CN114016083B - Method for regenerating alkali metal reducing agent in process of preparing metal by alkali metal thermal reduction of metal oxide - Google Patents
Method for regenerating alkali metal reducing agent in process of preparing metal by alkali metal thermal reduction of metal oxide Download PDFInfo
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- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 78
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 230000008569 process Effects 0.000 title claims abstract description 35
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 33
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 15
- 230000009467 reduction Effects 0.000 title claims description 62
- 150000003839 salts Chemical class 0.000 claims abstract description 184
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- 239000006227 byproduct Substances 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 26
- 230000002829 reductive effect Effects 0.000 claims abstract description 17
- 230000004907 flux Effects 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 17
- 239000010416 ion conductor Substances 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 15
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 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
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000011195 cermet Substances 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 14
- 238000011069 regeneration method Methods 0.000 abstract description 14
- 239000011734 sodium Substances 0.000 description 73
- 238000006722 reduction reaction Methods 0.000 description 58
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 50
- 239000011780 sodium chloride Substances 0.000 description 31
- 229910052760 oxygen Inorganic materials 0.000 description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 22
- 239000004020 conductor Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 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 16
- 239000003792 electrolyte Substances 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 16
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 13
- 238000011065 in-situ storage Methods 0.000 description 12
- 238000011946 reduction process Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011532 electronic conductor Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000843 powder 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
- 229910052715 tantalum Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine 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
- 238000005342 ion exchange Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 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
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- 229910014103 Na-S Inorganic materials 0.000 description 1
- 229910020949 NaCl—CaCl2 Inorganic materials 0.000 description 1
- 229910014147 Na—S Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 150000001450 anions Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 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
- 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle 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
- 238000011084 recovery Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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
Abstract
The application discloses a method for regenerating an alkali metal reducing agent in the process of preparing metal by thermally reducing metal oxide by alkali metal. It comprises the following steps: to be melted O 2‑ Ion conducting molten salt medium charge with O 2‑ In an ion-conducting vessel; will be filled with molten O 2‑ Ion-conducting molten salt medium with O 2‑ Placing the ion-conducting container into a byproduct generated in the process of preparing metal by thermally reducing metal oxide by alkali metal; in the molten O 2‑ 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 by alkali metal; constitute "inert anode, O 2‑ Ion-conducting molten salt mediator |O 2‑ An ionic solid conductor-by-product, an inert cathode "electrolytic cell; and carrying out electrolytic reaction on the electrolytic cell. The method improves the current efficiency of auxiliary electrolysis, and is helpful for efficiently reducing the concentration of (MeO) and improving the concentration of (Ma); 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 application relates to the technical field of metal material preparation, in particular to a method for regenerating an alkali metal reducing agent in the process of preparing metal by thermally reducing metal oxide by alkali metal.
Background
Metallothermic reduction is one of the methods for preparing metals from metal compounds. The principle of the method is to use the active metal M 1 Thermal reduction of a compound M of another metal 2 X for preparing metal M 2 The total reaction is expressed as follows:
M 2 X+M 1 ＝M 2 +M 1 X (1)
reaction (1) is always exothermic, wherein M 1 Is an active metal (e.g. alkali metal, alkaline earth metal, al, si) used asA reducing agent; m is M 2 X is a metal compound, wherein M 2 Is the metal to be prepared, and X is a nonmetallic element, which may be oxygen, chlorine, fluorine, sulfur, carbon, nitrogen, etc. And M is as follows 2 In comparison, M 1 Has stronger affinity for X, that is, M 1 Thermodynamic stability ratio M of X 2 X is high. Thus, the standard reaction free energy change (Δg°) of reaction (1) is always negative. The metallothermic reduction process has been industrially applied to the production of certain high purity metals, for example, the separate thermal reduction of TiCl by magnesium 4 Or ZrCl 4 Production of titanium or Zirconium metal sponges (Trans. Electrochem. Soc.,1940,78,35-47; "Zirconium" CRC Handbook of chem. Phys.4,2007-2008,New York,CRC Press,42), K 2 TaF 7 Sodium reduction to produce tantalum metal powder (U.S. patent 3012877,1961, 12 months and 12 days), and thermite reduction of iron oxide and vanadium aluminum oxide mixtures to produce ferrovanadium alloys (Minerals eng.,2003,16,793-805).
The metallothermic reduction process requires the consumption of an excess of active metal reducing agent M 1 So that the reaction (1) is thoroughly carried out, and all the active metals are high in price, thereby improving the production cost of the thermal reduction method. From an economic standpoint, the metallothermic reduction process is only suitable for producing metals that are more expensive than the metal reducing agent. In addition, the metal thermal reduction process is accompanied by releasing a large amount of reaction heat, so that the metal products after reduction are easily sintered in situ to cause particle agglomeration and coarsening.
In the metallothermic reduction process, alkali metals (Ma) and alkaline earth metals (Me) have been widely used as reducing agents in the metallothermic reduction process for preparing various metals, which have the main disadvantages: (1) The price of alkali metal and alkaline earth metal is high, so that the cost of the reduction process is high; (2) Because of the chemical activity of alkali metal and alkaline earth metal, the direct use of the metal reducing agents causes operational danger, high safety management requirement and great difficulty; (3) The thermal reduction process releases a large amount of reaction heat, which is easy to cause local sintering of reaction products, (4) chemical corrosion to furnace lining materials is easy to occur due to strong volatility of alkali metal and alkaline earth metal at high temperature; (5) complex production process; 6) The production period is long, and the cost is high; (7) the energy consumption of the process is high; (8) The process is a mass production process, and it is difficult to achieve continuity or semicontinuity.
Alkali metals have a far lower melting point than alkaline earth metals, but only 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 ℃, whereas alkaline earth metals are more suitable for thermal reduction with higher reduction temperatures, e.g. above 750 ℃. The great advantage of low-temperature metal thermal reduction is that it can greatly reduce the heat energy loss in the process, and simultaneously effectively reduce the local sintering degree of the product, so that the structural performance of the product is more consistent.
Molten salts are widely used as reaction medium in alkali or alkaline earth metal thermal reduction. For example, U.S. Pat. No. 4992096 (12/1991) discloses a method for producing a CaCl 2 And preparing rare earth metal and alloy thereof by calcium thermal reduction of rare earth metal chloride in molten salt medium. At CaCl 2 Preparation of rare earth metals and alloys (U.S. Pat. No. 3,25/4578242,1986) by thermal reduction of rare earth metal oxides with calcium in NaCl molten salt medium, in CaCl 2 Preparation of rare earth metals and alloys thereof (U.S. Pat. No. 5314526,1994, 5, 24) by thermal reduction of rare earth metal fluorides with calcium in molten salt medium, mgCl 2 -NdCl 3 Magnesian reduction of UO in molten salt medium 2 And other actinide metal oxides recovery metal values (U.S. Pat. No. 3,1 at 590337,1994), caCl 2 -CaF 2 Thermal reduction of TiO by calcium in molten salt medium 2 Or ZrO(s) 2 Preparation of metallic titanium or zirconium (US 6117208,2000, 9, 12 days), sodium thermal reduction of Ta in alkali and alkaline earth chlorides 2 O 5 And Nb (Nb) 2 O 5 Metallic tantalum and niobium were prepared (CN 1410209a, 16, 4, 2003). The main advantages of molten salt medium are:
(i) The fused salt medium has good heat transfer property, is easy to maintain the uniformity of the medium temperature, can effectively reduce the local sintering of the reduction product, and is favorable for ensuring the consistency of the product performance;
(i i) the alkali and alkaline earth metals have a certain degree of melting in their molten halides, and certain thermal reduction reaction by-products (alkaline earth metal oxides MeO) have a considerable degree of melting in their molten halide salts, which properties facilitate the direct contact of the alkali metal reducing agent with the oxide MO and accelerate the reaction rate.
However, the above-described metallothermic reduction process directly uses calcium or sodium in metallic form as a reducing agent. Thus, despite the use of molten salt media, the above-described disadvantages (1), (2), (5), (6), (7) and (8) of the alkali metal, alkaline earth metal thermal reduction method remain insurmountable.
Patent CN105274576B discloses a method for preparing metal by continuous reduction in molten salt medium, which aims at the defects of the existing alkali metal thermal reduction oxide MO in molten salt medium to solve or overcome the following defects:
(i) The special 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 for directly adding the alkali metal reducing agent are overcome; solves the problems of high requirements and great difficulty in the safety management of alkali metal treatment and operation;
(ii) Auxiliary electrolysis of alkaline earth metal oxide-containing MeO molten salt medium to generate and regenerate alkali metal reducing agent in situ: solves the problem that the prior alkali metal thermal reduction is excessive in use of the alkali metal reducing agent; overcomes the defect that the existing batch production process of metal thermal reduction is difficult to realize continuity.
The process of patent CN105274576B is carried out by melting MaY-MeY 2 Adding MeO-MeY mixture into flux, and preparing reducing molten salt medium MaY-MeY by auxiliary electrolysis 2 - (Ma) then in a reducing molten salt medium MaY-MeY 2 Adding metal oxide into- (Ma) to make electrolysis to prepare metal material. In the actual production process, the regeneration efficiency of alkali metal is low by the special CN105274576B method, so that the production efficiency of preparing metal by thermally reducing metal oxide by alkali metal is affected.
It should be noted that the information disclosed in the above background section is only for enhancing understanding of the background of the application and thus may include information that does not form the prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
The present application aims to solve, at least to some extent, one of the technical problems indicated in the background art.
The technical problems to be solved by the application are realized by the following technical scheme:
a method for regenerating an alkali metal reducing agent in the preparation of metals from alkali metal thermal reduction metal oxides comprising the steps of:
to be melted O 2- Ion conducting molten salt medium charge with O 2- In an ion-conducting vessel;
will be filled with molten O 2- Ion-conducting molten salt medium with O 2- Placing the ion-conducting container into a byproduct generated in the process of preparing metal by thermally reducing metal oxide by alkali metal;
in the molten O 2- 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 by alkali metal; constitute "inert anode, O 2- Ion-conducting molten salt mediator |O 2- An ionic solid conductor | by-product, an inert cathode "electrolytic cell;
then, the electrolytic cell is subjected to electrolysis.
The inventor finds that through a great deal of experimental study: in the molten O 2- 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 by alkali metal; constitute "inert anode, O 2- Ion-conducting molten salt mediator |O 2- The ionic solid conductor-by-product, inert cathode "electrolytic cell, undergoes electrolytic reaction so that the anode and cathode electrolytes are replaced by O 2- The ion conductor vessel diaphragms being completely separated, only O 2- Ion energy in anode and cathode electrolytes and O 2- Migration within the ion conductor membrane. The solid-liquid contact area is larger than that of the traditional solid-solid interface, thus being beneficial to improving O 2- The ion migration efficiency can greatly improve the current efficiency of auxiliary electrolysis; the defect of the reverse reaction between anodic oxygen and the reducing molten salt medium in the patent CN105274576B is overcome, and the concentration of (MeO) is effectively reduced and the concentration of (Ma) is improved; improves the regeneration efficiency of alkali metal, and further improves the oxidation of alkali metal by thermal reductionAnd the production efficiency of the metal prepared by the product is improved.
The patent CN105274576B is an application of the inventor in the earlier stage, and the inventor further discovers that the technical problem of low production efficiency exists in the process of preparing the metal material by adopting the method of the patent CN105274576B in actual production; in order to solve the technical problem of low production efficiency, the inventor searches for the reason of low production efficiency through a large number of experimental researches, and finally discovers that: the method adopting the patent CN105274576B is to prepare a reducing molten salt medium by taking a MeO/MaY mixture as a raw material, and the speed of melting 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 unmelted MeO; and the increase in viscosity of the molten salt leads to a reduction rate decrease, which in turn leads to a low production efficiency. The method for regenerating the alkali metal reducing agent in the process of preparing metal by thermally reducing the metal oxide of the alkali metal can remove MeO while regenerating the alkali metal; therefore, the method can also solve the technical problems that the speed of melting MeO in a molten salt medium is too slow near a reaction product in the method of CN105274576B, and the unmelted MeO increases the viscosity of surrounding molten salt, thereby promoting the improvement of production efficiency.
In addition, the inventors have found that the rate of dissolution of MeO in the molten salt medium near the reaction product is too slow, and unmelted MeO increases the viscosity of the surrounding molten salt; the uniformity of 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 uniformity of a product is easily deteriorated due to the local or excessive sintering of a metal product; and at the same time, the energy consumption and the production cost are increased. The method for regenerating the alkali metal reducing agent in the process of preparing metal by thermally reducing the metal oxide of the alkali metal can remove MeO while regenerating the alkali metal; therefore, the method can also solve the technical problems that the speed of melting MeO in a molten salt medium is too slow near a reaction product in the method of CN105274576B, and the unmelted MeO increases the viscosity of surrounding molten salt, so that the technical problems of poor product consistency and high energy consumption in the method of CN105274576B are solved.
Preferably, said O 2- The ion conduction molten salt medium is Ma 2 O-MaOH-Ma 2 CO 3 -a mecl medium; wherein Ma represents an alkali metal.
Preferably, the byproduct generated in the process of preparing metal by thermally reducing metal oxide by alkali metal is a reducing molten salt medium MaY-MeY 2 - (Ma) carrying out (Ma) thermal reduction of by-products produced during the metal process; wherein, ma represents an alkali metal, and Me represents an alkaline earth metal; y represents a halogen element.
Further preferably, the reducing molten salt medium is MaY-MeY 2 - (Ma) is obtained by melting MaY-MeY 2 Adding auxiliary electrolytic MaOH-Ma into flux 2 CO 3 -MaCl molten salt generated Ma.
The method comprises the following specific steps:
in the form of mixed salt MaOH-Ma 2 CO 3 -MaCl as starting material for Ma, in mixture of MaY-MeY 2 A flux for thermally reducing molten salt medium; charging a mixed salt feedstock into Ma + Ion-conducting vessels will then have Ma + Ion conductive container is put into MaY-MeY 2 In the fused salt medium flux, there is Ma + The ion-conducting vessel is used as a membrane, the outside of which is directly associated with May-MeY 2 Molten salt medium flux contacts so that molten MaOH-Ma 2 CO 3 -MaCl molten salt and MaY-MeY 2 Completely isolating the fused salt medium flux;
in MaOH-Ma 2 CO 3 -inserting an electron conductor rod into the magl molten salt as an inert or graphite anode; in MaY-MeY 2 Inserting an electronic conductor bar into the fused salt medium flux to serve as an inert cathode; constitute "inert or graphite anode, maOH-Ma 2 CO 3 -mecl (anolyte) |ma+ ion solid conductor|may-MeY 2 (catholyte), inert cathode "electrolytic cells;
carrying out electrolytic reaction on the electrolytic cell to obtain the reducing molten salt medium MaY-MeY 2 - (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-Ma 2 CO 3 Further research shows that MaCl is produced by adopting the method of Chinese application patent CN105274576B in preparation of reducing molten salt mediumThe dissolution of the Ma into molten salt medium can cause the remarkable increase of the electron conductivity ratio of the medium and the decrease of the electrolysis current efficiency, thereby leading to the low efficiency of preparing the Ma reducer, and finally leading to the low production efficiency, the high energy consumption and the high production cost in the production process.
Based on the findings, the inventors have found that MaOH-Ma during electrolysis 2 CO 3 -molten salt of MaCl is placed in a molten salt bath with Ma + In an ion-conducting vessel; will then have Ma + Ion-conducting vessels into molten May-MeY 2 In the fused salt medium flux, there is Ma + Ion-conducting container exterior directly to May-MeY 2 Molten salt medium flux is contacted to make MaOH-Ma 2 CO 3 -MaCl molten salt and molten MaY-MeY 2 Completely isolating the fused salt medium flux; constitute "inert anode, maOH-Ma 2 CO 3 -mecl (anolyte) |ma + Ion solid conductor |MaY-MeY 2 (catholyte), inert cathode "electrolytic cells. Based on the electrolytic cell, the problem that MaY-MeY is formed after electrolysis in Chinese patent No. CN105274576B is overcome 2 The- (Ma) molten salt medium has the defect of ion/electron mixed conduction, and greatly improves the current efficiency of electrolysis so as to realize efficient preparation of the Ma reducer, and finally promote the improvement of the production efficiency and the reduction of the energy consumption in the production process.
The method adopting the patent CN105274576B is to prepare a reducing molten salt medium by taking a MeO/MaY mixture as a raw material, and the speed of melting 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 unmelted MeO; and the increase in viscosity of the molten salt leads to a reduction rate decrease, which in turn leads to a low production efficiency. Based on the findings of this reason, the inventors replaced the raw material MeO/MaY in patent CN105274576B with the raw material MaOH-Ma 2 CO 3 MaCl is used for preparing the reducing molten salt medium, and an inert anode, maOH-Ma is adopted 2 CO 3 -mecl (anolyte) |ma + Ion solid conductor |MaY-MeY 2 (catholyte), an inert cathode "cell" can be used to electrolyze the raw material MaOH-Ma 2 CO 3 -MaClMaY-MeY 2 Isolating so that the molten salt medium flux MaY-MeY 2 The MeO added in the adding part is not added, so that the melting of the generated MeO is facilitated, and the problem that the speed of melting the MeO in a molten salt medium is too slow is solved; and further, the method successfully solves the problems that the reduction speed is reduced and the production efficiency is low due to the fact that the speed of melting MeO in a molten salt medium is too slow near a reaction product in the method of the patent CN 105274576B.
In addition, an "inert anode, maOH-Ma" is used 2 CO 3 -mecl (anolyte) |ma + Ion solid conductor |MaY-MeY 2 The inert cathode electrolytic cell is used for electrolysis, so that the anode product oxygen and water vapor are completely separated from the cathode product alkali metal Ma, and the reverse reaction of the oxygen and the active metal Ma is avoided. By placing an inert cathode in the MaY-MeY 2 The molten salt medium flux is at different positions, so that Ma can be separated out from a cathode at any required position in the molten salt medium flux and is locally fused into the molten salt medium flux to diffuse to the periphery of the cathode, and the MO homogenizing and thermal reduction process of the Ma in the medium is enhanced.
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, the said one with Ma + The active material in the ion-conducting vessel being a solid conductor Ma + β-Al 2 O 3 。
Preferably, the said one with Ma + The ion conduction container is prepared by the following method: will be made of Na 2 O and Al 2 O 3 Na prepared from raw materials + β-Al 2 O 3 The container is immersed in a solution containing Ma + Ion exchange is carried out in the ion molten salt to obtain the Ma-containing material + A container for ion conduction;
alternatively, the said one with Ma + The ion-conducting container is made of Ma oxide or carbonate and Al 2 O 3 Is prepared from the raw materials.
Preferably, said composition contains Ma + The molten salt of the ion is MaY-MeY 2 The molten salt is mixed.
Preferably, the materials of the inert cathode and the inert anode electron conductor bars are the same or different in the preparation of the reductive molten salt medium electrolysis reaction.
Preferably, an inert anode and an inert cathode are selected for the auxiliary electrolysis process;
wherein the material of the inert anode electron conductor bar is selected from the group consisting of: metals, alloys, electronic ceramics, cermets; the material of the inert cathode electron conductor bar is selected from Fe, ni, stainless steel, mo and W or the same material as the prepared metal in a chloride molten salt system; in the fluoride molten salt system, W, mo or the same material as the prepared metal.
Preferably, in the preparation of the reducing molten salt medium electrolysis reaction, the electrolysis voltage in the electrolysis reaction is controlled to be higher than the actual decomposition voltage of MaOH/lower than Ma 2 CO 3 Or higher than Ma 2 CO 3 Is lower than the actual decomposition voltage of the mecl or is higher than the actual decomposition voltage of the mecl.
Most preferably, in the preparation of the reducing molten salt medium electrolytic reaction, the actual electrolytic voltage in the electrolytic reaction is controlled to be higher than the actual decomposition voltage of MaOH/lower than Ma 2 CO 3 The actual decomposition voltage ensures the current efficiency of electrolysis, reduces the electric energy consumption, and ensures that only oxygen and water vapor are released at the anode, so that the process has the advantages of green and environmental protection.
Preferably, the byproduct generated in the process of preparing metal by thermally reducing metal oxide of alkali metal is MaY-MeY 2 - (Ma) - (MeO) molten salt.
Preferably, the said catalyst has O 2- The ion-conducting container is made of CeO 2 Radical O 2- A container made of ion conductor material.
Most preferably, said CeO 2 Radical O 2- The ion conductor material is Ce 0.90 Gd 0.10 O 1.95 。
Preferably, the material of the inert anode is selected from: a metal, alloy, electronic ceramic, cermet, or graphite.
Preferably, the material of the inert cathode is selected from: in a chloride molten salt system, a material selected from Fe, ni, stainless steel, mo, W, or the same as the prepared metal; in the fluoride molten salt system, W, mo or the same material as the prepared metal.
Preferably, the electrolysis voltage in the electrolysis reaction is controlled to be higher than that of the electrolysis solution in the molten MaY-MeY 2 The actual decomposition voltage of (MeO) in the- (Ma) - (MeO) catholyte is lower than that of MaY and MeY 2 The actual decomposition voltage of the molten salt.
In the present application "-" represents a composition, e.g. Ma 2 O-MaOH-Ma 2 CO 3 -MaCl medium representation by Ma 2 O、MaOH、Ma 2 CO 3 And a medium composed of MaCl.
The beneficial effects are that: the method has the advantages that (1) common metal or alloy can be conveniently used for replacing noble metal with high value as an oxygen inert anode material, and the cost is reduced; (2) By O 2- Ion conductive molten salt medium (melt Ma) 2 O-MaOH-Ma 2 CO 3 -MaCl)∣O 2- Ion solid conductor (CeO) 2 Radical O 2- Solid conductor) having a larger contact area than conventional solid-solid interfaces, contributing to an improvement in O 2- Ion migration efficiency; (3) Using "inert anodes, O 2- Ion-conducting molten salt medium (anode electrolyte) | CeO 2 Radical O 2- Ionic solid conductor-byproduct (catholyte), inert cathode "liquid O of electrolytic cell 2- Ion molten salt medium Ma 2 O-MaOH-Ma 2 CO 3 -MaCl and solid CeO 2 Radical O 2- Ion conductors (e.g. Ce 0.90 Gd 0.10 O 1.95 ) Solid-liquid combination O 2- The ion conductor system can exclude O 2- The ion solid conductor may have electron conduction effect inside, so that the system is pure O 2- The ion conductor can greatly improve the current efficiency of auxiliary electrolysis; (4) O (O) 2- Ion solid conductor (CeO) 2 Radical O 2- Solid electrolyte) container also overcomes the inert anode evolved oxygen and oxygen in patent CN105274576BThe defect of reverse reaction of the reducing molten salt medium is beneficial to efficiently reducing the concentration of (MeO) and improving the concentration of (Ma), so that the reducibility and the metal thermal reduction capability of the external molten salt medium are enhanced; (5) The molten Ma is filled in 2 O-MaOH-Ma 2 CO 3 O of MaCl anolyte 2- When the ion conductor vessel is naturally cooled from its outer molten salt medium, the presence of the inner molten medium helps to mitigate O 2- The ion conductor is cooled down quickly, so that the cracking of the container material caused by thermal shock can be prevented, and the solid O is prolonged 2- The service life of the ion conductor is prolonged, and the cost is reduced; (6) The (MeO) concentration of the reducing molten salt medium is reduced in time, the medium viscosity is also reduced, the speed of melting the MeO in the molten salt medium and the efficiency of removing the (MeO) are improved, the thermodynamic driving force of (Ma) thermal reduction MO is enhanced, the in-situ regeneration yield of the Ma is improved, and the production cost is reduced; (7) Molten ionic medium (Ma) 2 O-MaOH-Ma 2 CO 3 -MaCl) and solid CeO 2 Radical O 2- Ion conductors (e.g. Ce 0.90 Gd 0.10 O 1.95 ) Form solid-liquid combination O 2- Ion-conducting system ensuring that the system is pure O 2- Conductors, also facilitating the use of low-priced O 2 Noble metal O with noble value avoided by inert anode 2 An inert anode material; (8) Using molten Ma 2 The O-MaOH electrolyte and the inert anode releasing oxygen can realize green and environment-friendly production in the in-situ regeneration process of removing (MeO) and (Ma) of the external reducing 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 application.
Fig. 2 is a schematic diagram of a process for regenerating an alkali metal reducing agent during the preparation of metals from alkali metal thermal reduction metal oxides.
FIG. 3 is a sodium thermal reduction Ta of example 1 2 O 5 X-ray diffraction (XRD) pattern of the tantalum powder product.
FIG. 4 is a sodium thermal reduction Ta of example 1 2 O 5 FESEM scanning electron micrograph of the tantalum powder product.
FIG. 5 is an implementationEXAMPLE 2 sodium thermal reduction of Ta 2 O 5 X-ray diffraction (XRD) pattern of the tantalum powder product.
FIG. 6 is a sodium thermal reduction Ta of example 2 2 O 5 FESEM scanning electron micrograph of the tantalum powder product.
Detailed Description
The present application is further explained below with reference to specific examples, which are not intended to limit the present application in any way.
The principle of medium reduction (MeO) concentration and in-situ regeneration of Ma of the reducing molten salt medium and the reaction principle in the application process are as follows:
1. electrochemical process for in situ preparation of alkali metal Ma reducing agents
Electrochemical decomposition of eutectic salt MaOH-Ma 2 CO 3 MaOH, ma in MaCl System 2 CO 3 And mecl are represented by the following reactions, respectively:
4(MaOH)＝4(Ma)+O 2 (g)+2H 2 O
(2a)
2(Ma 2 CO 3 )＝4Ma+O 2 (g)+2CO 2 (g) (2b)
2(MaCl)＝2Ma+Cl 2 (g) (2c)
addition of Ma to molten MaOH 2 CO 3 And the purpose of the MaCl is to be able to properly reduce the activity of the MaOH molten salt and the melting point of the molten salt mixture. Standard free energy change Δg of reaction 2 above 0 550℃ All positive values indicate that these reactions do not proceed spontaneously, but that these alkali metal salts are decomposed by molten salt electrolysis. Taking ma=na as an example, at 550 ℃, the standard cell potential values for reactions (2 a), (2 b) and (2 c) are respectively: -2.4, -2.6 and-3.5V. For example, controlling the cell voltage to be 2.4-2.6V, the reaction (2 a) will occur, naOH will be decomposed, na will be separated out from the cathode, O will be released from the inert anode 2 (g) And H 2 O (g). Through auxiliary electrolysis, ma is separated out at a cathode and then is melted in a fused salt medium MaY-MeY 2 Form the reducing molten salt medium MaY-MeY 2 -(Ma)。
2. Preparation of metal M by thermal reduction of MO by alkali metal Ma in reducing molten salt medium
The Ma thermal reduction MO is represented by reaction 3:
MO+2(Ma)+MeY 2 ＝M+2MaY+(MeO) (3)
wherein in the reaction (3), (MeO) is a reaction byproduct of the reaction (3), and is then dissolved in the reducing MaY-MeY 2 Formation of May-MeY in- (Ma) molten salt medium 2 -(Ma)-(MeO)。MeY 2 Also participate in the Ma thermal reduction MO reaction, and MeY exists in the fused salt medium 2 So that ΔG of reaction 3 0 2 The thermodynamic driving force of the Ma thermal reduction MO for preparing the metal M is further improved.
Molten salt medium MaY-MeY formed in process of thermally reducing MO by Ma 2 The reducing power (or reducibility) of the- (Ma) - (MaO) is expressed by the oxygen level of the molten salt medium, the lower the oxygen level, the stronger the reducing power (or reducibility) of the molten salt medium. Molten salt medium MaY-MeY 2 The oxygen position of- (Ma) - (MaO) is controlled by the (Me)/(MeO) balance:
(Me)+1/2O 2 ＝(MeO) (4)
the equilibrium oxygen position is expressed by the following formula:
wherein, the liquid crystal display device comprises a liquid crystal display device,is MaY-MeY 2 - (Ma) - (MaO) equilibrium oxygen position of molten salt medium, K is the equilibrium constant of reaction (4), a Meo And a Me The activities of MeO and Me in the molten salt medium are respectively. The lower the oxygen level, the more reducing power (or reducibility) the molten salt medium. Equation 1 shows that at a certain temperature, the molten salt medium MaY-MeY 2 - (Ma) - (MaO) equilibrium oxygen positionThe ratio is proportional and inversely proportional to the reducing power. Decrease->The value can reduce the oxygen level of molten salt medium and improve the reducing capability of the medium, and finally is helpful for strengthening the Ma thermal reduction MO process.
Table 1 provides a table with mo=ta 2 O 5 Y=cl and ma=na, K, li; me=ca, mg, ba and Sr are examples, thermodynamic data for reaction 3 at 550 ℃.
TABLE 1 MaCl-MeCl 2 - (Ma) hot reduction of Ta in molten salt medium at 550 DEG C 2 O 5 Thermodynamic data for the preparation of metallic tantalum
As can be seen from Table 1, the standard free energy change (. DELTA.G. °) of reaction 3 550℃ ) The equilibrium constant K is extremely large and the M can be spontaneously generated by the Ma thermal reduction MO under the standard state, and the M can be completely generated. In addition, the reaction completion of reaction 3 was equal to that of MeY employed 2 Regarding the degree of thermodynamic reaction, the order is: mgCl 2 >CaCl 2 >SrCl 2 >BaCl 2 。
Table 2 is the equilibrium reaction (reaction 4) and related thermodynamic data for controlling the oxygen level of various molten salt media at 550 ℃.
TABLE 2 equilibrium reaction (reaction 4) controlling oxygen level of various molten salt media and related thermodynamic data (550 ℃ C.)
Table 2 shows that the molten salt medium (Ma) -MaY-MeY 2 The reducibility of the- (MeO) is related to the generated (MeO), and the reducibility is as follows: caO (CaO)>MgO>SrO>BaO。
In order to effectively reduce the content of dissolved oxygen in tantalum powder, the oxygen concentration of the tantalum powder is reduced by (Ma) - (MaY) -MeY 2 -(Me 2 O) in a molten salt medium, preferably MeY 2 ＝CaCl 2 。
The thermodynamic analysis results in tables 1 and 2 provide the necessary theoretical basis for the preparation of metal M by the alkali metal reduction MO of the present application.
3. Reducing (MeO) concentration in molten salt medium and in situ regeneration of Ma
To enhance the reducing molten salt medium MaY-MeY 2 The reducing power of- (Ma) - (MeO), the increasing degree of thermal reduction, and the decreasing of the oxygen content of M, the reduction of (MeO) concentration and the in situ regeneration of the reducing agent Ma using a combination of electrochemical and chemical methods are represented by the following overall reaction 5:
2(MeO)+4MaY＝4(Ma)+2MeY 2 +O 2 (g) (5)
the overall reaction (5) consists of i) electrochemical decomposition (MeO) and ii) chemical displacement reactions:
2(MeO)＝2(Me)+O 2 (g) (5a)
2(Me)+4MaY＝4(Ma)+2MeY 2
(5b)
wherein in the reactions (5 a, b), the application calls for a selection of MaY and MeY 2 The activity ratio is high enough to give the Δg° of reaction (5 b) a sufficiently large negative value to ensure that the concentration of (Ma) in the molten salt medium is much higher than the concentration of (Me).
The above () indicates that the salt, metal or metal oxide, respectively, is dissolved in the corresponding molten salt medium.
When the molten salt electrolysis is carried out under the above conditions, a corresponding loss amount of salt may be continuously added to maintain the molten eutectic salt MaOH-Ma 2 CO 3 The composition of the MaCl is essentially unchanged.
Table 3 is based on the total reaction 5 pair MaY-MeY, taking Me=Ca and Y=Cl as examples 2 Thermodynamic data of (Ma) - (MeO) molten salt medium at 550 ℃ were performed for removal (MeO) and regeneration (Ma).
TABLE 3 MaCl-CaCl 2 Thermodynamic data of removal (CaO) and regeneration (Ma) in- (Ma) - (CaO) molten salt medium
As can be seen from the data in Table 3, the removal of MaCl-CaCl by molten salt electrolysis at 550 ℃ 2 (CaO) in a- (Ma) - (CaO) molten salt medium and in-situ regeneration (Ma) and oxygen production, require cell voltages of at least 3.1V. When ma=na, reaction 5b has the greatest reaction equilibrium constant K value, that is, at nacl—cacl 2 (Na) produced after the (Ca) produced by reaction 5a replaced NaCl in the- (Na) - (CaO) molten salt medium has the highest equilibrium activity.
The order of thermodynamic stability of the alkaline earth oxide MeO is: caO > MgO > SrO > BaO, therefore, when decomposing (MeO) by molten salt electrolysis in a molten salt medium, the highest cell voltage is required for the decomposition (CaO).
The application adopts molten salt electrolysis in-situ regeneration (Me) to obtain high MaY/MeY 2 Concentration ratio (Me) in molten salt medium is used for spontaneously generating (Ma) by replacing MaY (reaction 5 b), so that MaY-MeY is realized 2 The concentration of (MeO) is reduced in the (Ma) - (MeO) molten salt medium and the (Ma) is regenerated in situ, so that the molten salt medium is ensured to always maintain extremely high reducibility in the process of (Ma) thermal reduction of MO so as to achieve the purpose of efficiently, continuously and thoroughly reducing MO to prepare M.
The application specifically adopts a solid ion conduction diaphragm to carry out the hot reduction of alkali metal Ma to metal oxide MO under the support of electrolysis to produce metal M. One solid ion conductor is conducted by cations and the other is conducted by anions. At present, the solid ion conductor widely used in industry is Na + β-Al 2 O 3 (Na 2 O·11Al 2 O 3 ) (about 350-1200 ℃ C., na) + Conduction) and ZrO 2 Radical (750-1400 ℃ C., O) 2- Conduction) ionic conductors (j.inorg.nucleic.chem., 1967,29,2453-2475; zirconia-An overlay. In. Advances in Ceramics, the American Ceramic Society, westerville,1-24; metall. Trans. A,1990,21A, 1223-1250). The former is Na + Ion conductors, mainly used in high temperature Na-S cells and electrochemical sensors (The Sodium Sulphur Battery, chapman and Hall, london,1985; phil. Trans.,1996,354,1595-1612); the latter is used as O 2- Ion conductor, application to new clean energy sources (e.g., high temperature solid fuel cells), sensor and high energyBulk density batteries (Material store, 2003, march, 30-37).
The literature has reported that when Na + β-Al 2 O 3 The conductor is immersed in molten other alkali metal chloride, nitrate or mixed salt thereof, na + β-Al 2 O 3 Na of (a) + The ions will be associated with Ma of molten salt + Ion exchange is carried out on the ions, and Ma can be prepared by immersing the ions in new fused salt for a plurality of times + β-Al 2 O 3 Conductors (J.Inorg.Nucl.chem., 1967,29,2453-2475;Solid State Ionics,1982,7,267-281). The application adopts the Na in the form of a container for the method + β-Al 2 O 3 In situ preparation of conductors Ma + β-Al 2 O 3 A conductor. Ma obtained by any other existing preparation method + β-Al 2 O 3 Conductors can also be used in the present application .
Example 1
1. Preparation of a reducing molten salt medium
This example uses mixed salt NaOH-Na 2 CO 3 -NaCl as raw material, the mixture NaCl-CaCl 2 Is a fused salt medium flux; wherein the mixed salt is NaOH-Na 2 CO 3 NaOH, na in NaCl 2 CO 3 And the mass ratio of NaCl is 59.65:15.67:24.68. Mixture NaCl-CaCl 2 Neutral NaCl and CaCl 2 The mass ratio of (2) was 34:66.
As shown in FIG. 1, (1) NaOH-Na 2 CO 3 Charging NaCl mixed salt raw material into Na + β-Al 2 O 3 The container is put into NaCl-CaCl 2 Molten salt medium. Na (Na) + β-Al 2 O 3 The outside of the container is directly connected with NaCl-CaCl 2 Molten salt medium flux contacts so that NaOH-Na 2 CO 3 -NaCl raw material and molten NaCl-CaCl 2 Completely isolating the fused salt medium flux; (2) When Na is + β-Al 2 O 3 NaOH-Na in a vessel 2 CO 3 After the NaCl raw material is melted into molten salt, inserting an electronic conductor nickel rod into the molten salt to serve as an inert anode; inserting an electronic conductor iron rod into NaCl-CaCl2 molten salt medium flux to serve as an inert cathode;the "Ni rod, naOH-Na2CO3-NaCl (anode electrolyte) |Na+ -beta-Al 2O 3|NaCl-CaCl 2 (cathode electrolyte), fe rod" electrolytic cell was constructed.
This example uses eutectic NaOH-Na 2 CO 3 The NaCl anode electrolyte is used as the raw material of the metal sodium reducing agent, the voltage of the electrolytic cell is controlled to be in the range of 2.4-2.5V at 550 ℃, auxiliary electrolysis is carried out between the anode and the inert cathode of the electrolysis Chi Duoxing shown in figure 1, and NaOH is electrochemically decomposed under the condition of 2.4-2.5V 2 CO 3 Na in NaCl anolyte 2 CO 3 And NaCl will not participate in the electrode reaction and act as an electrolyte flux. Oxygen and water vapor are released at the anode, na from NaOH + Ion from Na + β-Al 2 O 3 The inner wall of the container passes through Na + β-Al 2 O 3 NaCl-CaCl entering the container from the container diaphragm 2 A cathode electrolyte, and high-purity liquid Na is separated out on an inert iron cathode, and then the Na is melted into the cathode electrolyte to form NaCl-CaCl with strong reducibility 2 - (Na) molten salt medium.
2. Preparation of metals by thermal reduction of metal oxides from alkali metals
Heating the reducing molten salt medium prepared by the reaction device shown in figure 1 at 550-580 ℃ and adding Ta under the protection of argon atmosphere 2 O 5 And (3) powder. Controlling the auxiliary electrolysis current between 2 and 12 amperes, and thermally reducing Ta 2 O 5 After a duration of 10-72 hours the reaction product is removed. Washing the product with water, immersing in aqueous solution of hydrochloric acid and nitric acid, washing with water and organic solvent, and drying with conventional drying technology to obtain dark grey powdery product.
3. Regeneration of alkali metal reducing agents
As shown in FIG. 2, (1) Na 2 O-NaOH-Na 2 CO 3 NaCl mixture (wherein Na 2 O、NaOH、Na 2 CO 3 Mass ratio to NaCl of 5:56.67:14.88:23.45) was charged with solid Ce 0.90 Gd 0.10 O 1.95 Made with O 2- In an ion-conducting vessel; (2) Melting the mixtureFused O 2- Placing the ion conduction container into the by-product NaCl-CaCl formed in the step (two) 2 - (Na) - (CaO) molten salt medium; (3) After the mixture is thoroughly melted, the mixture is melted with Na 2 O-NaOH-Na 2 CO 3 Inserting a nickel inert anode into the NaCl medium, and forming a byproduct NaCl-CaCl in the step (II) 2 Inserting a stainless steel inert cathode into the- (Na) - (CaO) molten salt; constitute "Ni rod, na 2 O-NaOH-Na 2 CO 3 -NaCl (anolyte) | CeO 2 Radical O 2- Ion solid conductor | NaCl-CaCl 2 - (Na) - (CaO) (catholyte), stainless steel rod "electrolytic cell; (4) carrying out electrolytic reaction on the electrolytic cell; the electrolysis voltage is 3.2V.
FIG. 3 shows the sodium thermal reduction of Ta 2 O 5 X-ray diffraction (XRD) patterns of the post-product, showing Ta being thermally reduced by sodium as described above 2 O 5 After the powder, the product obtained is tantalum only. FIG. 4 shows the sodium thermal reduction of Ta 2 O 5 FESEM scanning electron micrograph of the tantalum powder product.
Example 2
1. Preparation of a reducing molten salt medium
In this example, mixed salt NaOH-NaCl was used as the raw material of sodium reducing agent, and the mixture NaCl-CaCl was used 2 Is a fused salt medium flux; wherein the mass ratio of NaOH to NaCl in the mixed salt NaOH-NaCl is 61.49:38.51. Mixture NaCl-CaCl 2 Neutral NaCl and CaCl 2 The mass ratio of (2) is 35:65.
As shown in FIG. 1, (1) NaOH-NaCl mixed salt raw material is charged into Na + β-Al 2 O 3 The container is put into NaCl-CaCl 2 Molten salt medium. Na (Na) + β-Al 2 O 3 The outside of the container is directly connected with NaCl-CaCl 2 Molten salt medium flux is contacted to make NaOH-NaCl raw material and molten NaCl-CaCl 2 Completely isolating the fused salt medium flux; (2) When Na is + β-Al 2 O 3 After the NaOH-NaCl raw material in the container is melted into molten salt, inserting an electronic conductor nickel rod into the molten salt to serve as an inert anode; in NaCl-CaCl 2 Inserting electronic conductor iron rod into molten salt medium flux as inert cathodeThe method comprises the steps of carrying out a first treatment on the surface of the Constitute "Ni rod, naOH-NaCl (anode electrolyte) —Na + β–Al 2 O 3 ∣NaCl-CaCl 2 (catholyte), fe rod "cell.
In the embodiment, eutectic NaOH-NaCl anode electrolyte is taken as a raw material of a sodium reducing agent, the voltage of an electrolytic cell is controlled to be in the range of 2.5-3.0V at 600 ℃, auxiliary electrolysis is carried out between an anode and an inert cathode of the electrolysis Chi Duoxing shown in fig. 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 are released at the anode, na from NaOH + Ion from Na + β-Al 2 O 3 The inner wall of the container passes through Na + β-Al 2 O 3 NaCl-CaCl entering the container from the container diaphragm 2 A cathode electrolyte, and high-purity liquid Na is separated out on an inert cathode, and then the Na is melted into the cathode electrolyte to form NaCl-CaCl with strong reducibility 2 - (Na) molten salt medium.
2. Preparation of metals by thermal reduction of metal oxides from alkali metals
The prepared NaCl-CaCl 2 The heat of the- (Na) fused salt medium is controlled within 600-630 ℃, and Ta is added under the protection of argon atmosphere 2 O 5 And (3) powder. Controlling the auxiliary electrolysis current between 2 and 12 amperes, and thermally reducing Ta 2 O 5 The reaction product and the byproducts are obtained after lasting for 5 to 20 hours, and the byproducts are NaCl-CaCl 2 - (Na) - (CaO) molten salt. Washing the product with water, immersing in aqueous solution of hydrochloric acid and nitric acid, washing with water and organic solvent, and drying with conventional drying technology to obtain dark grey powdery product.
3. Regeneration of alkali metal reducing agents
As shown in FIG. 2, (1) Na 2 O-NaOH-Na 2 CO 3 NaCl mixture (wherein Na 2 O、NaOH、Na 2 CO 3 Mass ratio to NaCl of 5:56.67:14.88:23.45) was charged with Ce 0.90 Gd 0.10 O 1.95 Made with O 2- In an ion-conducting vessel; (2) O to be filled with the mixture 2- Ion-conducting containers are placedThe byproduct NaCl-CaCl generated in the step (two) 2 - (Na) - (CaO) molten salt; (3) In molten Na 2 O-NaOH-Na 2 CO 3 Inserting a nickel inert anode into the NaCl medium, and forming a byproduct NaCl-CaCl in the step (II) 2 Inserting a stainless steel rod inert cathode into the- (Na) - (CaO) molten salt; constitute "Ni rod, na 2 O-NaOH-Na 2 CO 3 -NaCl (anolyte) | CeO 2 Radical O 2- Ion solid conductor | NaCl-CaCl 2 - (Na) - (CaO) (catholyte), stainless steel rod "electrolytic cell; (3) And (3) electrolyzing the electrolytic cell, wherein the electrolysis voltage is 3.1V.
FIG. 5 shows the sodium thermal reduction of Ta 2 O 5 X-ray diffraction (XRD) patterns of the resulting product showed Ta thermally reduced by sodium as described above 2 O 5 After the powder, the product obtained is tantalum only. FIG. 6 is a sodium thermal reduction Ta of the present example 2 O 5 FESEM scanning electron micrograph of the tantalum powder product.
Claims (5)
1. A method for regenerating an alkali metal reducing agent in the preparation of metals from alkali metal thermal reduction metal oxides, comprising the steps of:
to be melted O 2- Ion conducting molten salt medium charge with O 2- In an ion-conducting vessel;
will be filled with molten O 2- Ion-conducting molten salt medium with O 2- Placing the ion-conducting container into a byproduct generated in the process of preparing metal by thermally reducing metal oxide by alkali metal;
in the molten O 2- Inserting an inert anode into the ion-conducting molten salt medium, and inserting an inert cathode into corresponding byproducts generated in the process of preparing metal by thermally reducing metal oxide by alkali metal; constitute "inert anode, O 2- Ion-conducting molten salt mediator |O 2- An ionic solid conductor-by-product, an inert cathode "electrolytic cell;
carrying out electrolytic reaction on the electrolytic cell;
said O 2- The ion conduction molten salt medium is Ma 2 O-MaOH-Ma 2 CO 3 -MaCl mediumQuality is improved; wherein Ma represents an alkali metal;
the byproduct generated in the process of preparing metal by thermally reducing metal oxide by alkali metal is a reducing molten salt medium MaY-MeY 2 - (Ma) carrying out (Ma) thermal reduction of the by-products produced during the metal oxide process; wherein, ma represents an alkali metal, and Me represents an alkaline earth metal; y represents a halogen element;
the reducing molten salt medium MaY-MeY 2 - (Ma) is obtained by melting MaY-MeY 2 Adding auxiliary electrolytic MaOH-Ma into flux 2 CO 3 -Ma generated by MaCl molten salt is prepared;
the byproduct generated in the process of preparing metal by thermally reducing metal oxide by alkali metal is MaY-MeY 2 - (Ma) - (MeO) molten salt.
2. The method for regenerating an alkali metal reducing agent in a process for producing a metal from an alkali metal thermal reduced metal oxide as claimed in claim 1, wherein said catalyst has an oxygen atom 2- The ion-conducting container is made of CeO 2 Radical O 2- A container made of ion conductor material.
3. The method for regenerating an alkali metal reducing agent in a process for preparing a metal from an alkali metal thermal reduced metal oxide according to claim 1, wherein the material of the inert anode is selected from the group consisting of: a metal, alloy, electronic ceramic, cermet, or graphite.
4. The method for regenerating an alkali metal reducing agent in the preparation of metals from alkali metal thermal reduction metal oxides according to claim 1, wherein the material of said inert cathode in the molten chloride salt system is selected from the group consisting of: fe, ni, stainless steel, mo, W, or the same material as the prepared metal; in the fluoride molten salt system, W, mo or the same material as the prepared metal.
5. The method for regenerating an alkali metal reducing agent in the production of a metal from an alkali metal thermal reduction metal oxide according to claim 1,characterized in that the electrolysis voltage in the electrolysis reaction is controlled to be higher than that of the molten MaY-MeY 2 The actual decomposition voltage of (MeO) in the- (Ma) - (MeO) catholyte is lower than that of MaY and MeY 2 The actual decomposition voltage of the molten salt.
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