reducing metal oxide with the alkali metal is further improved. Meanwhile, the method also solves the technical problems that the speed of dissolving the MeO in the molten salt medium near the reaction product is too low and the undissolved MeO increases the viscosity of the surrounding molten salt in the CN105274576B method, thereby promoting the improvement of the production efficiency and solving the technical problems of poor product consistency and high energy consumption.
Claims (10)
1. An apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal, comprising:
a first vessel containing a molten first molten salt medium;
a second vessel containing a molten second molten salt medium;
the first electrode is an anode;
the second electrode is a cathode;
a first electrolysis power supply;
the second container is composed of a container with Ma+A vessel of ion conducting material, said second vessel being disposed in the first vessel, said first electrode being inserted into the molten second molten salt medium contained in the second vessel, said second electrode being the first vessel and functioning as both a cathode and as a reservoir for the molten first molten salt medium; the first electrode and the second electrode are electrically connected to the positive electrode and the negative electrode of the first electrolysis power supply, respectively.
2. An apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal according to claim 1, wherein the second container is a container made of a material having an alkali metal ion conducting action.
3. An apparatus for producing a metal by the thermal reduction of a metal oxide with an alkali metal according to claim 1 wherein the first molten salt medium is a halide of an alkali metal or a halide of an alkaline earth metal or a mixture of both.
4. The apparatus for preparing metal by thermally reducing metal oxide with alkali metal according to claim 3, wherein the halide of alkali metal is NaCl, KCl, LiCl, NaF, KF or LiF; the halide of the alkaline earth metal is CaCl2、SrCl2、BaCl2、CaF2、SrF2Or BaF2。
5. The apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal according to claim 1, wherein the second molten salt medium is a mixture of an alkali metal salt and a hydroxide of an alkali metal.
6. The apparatus for preparing metal by thermally reducing metal oxide with alkali metal according to claim 5, wherein the alkali metal salt is NaCl, KCl, LiCl, NaF, KF, LiF, Na2CO3、K2CO3Or K2CO3(ii) a The hydroxide of the alkali metal is NaOH, KOH or LiOH.
7. The apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal according to claim 1, further comprising:
a third vessel containing a molten third molten salt medium;
a third electrode, said third electrode being an anode;
the second electrode is a cathode;
a second electrolysis power supply;
the third container is arranged in the first container, the third electrode is inserted into the molten third molten salt medium stored in the third container, and the second electrode is the first container and has the functions of serving as a cathode and storing the molten first molten salt medium; the third electrode and the second electrode are electrically connected with the anode and the cathode of the second electrolysis power supply respectively.
8. The apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal according to claim 7, wherein the third vessel is made of a material having O2-A container made of ion conducting material.
9. The apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal according to claim 7, wherein the third molten salt medium is a mixture of an alkali metal oxide with an alkali metal salt and an alkali metal hydroxide.
10. The apparatus for producing a metal by thermally reducing a metal oxide with an alkali metal according to claim 9, wherein the alkali metal oxide is Na2O、K2O or Li2O; the alkali metal salt is NaCl, KCl, LiCl, NaF, KF, LiF, Na2CO3、K2CO3Or K2CO3(ii) a The hydroxide of the alkali metal is NaOH, KOH or LiOH.
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