CN114016083A - Method for regenerating alkali metal reducing agent in process of preparing metal by thermally reducing metal oxide with alkali metal - Google Patents
Method for regenerating alkali metal reducing agent in process of preparing metal by thermally reducing metal oxide with alkali metal Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 84
- 230000001603 reducing effect Effects 0.000 title claims abstract description 73
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 72
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 70
- 239000002184 metal Substances 0.000 title claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 230000008569 process Effects 0.000 title claims abstract description 36
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 31
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 181
- 230000009467 reduction Effects 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000006227 byproduct Substances 0.000 claims abstract description 26
- 239000004020 conductor Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 230000008929 regeneration Effects 0.000 claims abstract description 14
- 238000011069 regeneration method Methods 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 22
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 17
- 239000010416 ion conductor Substances 0.000 claims description 17
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000011195 cermet Substances 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 14
- 239000011734 sodium Substances 0.000 description 61
- 238000006722 reduction reaction Methods 0.000 description 58
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 46
- 239000011780 sodium chloride Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 26
- 239000000047 product Substances 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 230000004907 flux Effects 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
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- 239000002994 raw material Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 15
- 229910020949 NaCl—CaCl2 Inorganic materials 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 13
- 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 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000011065 in-situ storage Methods 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000001110 calcium chloride Substances 0.000 description 8
- 229910001628 calcium chloride Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000011946 reduction process Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011532 electronic conductor Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- -1 rare earth metal chloride Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
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- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
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- 230000002441 reversible effect Effects 0.000 description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052712 strontium 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910014103 Na-S Inorganic materials 0.000 description 1
- 229910014147 Na—S Inorganic materials 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 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
- 239000011149 active material Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000000265 homogenisation 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
- 230000002045 lasting effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- 230000002035 prolonged effect Effects 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
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for regenerating an alkali metal reducing agent in a metal preparation process by thermally reducing a metal oxide with an alkali metal. It includes: melting O2‑Charging ion-conducting molten salt medium with O2‑A container for ion conduction; will contain molten O2‑Of ion-conducting molten salt media with O2‑The container with the function of ion conduction is put into a byproduct generated in the process of preparing metal by thermally reducing metal oxide with alkali metal; in molten O2‑Inserting an inert anode into the ion-conducting molten salt medium, and inserting an inert cathode into a reaction byproduct generated in the process of preparing metal by thermally reducing metal oxide with alkali metal; form an "inert anode, O2‑Ion-conducting molten salt medium | O2‑Ion solid conductor byproduct, inert cathode electrolytic cell; and carrying out electrolytic reaction on the electrolytic cell. The method improves the current of auxiliary electrolysisEfficiency, contributing to efficient reduction of (MeO) concentration and increase of (Ma) concentration; the regeneration efficiency of the alkali metal is improved, the production efficiency of preparing the metal by thermally reducing the metal oxide by the alkali metal is further improved, and the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of metal material preparation, in particular to a method for regenerating an alkali metal reducing agent in a metal preparation process by thermally reducing metal oxide with alkali metal.
Background
Metallothermic reduction is one of the methods for producing metals from metal compounds. The principle of the method isBy means of an active metal M1Thermally reducing compounds M of another metal2X to produce a metal M2The overall response is expressed as follows:
M2X+M1＝M2+M1X (1)
reaction (1) is always an exothermic reaction, where M1Is an active metal (e.g., alkali metal, alkaline earth metal, Al, Si) used 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. And M2In contrast, M1Has a stronger affinity for X, that is, M1Thermodynamic stability ratio M of X2X is high. Thus, the standard reaction free energy change (. DELTA.G ℃) of reaction (1) is always negative. 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.4,2007-2008, New York, CRC Press,42), K2TaF7Sodium reduction produces metallic tantalum powder (12.12. 3012877,1961), and 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, the release of a large amount of reaction heat during the metallothermic reduction process is accompanied, so that the metal products are easy to sinter mutually in situ after reduction, and the particles are agglomerated and coarsened.
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 have a much lower melting point than alkaline earth metals, but only a slightly lower boiling point than alkaline earth metals. Thus, alkali metals are more suitable for thermal reduction processes with lower reduction temperatures, e.g. below 700 ℃, while alkaline earth metals are more suitable for thermal reduction with higher reduction temperatures, e.g. above 750 ℃. 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 (3.25.3. 4578242,1986) in CaCl2Preparation of rare earth metals and their alloys (5.24. 5314526,1994 years) by thermal reduction of rare earth metal fluorides with calcium in molten salt medium2-NdCl3Magnesiothermic reduction of UO in molten salt medium2And other actinide metal oxides (3.1.3. 590337,1994) in CaCl2-CaF2Thermal reduction of TiO by calcium in molten salt medium2Or ZrO2Preparation of metallic titanium or zirconium (9.12. 6117208,2000 U.S.) by sodium thermal reduction of Ta 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;
(i i) alkali and alkaline earth metals have certain solubility in their molten halide, and some thermal reduction reaction by-products (alkaline earth metal oxides MeO) have equivalent solubility in their molten halide salts, which are favorable for the direct contact of the alkali metal reducing agent with the oxides MO and increase the reaction rate.
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 specially selected alkaline earth metal oxide MeO/alkali metal halide MaY mixture is adopted to replace the alkali metal reducing agent in a metal form, so that 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.
The method of patent CN105274576B is carried out by melting MaY-MeY2Adding MeO-MaY mixture into the flux, and preparing the reducing molten salt medium MaY-MeY through auxiliary electrolysis2- (Ma) and then in a reducing molten salt medium MaY-MeY2Adding metal oxide into (Ma) to electrolyze to prepare metal material. In the actual production process, the regeneration efficiency of alkali metal is low by the method of special CN105274576B, thereby influencing the production efficiency of preparing metal by thermally reducing metal oxide with alkali metalAnd (4) rate.
It is to be noted that the information disclosed in the above background section is only for enhancement of understanding of the background of the present application and therefore may include information that does not constitute prior art known to a person of ordinary skill in the art.
Disclosure of Invention
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 invention is realized by the following technical scheme:
a method for regenerating an alkali metal reducing agent in a process for preparing a metal by thermally reducing a metal oxide with an alkali metal, comprising the steps of:
melting O2-Charging ion-conducting molten salt medium with O2-A container for ion conduction;
will contain molten O2-Of ion-conducting molten salt media with O2-The container with the function of ion conduction is put into a byproduct generated in the process of preparing metal by thermally reducing metal oxide with alkali metal;
in molten O2-Inserting an inert anode into the ion-conducting molten salt medium, and inserting an inert cathode into a reaction byproduct generated in the process of preparing metal by thermally reducing metal oxide with alkali metal; form an "inert anode, O2-Ion-conducting molten salt medium | O2-Ion solid conductor byproduct, inert cathode electrolytic cell;
then, the electrolytic cell is electrolyzed.
The inventor finds out through a large amount of experimental researches that: in molten O2-Inserting an inert anode into the ion-conducting molten salt medium, and inserting an inert cathode into a reaction byproduct generated in the process of preparing metal by thermally reducing metal oxide with alkali metal; form an "inert anode, O2-Ion-conducting molten salt medium | O2-The ionic solid conductor byproduct, an inert cathode cell, 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. The solid-liquid contact area is larger than that of the traditional solid-solid interface, thereby being beneficial to increasing O2-The ion transfer efficiency can greatly improve the current efficiency of the auxiliary electrolysis; the defect of reverse reaction between anode oxygen and a reducing molten salt medium in a 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.
The patent CN105274576B is a previous invention of the inventor, and the inventor further found that the method of the patent CN105274576B has a technical problem of low production efficiency in the process of preparing the metal material in actual production; in order to solve the technical problem of low production efficiency, the inventors have conducted a great deal of experimental studies to find the cause of low production efficiency, and finally found that: the method adopting patent CN105274576B is to prepare a reducing molten salt medium by taking a MeO/MaY mixture as a raw material, the speed of dissolving MeO in the molten salt medium near a reaction product by adopting the reducing molten salt medium is too slow, and the viscosity of surrounding molten salt is increased by the undissolved MeO; and the increase of the viscosity of the molten salt leads to the reduction speed reduction, thereby leading to the low production efficiency. The method for regenerating the alkali metal reducing agent in the process of preparing the metal by thermally reducing the metal oxide by the alkali metal can regenerate the alkali metal and remove MeO at the same time; therefore, the method can also solve the technical problem that the MeO in the vicinity of the reaction product is too slowly dissolved in the molten salt medium and the undissolved MeO increases the viscosity of the surrounding molten salt in the CN105274576B method, thereby promoting the improvement of the production efficiency.
Furthermore, the inventors have found that the rate of MeO dissolution in the molten salt medium is too slow in the vicinity of the reaction product, and that the unmelted MeO increases the surrounding molten salt viscosity; 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 the local or excessive sintering of a metal product; and also causes an increase in energy consumption and production cost. The method for regenerating the alkali metal reducing agent in the process of preparing the metal by thermally reducing the metal oxide by the alkali metal can regenerate the alkali metal and remove MeO at the same time; therefore, the method can also solve the technical problems that the MeO is dissolved in the molten salt medium at a too low speed near the reaction product and the viscosity of the surrounding molten salt is increased by the unmelted MeO in the method of CN105274576B, and further solve the technical problems of poor product consistency and high energy consumption in the method of CN 105274576B.
Preferably, said O is2-The ion-conducting molten salt medium is Ma2O-MaOH-Ma2CO3-a MaCl medium; wherein Ma represents an alkali metal.
Preferably, the byproduct generated in the process of preparing metal by thermally reducing metal oxide with alkali metal is a reducing molten salt medium MaY-MeY2- (Ma) carrying out (Ma) a thermal reduction of the metal by-products produced during the process; wherein, Ma represents alkali metal, Me represents alkaline earth metal; y represents a halogen element.
Further preferably, the reducing molten salt medium MaY-MeY2- (Ma) by melting MaY-MeY2Adding auxiliary electrolytic MaOH-Ma into flux2CO3-Ma obtained by MaCl molten salt formation.
The method comprises the following specific steps:
with mixed salts MaOH-Ma2CO3-MaCl as a raw material for Ma, in the form of a mixture MaY-MeY2Is a thermal reduction molten salt medium flux; charging mixed salt raw materials into Ma+Ion-conducting container, and then has Ma+The ion-conducting container is placed in a MaY-MeY2In a flux of molten salt medium, having Ma+The ion-conducting container is used as a separator, the exterior of which is directly connected with MaY-MeY2Molten salt medium flux contact, so that molten MaOH-Ma2CO3-MaCl fused salt and MaY-MeY2The molten salt medium flux is completely isolated;
in MaOH-Ma2CO3-inserting an electron conductor rod into the MaCl molten salt as an inert or graphite anode; in MaY-MeY2An electronic conductor bar is inserted into the fused salt medium flux to be used as an inert cathode; forming an "inert or graphite anode, MaOH-Ma2CO3-MaCl (anolyte) | Ma + ion solid conductor | MaY-MeY2(catholyte), inert cathodeA polar "electrolytic cell;
carrying out electrolytic reaction on the electrolytic cell to obtain the reducing molten salt medium MaY-MeY2- (Ma); wherein Ma represents an alkali metal; me represents an alkaline earth metal; y represents a halogen element.
The inventor adopts the raw material MaOH-Ma2CO3And the further research shows that the dissolution of Ma produced by adopting the method of the Chinese invention patent CN105274576B into the molten salt medium can cause the remarkable increase of the electron conduction ratio of the medium and the reduction of the electrolysis current efficiency, thereby causing the low efficiency of preparing the Ma reducing agent, and finally causing the low production efficiency, the high energy consumption and the high production cost in the production process.
Based on the discovery of the reason, the inventor converts MaOH-Ma into MaOH-Ma in the electrolytic process2CO3-MaCl molten salt put into the reactor with Ma+A container for ion conduction; will then have Ma+The ion-conducting container is filled with molten MaY-MeY2In a flux of molten salt medium, having Ma+Ion-conducting container external direct contact with MaY-MeY2Contact of molten salt medium with flux to make MaOH-Ma2CO3-MaCl fused salt with molten MaY-MeY2The molten salt medium flux is completely isolated; forming an "inert anode, MaOH-Ma2CO3-MaCl (anolyte) | Ma+Ion solid conductor |. MaY-MeY2(catholyte), inert cathode "cell. The electrolysis is carried out based on the electrolytic cell, and the defect that MaY-MeY is formed after electrolysis in the Chinese invention patent CN105274576B is overcome2The- (Ma) molten salt medium has the defect of ion/electron mixed conduction, greatly improves the current efficiency of electrolysis, can realize the efficient preparation of the Ma reducing agent, and finally promotes the improvement of the production efficiency and the reduction of energy consumption in the production process.
The method adopting patent CN105274576B is to prepare a reducing molten salt medium by taking a MeO/MaY mixture as a raw material, the speed of dissolving MeO in the molten salt medium near a reaction product by adopting the reducing molten salt medium is too slow, and the viscosity of surrounding molten salt is increased by the undissolved MeO; the viscosity of the molten salt is increased to reduce the reduction speed, thereby leading to the production efficiencyLow. Based on the discovery of the reason, the inventor replaces the raw material MeO/MaY in the patent CN105274576B with the raw material MaOH-Ma2CO3-MaCl for preparing reducing molten salt medium by using inert anode, MaOH-Ma2CO3-MaCl (anolyte) | Ma+Ion solid conductor |. MaY-MeY2(catholyte), inert cathode "electrolytic cell, raw material MaOH-Ma can be electrolyzed2CO3-MaCl and MaY-MeY2Separated to lead the fused salt medium flux MaY-MeY2The method has no addition of MeO, is beneficial to the melting of the generated MeO, and solves the problem that the speed of dissolving the MeO in a molten salt medium is too slow; further successfully overcomes the problem that the method disclosed in the patent CN105274576B has low reduction speed and low production efficiency due to the fact that the speed of dissolving MeO in a molten salt medium near a reaction product is too low.
In addition, an "inert anode, MaOH-Ma is used2CO3-MaCl (anolyte) | Ma+Ion solid conductor |. MaY-MeY2The electrolysis is carried out by an inert cathode electrolytic cell, so that the oxygen and the water vapor of the anode product are completely separated from the alkali metal Ma of the cathode product, and the reverse reaction of the oxygen and the active metal Ma is avoided. By placing an inert cathode on MaY-MeY2Different positions of the molten salt medium flux can ensure that Ma is separated out from the cathode at any required position in the molten salt medium flux and is locally melted into the molten salt medium flux to be diffused to the periphery of the cathode, thereby strengthening the homogenization and thermal reduction MO process of (Ma) in the medium.
Preferably, the alkali metal is Li, Na or K; the alkaline earth metal is Ca, Sr or Ba; the halogen element is Cl or F.
Preferably, said has Ma+The active material in the ion-conducting container is a solid conductor Ma+β-Al2O3。
Preferably, said has Ma+The ion-conducting container is prepared by the following method: will consist of Na2O and Al2O3Na prepared by using raw materials+β-Al2O3The container is immersed inContaining Ma+Ion exchange is carried out in the ion molten salt to obtain the compound with Ma+A container for ion conduction;
or, said has Ma+The ion-conducting container is made of Ma oxide or carbonate and Al2O3Is prepared from the raw materials.
Preferably, said group containing Ma+The ionic molten salt is MaY-MeY2The molten salt is mixed.
Preferably, the inert cathode and inert anode electron conductor rods are made of the same or different materials in the preparation of the reducing molten salt medium electrolysis reaction.
Preferably, an inert anode and an inert cathode are selected in the auxiliary electrolysis process;
wherein the inert anode electron conductor rod is made of a material selected from the group consisting of: metals, alloys, electronic ceramics, cermets; the inert cathode electronic conductor bar is made of a material selected from Fe, Ni, stainless steel, Mo and W or a material the same as the prepared metal in a chloride molten salt system; w, Mo or the same material as the prepared metal in a fluoride molten salt system.
Preferably, in the electrolytic reaction for preparing the reducing molten salt medium, the electrolytic voltage in the electrolytic reaction is controlled to be higher than the actual decomposition voltage of MaOH/lower than Ma2CO3Or higher than Ma, or2CO3Lower than the actual decomposition voltage of MaCl or higher than the actual decomposition voltage of MaCl.
Most preferably, in the electrolytic reaction for preparing the reducing molten salt medium, the actual electrolytic voltage in the electrolytic reaction is controlled to be higher than the actual decomposition voltage of MaOH/lower than Ma2CO3The actual decomposition voltage not only ensures the current efficiency of electrolysis and reduces the electric energy consumption, but also ensures that only oxygen and water vapor are released at the anode, so that the process has the advantages of environmental protection.
Preferably, the byproduct generated in the process of preparing metal by thermally reducing metal oxide with alkali metal is MaY-MeY2- (Ma) - (MeO) molten salt.
Preferably, theHaving O of2-The ion-conducting container is made of CeO2Radical O2-A container made of an ion conductor material.
Most preferably, the CeO2Radical O2-The ionic conductor material is Ce0.90Gd0.10O1.95。
Preferably, the material of the inert anode is selected from: a metal, an alloy, an electroceramic, a cermet, or graphite.
Preferably, the material of the inert cathode is selected from: in a chloride molten salt system, selected from Fe, Ni, stainless steel, Mo, W, or the same material as the prepared metal; w, Mo or the same material as the prepared metal in a fluoride molten salt system.
Preferably, the voltage of electrolysis in the electrolysis reaction is controlled to be higher than that of the electrolyte dissolved in the molten MaY-MeY2Actual decomposition voltage of (MeO) in the (Ma) - (MeO) catholyte, lower than that of MaY and MeY2Actual decomposition voltage of the molten salt.
In the present invention, "-" between the components represents a composition, such as Ma2O-MaOH-Ma2CO3-MaCl medium represented by Ma2O、MaOH、Ma2CO3And a medium consisting of MaCl.
Has the advantages that: the method has the advantages that (1) common metal or alloy is convenient to replace valuable noble metal as the oxygen inert anode material, and the cost is reduced; (2) by the use of O2-Ion-conducting molten salt medium (molten Ma)2O-MaOH-Ma2CO3-MaCl)∣O2-Ion solid conductor (CeO)2Radical O2-Solid conductor) having a larger contact area than a conventional solid-solid interface, which is advantageous for increasing O2-Ion transfer efficiency; (3) using "inert anodes, O2-Ion-conducting molten salt medium (anolyte) | CeO2Radical O2-Ionic solid conductor by-product (catholyte), liquid O in an inert cathode cell2-Ionic molten salt medium Ma2O-MaOH-Ma2CO3-MaCl and CeO in solid form2Radical O2-An ion conductor (for example:Ce0.90Gd0.10O1.95) Solid-liquid combination O2-The ionic conductor system being capable of excluding O2-The influence of electron conduction can occur inside the ionic solid conductor, so that the system is pure O2-The ionic conductor can greatly improve the current efficiency of the auxiliary electrolysis; (4) o is2-Ion solid conductor (CeO)2Radical O2-Solid electrolyte) container, which overcomes the defect of reverse reaction between oxygen separated out from the inert anode and the reducing molten salt medium in patent CN105274576B, is beneficial to efficiently reducing the concentration of (MeO) and improving the concentration of (Ma), and enhances the reducing property and the metal heat reducing capability of the external molten salt medium; (5) the interior is filled with molten Ma2O-MaOH-Ma2CO3O of MaCl anolyte2-When the ion conductor container is taken out from the external molten salt medium and naturally cooled, the existence of the internal molten medium is helpful for reducing O2-The rapid cooling of the ion conductor can prevent the container material from cracking caused by thermal shock and prolong the solid O2-The service life of the ion conductor is prolonged, and the cost is reduced; (6) the concentration of (MeO) in the reducing molten salt medium is reduced in time, the viscosity of the medium can be reduced, the speed of dissolving the MeO in the molten salt medium is increased, the efficiency of removing the MeO is improved, the thermodynamic driving force of thermal reduction MO of (Ma) is enhanced, the yield of local regeneration of the Ma is improved, and the production cost is reduced; (7) molten ionic medium (Ma)2O-MaOH-Ma2CO3-MaCl) with solid CeO2Radical O2-Ion conductor (e.g., Ce)0.90Gd0.10O1.95) Form a solid-liquid combination O2-Ion-conducting system, ensuring that the system is pure O2-Conductor, and is convenient for use of low-price O2Inert anode avoiding precious noble metal O2An inert anode material; (8) using molten Ma2The O-MaOH electrolyte and the inert anode which releases oxygen can realize green and environment-friendly production in the in-situ regeneration process of removing (MeO) and (Ma) of the external reductive molten salt medium.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a reducing molten salt medium and a reaction process of thermally reducing metal oxide MO according to the present invention.
FIG. 2 is a schematic diagram of the process of regenerating an alkali metal reducing agent in the process of preparing a metal by thermally reducing a metal oxide with an alkali metal.
FIG. 3 is the sodium thermal reduction of Ta from example 12O5X-ray diffraction (XRD) pattern of the product tantalum powder.
FIG. 4 is the sodium thermal reduction of Ta from example 12O5FESEM scanning electron micrograph of the product tantalum powder.
FIG. 5 is a drawing showing the sodium thermal reduction of Ta of example 22O5X-ray diffraction (XRD) pattern of the product tantalum powder.
FIG. 6 is the sodium thermal reduction of Ta from example 22O5FESEM scanning electron micrograph of the product tantalum powder.
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.
The principles of the reduction in the concentration of MeO (MeO) and the in-situ regeneration Ma of the reducing molten salt medium and the reaction principles in the application process are as follows:
1. electrochemical process for in situ preparation of alkali metal Ma reducing agent
Electrochemical method for decomposing eutectic mixed salt MaOH-Ma2CO3MaOH, Ma in the-MaCl system2CO3And MaCl are represented by the following reactions, respectively:
4(MaOH)＝4(Ma)+O2(g)+2H2O
(2a)
2(Ma2CO3)＝4Ma+O2(g)+2CO2(g) (2b)
2(MaCl)＝2Ma+Cl2(g) (2c)
adding Ma into molten MaOH2CO3And the aim of MaCl is to properly reduce the activity of the MaOH molten salt and the melting point of the molten salt mixture. Standard free energy Change Δ G of the above reaction 20 550℃Both positive values indicate that these reactions do not proceed spontaneously, but that the alkali metal salts can be decomposed by molten salt electrolysis. Taking Ma as an example, reacting at 550 DEG C(2a) The standard cell potential values of (2b) and (2c) are: -2.4, -2.6 and-3.5V. For example, by controlling the cell voltage at 2.4-2.6V, the reaction (2a) will occur, NaOH will be decomposed, Na will be precipitated at the cathode, O will be released at the inert anode2(g) And H2O (g). Through auxiliary electrolysis, Ma is separated out at the cathode and then dissolved in a molten salt medium MaY-MeY2To form a reducing molten salt medium MaY-MeY2-(Ma)。
2. Preparation of metal M by thermal reduction of MO with alkali metal Ma in reducing molten salt medium
Ma thermal reduction MO is represented by reaction 3:
MO+2(Ma)+MeY2＝M+2MaY+(MeO) (3)
wherein in the reaction (3), (MeO) is a reaction by-product of the reaction (3), and then dissolved in the reducing MaY-MeY2Formation of MaY-MeY in (Ma) molten salt medium2-(Ma)-(MeO)。MeY2Also participate in the heat reduction MO reaction of Ma, and MeY exists in a molten salt medium2Δ G for reaction 30 2The value of (A) is more negative, and the thermodynamic driving force of preparing metal M by thermally reducing MO by Ma is further improved.
Molten salt medium MaY-MeY formed in process of thermally reducing MO by Ma2The reducing power (or reducing power) of (Ma) - (MaO) is expressed by the oxygen level of the molten salt medium, and the lower the oxygen level, the stronger the reducing power (or reducing power) of the molten salt medium. Molten salt medium MaY-MeY2The oxygen sites of (Ma) - (MaO) are controlled by the (Me)/(MeO) equilibrium:
(Me)+1/2O2＝(MeO) (4)
the equilibrium oxygen level is expressed by the following equation:
wherein the content of the first and second substances,
is MaY-MeY2- (Ma) - (MaO) equilibrium oxygen position of molten salt medium, K is equilibrium constant of reaction (4), aMeoAnd aMeAre respectivelyThe activity of MeO and Me in the molten salt medium. The lower the oxygen level, the greater the reducing power (or reducibility) of the molten salt medium. Formula 1 shows that at a certain temperature, the molten salt medium MaY-MeY2Equilibrium oxygen sites of (Ma) - (MaO)
The ratio is proportional and inversely proportional to the reducing power. Reduce
The oxygen level of the molten salt medium can be reduced, the reducing capability of the medium is improved, and finally the Ma thermal reduction MO process is enhanced.
Table 1 provides MO ═ Ta2O5Y ═ Cl and Ma ═ Na, K, Li; me ═ Ca, Mg, Ba, and Sr are examples, and reaction 3 thermodynamic data at 550 ℃.
TABLE 1 in MaCl-MeCl2Neutralization in (Ma) molten salt medium at 550 ℃, and heat reduction of Ta by Ma2O5Thermodynamic data for the production of metallic tantalum
As is clear from Table 1, the standard free energy change (. DELTA.G. °) of reaction 3 is550℃) The equilibrium constant K is extremely large and is negative, and the M generated by the MO thermally reduced by Ma under the standard state can be spontaneously generated and can be completely generated. Furthermore, the reaction completeness of reaction 3 corresponds to the MeY employed2In relation, the degree of thermodynamic reaction is in order: MgCl2>CaCl2>SrCl2>BaCl2。
Table 2 is an equilibrium reaction (reaction 4) and related thermodynamic data for controlling oxygen levels at 550 ℃ for various molten salt media.
TABLE 2 control of equilibrium reactions at oxygen level in various molten salt media (reaction 4) and associated thermodynamic data (550 deg.C)
Table 2 shows that the molten salt medium (Ma) -MaY-MeY2The reducibility of the- (MeO) is related to the (MeO) formed, and the strength of the reducibility is in the order of: CaO (CaO)>MgO>SrO>BaO。
In order to effectively reduce the content of dissolved oxygen in tantalum powder, (Ma) - (MaY) -MeY2-(Me2O) molten salt medium, preferably MeY2＝CaCl2。
The results of the thermodynamic analysis in tables 1 and 2 provide the necessary theoretical basis for the reduction of MO to produce metal M by the alkali metal of the present invention.
3. Reducing (MeO) concentration in molten salt medium and in situ regeneration of Ma
For reinforcing reducing molten salt medium MaY-MeY2The reducing power of (Ma) - (MeO), the increase of the degree of thermal reduction, and the reduction of the oxygen content of M, the reduction of the (MeO) concentration and the in-situ regeneration of the reducing agent Ma by means of a combination of electrochemical and chemical methods are represented by the following overall reaction 5:
2(MeO)+4MaY＝4(Ma)+2MeY2+O2(g) (5)
the overall reaction (5) consists of the following i) electrochemical decomposition (MeO) and ii) chemical displacement reactions:
2(MeO)＝2(Me)+O2(g) (5a)
2(Me)+4MaY＝4(Ma)+2MeY2 (5b)
wherein, in the reactions (5a, b), the invention requires the selection of MaY and MeY2The activity ratio is high enough to make Δ G ° of reaction (5b) sufficiently negative to ensure that the concentration of (Ma) in the molten salt medium is much higher than the concentration of (Me).
The () above means that the salt, metal or metal oxide is dissolved in the molten salt medium in which they are respectively melted.
When the molten salt electrolysis is carried out under the above conditions, the corresponding amount of the lost salt may be continuously added to maintain the molten eutectic mixture salt MaOH-Ma2CO3The composition of the-MaCl is essentially unchanged.
Table 3 illustrates Me-Ca and Y-Cl as an example for the total reaction of 5 pairs of MaY-MeY2Thermodynamic data at 550 ℃ for removal (MeO) and regeneration (Ma) of a (Ma) - (MeO) molten salt medium.
TABLE 3.MaCl-CaCl2Thermodynamic data for removal (CaO) and regeneration (Ma) in (Ma) - (CaO) molten salt medium
As can be seen from the data in Table 3, MaCl-CaCl was removed by molten salt electrolysis at 550 deg.C2(CaO) and in situ regeneration (Ma) and oxygen production in a molten salt medium of- (Ma) - (CaO) require the cell voltage to be controlled to at least 3.1V. Reaction 5b had the largest value for the equilibrium constant K for the reaction when Ma ═ Na, that is, in NaCl-CaCl2The (Na) produced in the fused salt medium (Na) - (CaO) after replacement of NaCl by the (Ca) produced by reaction 5a has the highest equilibrium activity.
The order of thermodynamic stability of the alkaline earth metal oxide MeO is: CaO > MgO > SrO > BaO, and therefore, when decomposing (MeO) by molten salt electrolysis in a molten salt medium, the highest cell voltage is required for decomposition (CaO).
The invention uses molten salt electrolysis to regenerate (Me) in situ at high MaY/MeY2The concentration ratio causes (Me) substitution MaY (reaction 5b) in the molten salt medium to spontaneously generate (Ma), and MaY-MeY is realized2The (MeO) concentration is reduced and the (Ma) is regenerated in situ in the- (Ma) - (MeO) molten salt medium, so that the molten salt medium is ensured to keep extremely high reducibility all the time in the (Ma) thermal reduction MO process, and the aim of efficiently, continuously and thoroughly reducing MO to prepare M is fulfilled.
The invention specifically adopts a solid ion conduction diaphragm to carry out the thermal reduction of metal oxide MO by alkali metal Ma under the support of electrolysis to produce metal M. One solid ionic conductor is conducted by cations and the other is a solid conductor conducted by anions. At present, Na is a solid ionic conductor widely used in industry+β-Al2O3(Na2O·11Al2O3) (about 350 ℃ C. and 1200 ℃ C., Na)+Conduction) and ZrO2Radical (750 ℃ C.; 1400 ℃ C.), O2-Conductive) ion conductor (j.inorg.nucl.chem.,1967,29, 2453-; Zirconia-An OVervin, Advances in Ceramics, The American Ceramics Society, Westerville, 1-24; trans.a,1990,21A, 1223-. The former being Na+Ion conductors, mainly used in high temperature Na-S batteries and electrochemical sensors (The Sodium Sulphur Battery, Chapman and Hall, London, 1985; Phil. Trans.,1996,354, 1595-; the latter being used as O2-Ion conductors, in the field of new clean energy (e.g. high temperature solid fuel cells), sensors and high energy density batteries (materialstorage, 2003, March, 30-37).
The literature reports that when Na is used+β-Al2O3The conductor is immersed in molten other alkali metal chloride, nitrate or mixed salts thereof, Na+β-Al2O3Na in (1)+Ma of which ions will react with molten salt +The ions are subjected to ion exchange, and the Ma can be prepared by immersing in new molten salt for multiple times+β-Al2O3Conductors (J.Inorg.Nucl.chem.,1967,29, 2453-2475; Solid State Ionics,1982,7, 267-281). The present invention adopts Na in the form of a container for the method+β-Al2O3Conductor in-situ preparation of Ma+β-Al2O3A conductor. Ma obtained by any other existing preparation method+β-Al2O3Conductors can also be used in the present invention .
Example 1
Preparation of reducing molten salt medium
This example uses the mixed salt NaOH-Na2CO3NaCl as raw material and NaCl-CaCl mixture2Is a molten salt medium flux; wherein the mixed salt is NaOH-Na2CO3NaOH and Na in NaCl2CO3And the mass ratio of NaCl is 59.65:15.67: 24.68. Mixture NaCl-CaCl2Neutralizing NaCl and CaCl2In a mass ratio of 34: 66.
As shown in FIG. 1, (1) NaOH-Na was added2CO3Charging raw materials of NaCl mixed salt into Na+β-Al2O3In a container, then putting the container into NaCl-CaCl2A molten salt medium. Na (Na)+β-Al2O3The outside of the container is directly connected with NaCl-CaCl2Molten salt medium flux phase contact, so that NaOH-Na2CO3-raw NaCl feed with molten NaCl-CaCl2The molten salt medium flux is completely isolated; (2) when Na is present+β-Al2O3NaOH-Na in the container2CO3After the NaCl raw material is melted into molten salt, inserting an electronic conductor nickel rod into the molten salt as an inert anode; inserting an electron conductor iron rod into a NaCl-CaCl2 molten salt medium flux as an inert cathode; form an electrolytic cell of ' Ni rod, NaOH-Na2CO3-NaCl (anolyte) | Na + -beta-Al 2O3 | -NaCl-CaCl 2 (catholyte) ', Fe rod '.
This example uses eutectic NaOH-Na2CO3NaCl anode electrolyte is the raw material of metallic sodium reducing agent, the voltage of the electrolytic cell is controlled within the range of 2.4-2.5V at 550 ℃, auxiliary electrolysis is carried out between the inert anode and the inert cathode of the electrolytic cell shown in figure 1, NaOH is electrochemically decomposed, and NaOH-Na is subjected to 2.4-2.5V2CO3Na in NaCl anolyte2CO3And NaCl will not participate in the electrode reaction and will act as an electrolyte flux. Oxygen and water vapor, Na from NaOH, are released at the anode+Ion from Na+β-Al2O3The inner wall of the container passes through Na+β-Al2O3NaCl-CaCl with container membrane entering the outside of the container2Cathode electrolyte, and high-purity liquid Na is separated out on the inert iron cathode, and then the Na is melted into the cathode electrolyte to form NaCl-CaCl with strong reducibility2- (Na) molten salt medium.
Secondly, preparing metal by thermally reducing metal oxide with alkali metal
Heating the reducing molten salt medium prepared by the reaction device shown in figure 1 to control the temperature within 550-580 ℃, and adding Ta under the protection of argon atmosphere2O5And (3) powder. Controlling the auxiliary electrolysis current between 2 and 12 amperes, and thermally reducing Ta2O5The reaction product was removed after a duration of 10-72 hours. And washing the product with water, soaking and washing with hydrochloric acid and nitric acid water solution, further washing with water and washing with an organic solvent, and drying by using a conventional drying technology to obtain a dark gray powdery product.
Third, regeneration of alkali metal reductant
As shown in FIG. 2, (1) mixing Na2O-NaOH-Na2CO3NaCl mixture (in which Na is present)2O、NaOH、Na2CO3Mass ratio to NaCl 5:56.67:14.88:23.45) with solid Ce0.90Gd0.10O1.95Prepared with O2-A container for ion conduction; (2) the molten O containing the mixture2-The container with ion conduction function is put into the byproduct NaCl-CaCl generated in the step (II)2- (Na) - (CaO) molten salt medium; (3) after the mixture has melted completely, in the presence of molten Na2O-NaOH-Na2CO3Inserting a nickel inert anode into the NaCl medium, and generating NaCl-CaCl as a byproduct in the step (two)2Inserting a stainless steel inert cathode into the (Na) - (CaO) molten salt; form "Ni rod, Na2O-NaOH-Na2CO3NaCl (anolyte) | CeO2Radical O2-Ion solid conductor-NaCl-CaCl2- (Na) - (CaO) (catholyte), stainless steel rod "electrolytic cell; (4) carrying out electrolytic reaction on the electrolytic cell; the electrolytic voltage is 3.2V.
FIG. 3 shows the sodium thermal reduction of Ta in this example2O5X-ray diffraction (XRD) pattern of the latter product, showing the thermal reduction of Ta by sodium as described above2O5After powdering, the only product obtained was tantalum. FIG. 4 shows the sodium-thermal reduction of Ta in this example2O5FESEM scanning electron micrograph of the product tantalum powder.
Example 2
Preparation of reducing molten salt medium
In this example, a mixed salt NaOH-NaCl was used as the sodium reductant raw material, and a mixture NaCl-CaCl was used2Is a molten salt medium flux; wherein the mass ratio of NaOH to NaCl in the mixed salt NaOH-NaCl is 61.49: 38.51. Mixture NaCl-CaCl2Neutralizing NaCl and CaCl2In a mass ratio of 35: 65.
As shown in FIG. 1, (1) the NaOH-NaCl mixed salt raw material was charged with Na+β-Al2O3In a container, then putting the container into NaCl-CaCl2A molten salt medium. Na (Na)+β-Al2O3The outside of the container is directly connected with NaCl-CaCl2The flux of the molten salt medium is contacted, so that the NaOH-NaCl raw material is contacted with the molten NaCl-CaCl2The molten salt medium flux is completely isolated; (2) when Na is present+β-Al2O3After NaOH-NaCl raw materials in a container are melted into fused salt, inserting an electronic conductor nickel rod into the fused salt as an inert anode; in NaCl-CaCl2An electronic conductor iron bar is inserted into the fused salt medium flux to be used as an inert cathode; form' Ni rod, NaOH-NaCl (anolyte) | Na+β–Al2O3∣NaCl-CaCl2(catholyte), Fe-rod "cell.
In the embodiment, eutectic NaOH-NaCl anode electrolyte is used as a raw material of a sodium reducing agent, the voltage of an electrolytic cell is controlled within the range of 2.5-3.0V at 600 ℃, auxiliary electrolysis is carried out between an inert anode and an inert cathode of the electrolytic cell shown in figure 1, NaOH is electrochemically decomposed, and NaCl in the anode electrolyte does not participate in electrode reaction and plays a role of an electrolyte flux. Oxygen and water vapor, Na from NaOH, are released at the anode+Ion from Na+β-Al2O3The inner wall of the container passes through Na+β-Al2O3NaCl-CaCl with container membrane entering the outside of the container2Cathode electrolyte, high-purity Na is separated out from the inert cathode and then is melted into the cathode electrolyte to form NaCl-CaCl with strong reducibility2- (Na) molten salt medium.
Secondly, preparing metal by thermally reducing metal oxide with alkali metal
The prepared NaCl-CaCl2Controlling the temperature of the (Na) molten salt medium within the range of 600 ℃ to 630 ℃, and adding Ta under the protection of argon atmosphere2O5And (3) powder. Controlling the auxiliary electrolysis current between 2 and 12 amperes, and thermally reducing Ta2O5After lasting for 5 to 20 hours, reaction products and byproducts are obtained, wherein the byproducts are NaCl-CaCl2Molten salt of- (Na) - (CaO). And washing the product with water, soaking and washing with hydrochloric acid and nitric acid water solution, further washing with water and washing with an organic solvent, and drying by using a conventional drying technology to obtain a dark gray powdery product.
Third, regeneration of alkali metal reductant
As shown in FIG. 2, (1) mixing Na2O-NaOH-Na2CO3NaCl mixture (in which Na is present)2O、NaOH、Na2CO3Mass ratio to NaCl 5:56.67:14.88:23.45) with Ce0.90Gd0.10O1.95Prepared with O2-A container for ion conduction; (2) will contain O of the mixture2-The container with ion conduction function is put into the byproduct NaCl-CaCl generated in the step (II)2- (Na) - (CaO) molten salt; (3) in molten Na2O-NaOH-Na2CO3Inserting a nickel inert anode into the NaCl medium, and generating NaCl-CaCl as a byproduct in the step (two)2Inserting a stainless steel rod inert cathode into the (Na) - (CaO) molten salt; form "Ni rod, Na2O-NaOH-Na2CO3NaCl (anolyte) | CeO2Radical O2-Ion solid conductor-NaCl-CaCl2- (Na) - (CaO) (catholyte), stainless steel rod "electrolytic cell; (3) and electrolyzing the electrolytic cell at the electrolytic voltage of 3.1V.
FIG. 5 shows the sodium-thermal reduction of Ta in this example2O5X-ray diffraction (XRD) pattern of the post-formed product, indicating the thermal reduction of Ta by sodium as described above2O5After powdering, the only product obtained was tantalum. FIG. 6 shows the sodium-thermal reduction of Ta in this example2O5FESEM scanning electron micrograph of the product tantalum powder.
Claims (9)
1. A method for regenerating an alkali metal reducing agent in a process of preparing metal by thermally reducing metal oxide with alkali metal is characterized by comprising the following steps:
melting O2-Charging ion-conducting molten salt medium with O2-A container for ion conduction;
will contain molten O2-Of ion-conducting molten salt media with O2-The container with the function of ion conduction is put into a byproduct generated in the process of preparing metal by thermally reducing metal oxide with alkali metal;
in molten O2-Inserting inert anode into ion-conducting molten salt medium to thermally reduce metal oxide in alkali metalInserting inert cathode into corresponding by-product produced in the process of preparing metal; form an "inert anode, O2-Ion-conducting molten salt medium | O2-Ion solid conductor byproduct, inert cathode electrolytic cell;
and carrying out electrolytic reaction on the electrolytic cell.
2. The method of claim 1, wherein O is the amount of reducing agent that is used to regenerate the alkali metal during the production of metal by the thermal reduction of a metal oxide with an alkali metal2-The ion-conducting molten salt medium is Ma2O-MaOH-Ma2CO3-a MaCl medium; wherein Ma represents an alkali metal.
3. The method of claim 1, wherein the byproduct generated during the process of preparing metal by thermally reducing metal oxide with alkali metal is MaY-MeY which is a reducing molten salt medium2- (Ma) carrying out (Ma) a thermal reduction of the metal by-products produced during the process; wherein Ma represents an alkali metal, Me represents an alkaline earth metal; y represents a halogen element.
4. The method of claim 3, wherein the reducing molten salt medium MaY-MeY is used as a reducing agent in the regeneration of alkali metal reducer during the preparation of metal by the thermal reduction of metal oxide with alkali metal2- (Ma) by melting MaY-MeY2Adding auxiliary electrolytic MaOH-Ma into flux2CO3Preparing Ma generated by-MaCl molten salt.
5. The method of claim 4, wherein the byproduct of the process of preparing metal from alkali metal oxide is MaY-MeY2- (Ma) - (MeO) molten salt.
6. The method for producing a metal by thermally reducing a metal oxide with an alkali metal according to claim 1A method for regenerating an alkali metal reducing agent in a process, characterized in that said alkali metal reducing agent has O2-The ion-conducting container is made of CeO2Radical O2-A container made of an ion conductor material.
7. The method of claim 1, wherein the inert anode is selected from the group consisting of: a metal, an alloy, an electroceramic, a cermet, or graphite.
8. The method of claim 1, wherein the inert cathode is selected from the group consisting of: fe, Ni, stainless steel, Mo, W, or the same material as the metal being produced; w, Mo or the same material as the prepared metal in a fluoride molten salt system.
9. The method of claim 5, wherein the electrolysis voltage is controlled to be higher than the voltage applied to the molten MaY-MeY solution2Actual decomposition voltage of (MeO) in the (Ma) - (MeO) catholyte, lower than that of MaY and MeY2Actual decomposition voltage of the molten salt.
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