CN108866578A - A kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium - Google Patents
A kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium Download PDFInfo
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- CN108866578A CN108866578A CN201810852037.5A CN201810852037A CN108866578A CN 108866578 A CN108866578 A CN 108866578A CN 201810852037 A CN201810852037 A CN 201810852037A CN 108866578 A CN108866578 A CN 108866578A
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- zirconium
- hafnium
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- salt electrolysis
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 40
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 32
- 238000000926 separation method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 13
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims abstract description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 230000010287 polarization Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 4
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000003682 fluorination reaction Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 3
- 229910020148 K2ZrF6 Inorganic materials 0.000 claims description 2
- 229910007998 ZrF4 Inorganic materials 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims 4
- 229910000975 Carbon steel Inorganic materials 0.000 claims 2
- 229910001626 barium chloride Inorganic materials 0.000 claims 2
- 239000010962 carbon steel Substances 0.000 claims 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 2
- 229910052715 tantalum Inorganic materials 0.000 claims 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 2
- 229910007828 Li2ZrF6 Inorganic materials 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910000792 Monel Inorganic materials 0.000 claims 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims 1
- 150000004673 fluoride salts Chemical class 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 4
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910003865 HfCl4 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- NMLQNVRHVSWEGS-UHFFFAOYSA-N [Cl].[K] Chemical compound [Cl].[K] NMLQNVRHVSWEGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- -1 salt aluminium potassium chlorate Chemical class 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 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
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium, avoids zirconium ion and forms the low chemical valence zirconates of indissoluble in electro-reduction process, and then obtain electrolysis zirconium metallic crystal.Separation of zirconium and hafnium is successfully realized with fused salt electrolysis process, removes most impurity elements in sponge zirconium, production preparation meets the high purity zirconium of nuclear leve requirement.Fused salt electrolysis process preparation nuclear leve high purity zirconium production process is fully sealed, and has many advantages, such as to can be continuously produced, is environment friendly and pollution-free, production cost is low, yield is big.
Description
Technical field
The present invention relates to a kind of methods for preparing nuclear leve high purity zirconium, more specifically for, in particular to a kind of molten-salt electrolysis
The process of separation of zirconium and hafnium preparation nuclear leve high purity zirconium.
Background technique
The performances such as zirconium and its alloy material have unique high temperature resistant, anticorrosive, thermal neutron absorption cross section is small, in atomic energy
In industry, zircaloy is used as reactor involucrum and structural material.In Aeronautics and Astronautics, the energy, chemical industry, metallurgy, electronics, light industry, machine
The fields such as tool, medical treatment zirconium metal and its alloy material are also widely used.In main zirconium hafnium production country of the world, zirconium hafnium
Industrialized development be all to be closely connected together with nuclear industry.
Zirconium and the natural symbiosis of hafnium, belong to the group ivb element in the periodic table of chemical element, there is similar outer-shell electron knot
Structure, and since hafnium is after lanthanide series, influenced by lanthanide contract it is very big so that the atomic radius of zirconium, hafnium, ion half
Diameter and structure etc. are all very close, cause their chemical property also extremely similar, become and are most difficult to separation in the periodic table of elements
Element to one of.The mass fraction 1.5%~3% of usual hafnium in natural zirconium resource.Atomic energy level sponge zirconium requires hafnium content <
100ppm.Therefore, separation of zirconium and hafnium technology is the key that production atomic energy level sponge zirconium.
Since the fifties in last century, the U.S., Japan, France etc. have carried out a large amount of research work to separation of zirconium and hafnium technique
Make, succeeded in developing atomic energy level separation of zirconium and hafnium technique and be used for industry life, sums up and be broadly divided into fire concentrate and wet process
Separation.
Wet separation mainly includes MIBK-HCNS method, TOA method, TBP-HCL-HNO3Method, improved N235-H2SO4Method and
Sulfoxide type extraction etc..
Its cardinal principle of fire concentrate is to utilize HfCl4With ZrCl4In fuse salt aluminium potassium chlorate (KAlCl4) in saturated vapor
The difference of pressure is separated in rectifying column, and finally obtaining HfCl4 content with the method separating zirconium, hafnium is 30%~50% enrichment
The ZrCl of object and atomic energy level4。
Either fused salt rectification method or wet separation method all have the shortcomings that production efficiency is low, high production cost, separation
Product purity is not high, is generally difficult to apply to production high purity zirconium.
Currently, the separation of zirconium and hafnium technology that industry is used widely is fused salt rectification method.The raw material that the technique uses is zirconium
Diamond stone produces thick zirconium chloride through fluidizing chlorination.Contain a certain amount of hafnium chloride in thick zirconium chloride.Utilize zirconium chloride, hafnium chloride
Mixture is in melting chlorine potassium aluminate (KAlCl4) in different vapour pressures characteristic, can be carried out in destilling tower zirconium hafnium divide
From.Since zirconium chloride, hafnium chloride fusing point are very close, only 3 DEG C of difference, fused salt rectification method controls essence to accuracy of temperature control, pressure
Degree requires high, unstable product quality, and impurity content fluctuation is big, and separation product is generally difficult to apply to production high purity zirconium.Fused salt
Rectification method has the disadvantages of energy consumption is high, production is discontinuous, single distillation output is low, and production efficiency low cost is high.
Patent《Zirconium oxide/hafnium oxide mixture fire concentrate method》(CN201310682029.8) it discloses a kind of molten
The method of salt rectification method separating zirconium and hafnium.Zirconium oxide, hafnium oxide are subjected to bromination first, generate the mixed of tetrabormated zirconium and hafnium
Object is closed, molten salt mixture is added.The fused salt is the molten mixture of potassium fluorozirconate and aluminum aluminum sulfate, in certain temperature and pressure item
Distillation separation is carried out under part.There is no solve disadvantage possessed by the fused salt way of distillation for this method.
Patent《A kind of Solvent Extraction Separation zirconium hafnium technique》(CN201511004574.7) a kind of solvent extraction is disclosed
Method separating zirconium and hafnium technique.Using the industrial goods of chloride zirconium acyl containing hafnium as raw material, prepared through processes such as water-soluble, alkali is heavy, washing, nitric acid dissolutions
Zirconium nitrate (hafnium) acyl solution out；Then preferential using TBP to add the TBP kerosin of phase modifying agent n-octyl alcohol as extractant
The characteristics of extracting zirconium extracts most of zirconium and minute quantity hafnium into organic phase by multi-stage counter current extraction；Load organic phases are with one
The nitric acid solution washing for determining concentration further removes most of hafnium in organic phase；Load organic phases after pickling are stripped with water
It takes, zirconium nitrate acyl solution can be obtained；Zirconium dioxide powder can be obtained through ammonia precipitation process, drying, calcining in the solution.The process flow
Complexity can not produce high purity product, and must pass through multi-stage counter current extraction, and production efficiency is low, and high production cost, there is also sewage
The problems such as discharge, is not suitable for large-scale industrial production.
Fused salt electrolysis process have many advantages, such as yield it is big, it is at low cost, can continuous production, be widely used in metal smelt, example
As aluminium, sodium, calcium, magnesium, potassium and rare earth metal extract；It is also applied to purification of metals, such as high purity copper, aluminium, titanium, gallium simultaneously
Deng.But for a long time, there is no applied well in metal zirconium purification and separation of zirconium and hafnium field for fused salt electrolysis process.This is
Since in halide molten salt system, Zr4After obtaining electronics, the low chemical valence halide (ZrCl) for being difficult to dissolve is generally formed, into
And precipitating is formed, it is unable to get metal zirconium.It is generally believed that should be ensured that abundance in electrolytic process, in molten salt electrolyte
Metal (metal to be purified) cation reduces activation polarization and concentration polarization, and then promotes metal ion transmission and reduction.This
Invention research shows that zirconium ion has the characteristic different from other metals, in Chlorides molten salts, only in larger polarization
Under the conditions of, just it is avoided that the generation of the low chemical valence zirconates of indissoluble.
In order to overcome discontinuous existing separation of zirconium and hafnium technology production, low output, production efficiency it is low, it is at high cost, can not produce
The shortcomings that high-purity nuclear grade zirconium product, a kind of fused salt electrolysis process separating zirconium and hafnium of the invention prepare technique of the nuclear leve without hafnium high purity zirconium
Method, this method has the characteristics that yield is big, can be continuously produced, product purity is high, at low cost, environment friendly and pollution-free.
Summary of the invention
In order to overcome foregoing problems, the purpose of the present invention is to provide a kind of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve is high-purity
The process of zirconium.
A kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium, comprises the steps of：
(1) alkali or alkaline earth metal halide electrolyte is uniformly mixed with the halide of zirconium, in 150-200 DEG C of temperature
Sufficiently dry 12h or more under degree, vacuum condition, then the dry 12h or more under 300-500 DEG C of vacuum condition, sufficiently removes electricity
Solve the Free water and the crystallization water in matter；
(2) it under inert protective gas environment, heats up 600-900 DEG C, keeps the temperature 5-8 hours, carry out pre- fused salt, make different electricity
Solution matter component is sufficiently mixed；
(3) using sponge zirconium as anode, using zirconium, stainless steel, nickel or molybdenum as cathode, at 600-900 DEG C, inert gas shielding item
It is electrolysed under part；
(4) electrolytic parameter controls.Cathode-current density is controlled in 0.01-2A/cm2, anodic current density control is in 0.01-
0.5A/cm2；
(5) after the completion of being electrolysed, electrolysate is moved into inert gas shielding environment and is cooled down；
(6) electrolysate after cooling is moved to supersonic wave cleaning machine to clean, cleaning temperature is controlled at 60-70 DEG C, is surpassed
The every cleaning of sound wave carries out 2 minutes mechanical stirrings after five minutes；
(7) the electrolysis zirconium product cleaned up is subjected to vacuum drying, then carries out vacuum preservation.
Further, alkali or alkaline earth metal halide electrolyte is LiCl, KCl, NaCl, CaCl2、NaF、KF、LiF
One of or more than one mixtures.
Further, the halide of the zirconium is ZrCl4、ZrF4、K2ZrF6、Na2ZrF6One or more kinds of mixtures.
Further, zirconium ion concentration is controlled in 0.08-5wt% (mass concentration) in electrolyte.
Further, sponge zirconium purity >=96%, hafnium content are 2-3%.
Further, sponge zirconium anode is contained in nickel basketry or stainless steel basketry.
Further, zirconium, stainless steel, nickel, molybdenum cathode are metal plate or metal bar.
Further, inert gas is argon gas or helium.
The invention has the advantages that avoid zirconium ion forms the low chemical valence zirconium of indissoluble in electro-reduction process
Salt, and then obtain electrolysis zirconium metallic crystal.Separation of zirconium and hafnium is successfully realized with fused salt electrolysis process, is removed exhausted most in sponge zirconium
Number impurity element, production preparation meet the high purity zirconium of nuclear leve requirement.It is complete that fused salt electrolysis process prepares nuclear leve high purity zirconium production process
Sealing has many advantages, such as to can be continuously produced, is environment friendly and pollution-free, and production cost is low, yield is big.
Specific embodiment
Embodiment 1
1, potassium chloride, lithium chloride are mixed according to 41: 59 molar ratios, adds 0.6wt% zirconium chloride (zirconium ion
Content is 0.23wt%), it is uniformly mixed.
2, electrolyte mixture is sufficiently dried to 18h under 200 DEG C of temperature, vacuum conditions, then in 300 DEG C of vacuum conditions
Lower dry 18h sufficiently removes Free water and the crystallization water in electrolyte.
3, it under ar gas environment, heats up 500 DEG C, keeps the temperature 5-8 hours, carry out pre- fused salt.
4, it using sponge zirconium as anode, using zirconium stick as cathode, is electrolysed under 500 DEG C, argon gas protective condition.
Sponge zirconium purity >=97%, hafnium content are 2.5%.
The sponge zirconium anode is contained in nickel basketry.
5, electrolytic parameter controls.Cathode-current density is 0.2A/cm2, anodic current density control is in 0.1A/cm2。
6, after the completion of being electrolysed, electrolysate is moved into argon gas protection environment and is cooled down.
7, electrolysate after cooling is moved to supersonic wave cleaning machine to clean, cleaning temperature is controlled at 60-70 DEG C, ultrasound
The every cleaning of wave carries out 2 minutes mechanical stirrings after five minutes, until can't detect chloride ion in cleaning solution.
8, the electrolysis zirconium product cleaned up is subjected to vacuum drying, is then monitored analysis.
Embodiment 2
2 operating procedure of case study on implementation and 1 parameter of case study on implementation are essentially identical, only difference is that zirconium ion concentration is
2wt%, zirconium chloride concentration 5.12wt%.
2 result of case study on implementation
Case study on implementation 3
3 operating procedure of case study on implementation and 1 parameter of case study on implementation are essentially identical, the difference is that cathode-current density is
0.85A/cm2
3 result of case study on implementation
Compare case study on implementation 1,2,3, it is known that in electrolysis of chloride plastidome, applying larger polarization condition (electrochemistry
Polarization, concentration polarization) under, simple substance zirconium metal could be obtained, this is very different with other metals.
Case study on implementation 4
1, lithium fluoride, potassium fluoride are mixed according to 51: 49 molar ratios, adding 8wt% zirconium tetrafluoride, (zirconium ion contains
Amount is 4.3wt%), it is uniformly mixed.
2, electrolyte mixture is sufficiently dried to 18h or more under 200 DEG C of temperature, vacuum conditions, then in 300 DEG C of vacuum
Under the conditions of dry 18h or more, sufficiently remove the Free water and the crystallization water in electrolyte.
3, it under ar gas environment, heats up 700 DEG C, keeps the temperature 5-8 hours, carry out pre- fused salt.
4, it using sponge zirconium as anode, using zirconium stick as cathode, at 700 DEG C, is electrolysed under the conditions of inert gas shielding.
Sponge zirconium purity >=97%, hafnium content are 2.5%.
The sponge zirconium anode is contained in nickel basketry.
5, electrolytic parameter controls.Cathode-current density is controlled in 0.2A/cm2, anodic current density control is in 0.1A/cm2。
6, after the completion of being electrolysed, electrolysate is moved into argon gas protection environment and is cooled down.
7, electrolysate after cooling is moved to supersonic wave cleaning machine to clean, cleaning temperature is controlled at 60-70 DEG C, ultrasound
The every cleaning of wave carries out 2 minutes mechanical stirrings after five minutes, until can't detect fluorine ion in cleaning solution.
8, the electrolysis zirconium product cleaned up is subjected to vacuum drying, is then monitored analysis.
4 result of case study on implementation
5 operating procedure of case study on implementation and 4 parameter of case study on implementation are essentially identical, only difference is that lithium fluoride, fluorination
Potassium is mixed according to 45: 65 molar ratios.
Apply 5 result of case
6 operating procedure of case study on implementation and 4 parameter of case study on implementation are essentially identical, only difference is that lithium fluoride, fluorination
Potassium is mixed according to 40: 60 molar ratios.
Apply 6 result of case
7 operating procedure of case study on implementation and 4 parameter of case study on implementation are essentially identical, only difference is that lithium fluoride, fluorination
Potassium is mixed according to 35: 65 molar ratios.
7 result of case study on implementation
It comparing known to case study on implementation 4,5,6,7 in electrolysis of fluorides plastidome, the content of lithium fluoride is greater than 40mol%,
It can avoid the generation of indissoluble low price chemical valence zirconates, and then obtain simple substance zirconium metal.Be fluorinated lithium content it is lower under the conditions of, then without
Method avoids the generation of the low chemical valence zirconates of indissoluble, can not obtain zirconium metal.
Claims (8)
1. a kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium, which is characterized in that yield is big, can serialization
Production, product purity are high, at low cost, environment friendly and pollution-free；
It comprises the steps of：
(1) alkali or alkaline earth metal halide electrolyte will be uniformly mixed with the halide of zirconium, 100-200 DEG C of temperature,
Sufficiently dry 5h or more under vacuum condition, then the dry 5h or more under 300-500 DEG C of vacuum condition, sufficiently removes in electrolyte
Free water and the crystallization water.
(2) it under inert protective gas environment, heats up 500-1000 DEG C, keeps the temperature 5-8 hours, carry out pre- fused salt, make different electrolysis
Matter component is sufficiently mixed；
(3) using sponge zirconium as anode, using zirconium, nickel, molybdenum, titanium, tantalum, stainless steel or straight carbon steel as cathode, at 500-1000 DEG C, inertia
It is electrolysed under the conditions of gas shield.
(4) electrolytic parameter controls.Cathode-current density is controlled in 0.01-5A/cm2, anodic current density control is in 0.01-10A/
cm2。
(5) after the completion of being electrolysed, electrolysate is moved into inert gas shielding environment and is cooled down；
(6) electrolysate after cooling is moved to supersonic wave cleaning machine to clean, cleaning temperature control is at 50-100 DEG C, ultrasonic wave
Every cleaning carries out 2 minutes mechanical stirrings after five minutes；
(7) the electrolysis zirconium product cleaned up is subjected to vacuum drying, then carries out vacuum preservation.
2. a kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium according to claim 1, feature
It is, the alkali or alkaline earth metal halide electrolyte is LiCl, KCl, NaCl, CsCl, CaCl2、MgCl2、BaCl2、
One of NaF, KF, LiF or more than one mixtures.
3. a kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium according to claim 1, feature
It is, the halide of the zirconium is ZrCl4、ZrF4、K2ZrF6、Na2ZrF6、Li2ZrF6One or more kinds of mixtures.
4. a kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium according to claim 1, feature
It is, zirconium ion concentration control is in 0.01-10wt% (mass concentration) in the electrolyte.
In LiCl, KCl, NaCl, CsCl, CaCl2、MgCl2、BaCl2In equal electrolysises of chloride plastidome, apply larger polarization item
Part (activation polarization, concentration polarization), zirconium ion content < 2wt%, cathode-current density > 0.15A/cm2。
In electrolysis of fluorides plastidome, the content > 40mol% of lithium fluoride can avoid the life of indissoluble low price chemical valence zirconates
At, and then obtain simple substance zirconium metal.Under the conditions of fluorination lithium content is lower, then the production of the low chemical valence zirconates of indissoluble is not can avoid
It is raw, zirconium metal can not be obtained.
5. a kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium according to claim 1, feature
It is, sponge zirconium purity >=96%, hafnium content is 2-3%.
6. a kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium according to claim 1, feature
It is, the sponge zirconium anode is contained in stainless steel, nickel tungsten or monel metal basketry.
7. a kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium according to claim 1, feature
It is, the zirconium, nickel, molybdenum, titanium, tantalum, stainless steel or straight carbon steel cathode are metal plate or metal bar.
8. a kind of process of molten-salt electrolysis separation of zirconium and hafnium preparation nuclear leve high purity zirconium according to claim 1, feature
It is, the inert gas is argon gas or helium.
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| CN110938838A (en) * | 2019-11-06 | 2020-03-31 | 东北大学 | Method for treating anode carbon slag of aluminum electrolysis cell by using NaCl molten salt extraction method |
| CN115305515A (en) * | 2021-05-08 | 2022-11-08 | 郑州大学 | Electrochemical method for zirconium-hafnium separation |
| CN115305512A (en) * | 2021-05-08 | 2022-11-08 | 中南大学 | Method for preparing metal zirconium by molten salt electrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110938838A (en) * | 2019-11-06 | 2020-03-31 | 东北大学 | Method for treating anode carbon slag of aluminum electrolysis cell by using NaCl molten salt extraction method |
| CN110938838B (en) * | 2019-11-06 | 2021-12-31 | 东北大学 | Method for treating anode carbon residue of aluminum electrolytic cell by NaCl molten salt extraction method |
| CN115305515A (en) * | 2021-05-08 | 2022-11-08 | 郑州大学 | Electrochemical method for zirconium-hafnium separation |
| CN115305512A (en) * | 2021-05-08 | 2022-11-08 | 中南大学 | Method for preparing metal zirconium by molten salt electrolysis |
| WO2022237488A1 (en) * | 2021-05-08 | 2022-11-17 | 郑州大学 | Electrochemical method for separating zirconium from hafnium |
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