CN103305870A - Ferro-nickel anticorrosion alloy material for inert anode - Google Patents
Ferro-nickel anticorrosion alloy material for inert anode Download PDFInfo
- Publication number
- CN103305870A CN103305870A CN 201310262234 CN201310262234A CN103305870A CN 103305870 A CN103305870 A CN 103305870A CN 201310262234 CN201310262234 CN 201310262234 CN 201310262234 A CN201310262234 A CN 201310262234A CN 103305870 A CN103305870 A CN 103305870A
- Authority
- CN
- China
- Prior art keywords
- inert anode
- alloy
- anode material
- base non
- ferronickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 67
- 229910000863 Ferronickel Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 46
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- 238000005260 corrosion Methods 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000004411 aluminium Substances 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 39
- 239000010405 anode material Substances 0.000 claims description 32
- 230000009972 noncorrosive effect Effects 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 239000011135 tin Substances 0.000 claims description 8
- 238000007669 thermal treatment Methods 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 238000005275 alloying Methods 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 238000005242 forging Methods 0.000 claims description 4
- 238000004663 powder metallurgy Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000007712 rapid solidification Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 description 20
- 229910052742 iron Inorganic materials 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910001092 metal group alloy Inorganic materials 0.000 description 5
- 229910003271 Ni-Fe Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000011701 zinc Chemical group 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000009768 microwave sintering Methods 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- -1 sodium aluminum fluoride Chemical compound 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 229910017091 Fe-Sn Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910017142 Fe—Sn Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UOBPHQJGWSVXFS-UHFFFAOYSA-N [O].[F] Chemical compound [O].[F] UOBPHQJGWSVXFS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229910001067 superalloy steel Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Chemical group 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Abstract
The invention discloses a ferro-nickel anticorrosion alloy material for an inert anode, relates to an alloy material which is used for electrolysis of metal molten salt and especially suitable for a carbon-free ferro-nickel metal inert anode of an aluminium cell. The ferro-nickel anticorrosion alloy material for the inert anode is characterized by comprising the components in percentage by mass: 35-65% of Ni, 20-50% of Fe, 3-15% of Cu, and 3-10% of Co. The alloy material suitable for the inert anode of the aluminum cell of the metal molten salt, provided by the invention, is suitable for a low-temperature (700-850 DEG C) electrolyte system; the alloy anode displays good high-temperature inoxidizability and electrolyte corrosion resistance in the electrolytic process; the quality of the electrolyzed aluminum product can be up to 99.7%.
Description
Technical field
A kind of ferronickel base non-corrosive metal inert anode material relates to a kind ofly for molten salt electrolysis of metals, is particularly useful for the alloy material of carbon-free, the ferronickel Base Metal inert anode of aluminium cell.
Background technology
As light metal, the application of aluminium and alloy thereof is significant for the saving of global energy, and for pursuing the Sustainable development of former Aluminium Electrolysis process, needs solution energy consumption is huge seriously to wait series of problems with environmental pollution.
At present, the widespread use in many metal metallurgy smelting fused salt electrolysis industry of the carbon anode of easy consumption is such as smelting of aluminium, rare earth metal etc.Than traditional carbon anode, the development of inert anode material and inert anode technology in the production process of primary aluminum and other metal, can be saved the energy significantly; Substitute the carbon anode of easy consumption with inert anode, the anode bubbing is by the CO that causes Greenhouse effect
2With strong greenhouse gases-fluorocarbon (such as CF
4And C
2F
6) replace with oxygen; Simultaneously, the application of inert anode can reduce the cost of aluminum production significantly, as the floor space of dwindling electrolyzer, reduces the manufacturing expense of carbon anode, and the input of economizing on the use of funds improves primary aluminum quality etc.
Become metal at metal oxide by electrolysis for production, especially aluminum oxide is smelted in fused salt electrolysis plastome in the process of primary aluminum, and the use of inert anode in electrolyzer obtained extensive concern and the further investigation of industry member.The more inert anode material of research mainly comprises stupalith, cermet material and metal alloy compositions at present.Because stupalith and sintering metal have the defective that itself is difficult to overcome, poor with thermal shock resistance such as electroconductibility, be difficult for connecting, be difficult to shape etc., and metal alloy does not have above defective, is to have the inert anode material of wishing to obtain commercial applications most.
Ni-fe-based alloy is important corrosion-resistant material, in galvanic corrosion and chemical corrosion environment, all have the good performances such as anti-general corrosion, local corrosion and stress corrosion, its comprehensive anti-corrosion capability is good more than stainless steel and other corrosion-resistant metallic material, especially is suitable for harsh bad border under the modern industrial technology.
Patent US4956068, US5069771 have described with nickel based super alloy such as Inconel, Monel etc. as body, skin is alloy coat, it consists of nickel/cobalt of (mass percent): 55-90%/iron, the chromium of 10-30%, about 15% aluminium, titanium, zirconium, yttrium, hafnium, niobium, the outer layer metal coating forms oxide ceramic layer through surface treatment, can stop that Sauerstoffatom is to the corrosion of body material.
Patent US 5510008 has described a kind of anode, and this anode obtains the porous metal matrix by powder such as nickel, iron, aluminium, copper through microwave sintering.Alloying element consists of the nickel of (mass percent): 60-67%, the aluminium of 3-10%, the iron of 5-20%, the copper of 5-15%.It is outer that porous metal form the rich ferriferous oxide with electrochemical activity through the original position anodic polarization.The sodium aluminum fluoride of good fluidity can be penetrated into the porous metal matrix in oxide film forming process, and hinder ionogen and when electrolytic reaction occurs, further permeate from the anode active outer layer, can the holding anode inner base still be the electrochemistry inertia like this.
Patent US 6361680 has described a kind of production method and material composition that is applicable to inert anode for aluminium electrolysis, and this anode is by nickel, aluminium, iron, copper and at least a active element such as silicon, and tin, zinc, vanadium, indium, hafnium, tungsten and rare earth element form.Matrix is metal and intermetallic compound behind the microwave sintering, and matrix surface is oxide skin, and this oxide skin can carry out anodic polarization and obtain in containing the electrolysis of fluorides matter of aluminum oxide, perhaps carry out pyroprocessing and obtain in the oxygen atmosphere.
Patent US 6562224 has described a kind of making method for aluminum electrolyzing cell used inert anode, and this anode is by the Ni-Fe matrix composition, and in oxygen atmosphere or air preoxidation, the preoxidation optimum temps is 1000-1100 ℃ before putting into electrolyzer.Stick one deck ferriferous oxide at the Ni-Fe matrix surface after the preoxidation outer, such as Fe
2O
3, this skin has poor conduction to oxonium ion, simultaneously the free oxygen atom is had the one direction conduction, can reduce oxygen diffusion inner to the Ni-Fe matrix in electrolytic process.
Patent US 6878247, US20030066755A1 have described a kind of inert anode for electrolysis of aluminum, and as body portion, matrix is outer to obtain the rich nickel dam of porous by surface treatment to this anode, can improve like this electrochemical activity of outer surface by the Ni-Fe alloy.Outermost layer is the iron-doped nickel oxide ceramic layer, and this ceramic layer is attached on the rich nickel dam of porous, can improve the refractory brine corrosion performance of anode material.In use, the hole of the rich nickel dam of outside porous is some or all of is filled by the oxide compound of iron and nickel, fluorochemical and oxygen fluorine cpd.
It is ferrous alloy that patent US20040216995A1 has described a kind of internal layer, skin is nickel-ferro alloy layer (Fe/Ni is than being 1-3), by adding the velocity of diffusion of rare earth element control ferro element, can slow down on the one hand ferro element enters the ionogen from the oxide skin dissolving, can reduce on the other hand outer ferriferous oxide thicknesses of layers, increase rete and bonding force matrix, stop ionogen to enter the inner corrosion of matrix.
Patent US20050205431A1 has described a kind of nickel-base alloy anode, and its component mass percent is: the nickel of 20-60%, the iron of 5-15%, the aluminium of 1.5-5%, the rare earth element of 0-2%, other elements of 0-2%, such as Mn, Si, C etc., remain and be Fe, keep Cu/Ni than being 0.2-0.3.This alloy adopts sand mold casting, generates the thick oxide film of 0.1-1.0mm at the electrolytic process situ, and electrolysis voltage is 3.5-4.0V, can be less than 0.03% when impurity Ni content is optimum in the primary aluminum.
Patent US2007278107 has described a kind of metal inert anode, and this anode is applicable in the aluminium cell, and it forms and mainly comprises nickel, copper, iron, tin.The alloy mass percentage composition is: the nickel of 15-50%, and the copper of 10-70%, the tin of 1-15% remains and is iron.The composition of further optimizing is: the nickel of 20-30%, and the copper of 10-20%, the tin of 2-5% remains and is iron.Than the Ni-Cu-Fe metal anode, because the increase of surface film oxide conductivity, the Ni-Cu-Fe-Sn anode in use can reduce voltage, thereby has more excellent performance.
Patent CN 1896327A has described a kind of inert anode material for aluminium electrolysis, its component comprises nickel, iron, aluminium, copper, and the alloying element compositing range is the nickel of (mass percent): 50-70%, the iron of 10-30%, the aluminium of 4-10%, the copper of 8-12%.
Although to having carried out research and exploration extensively and profoundly to replace carbon anode as the inert anode material of target, still do not have successful inert anode material to enter industrial application at present.Currently still need to seek more suitable inert anode material, these anode materials need to have better robust and interference free performance to temperature fluctuation and the electrolyte ingredient fluctuation that is caused by the distribution of current inequality.
Ferronickel base corrosion resistant alloy material commonly used all is by Al, Cr isoreactivity element at present, forms Al in high-temperature corrosion environment
2O
3Or Cr
2O
3Protective membrane protect body material, can say, at present ferronickel corrosion resistant alloy material (comprising superalloy and stainless steel etc.) commonly used all contains the elements such as Al, Cr.But in aluminium electrolysis process, because Al
2O
3And Cr
2O
3The non-constant of electroconductibility, overtension in the electrolytic process can not reach the energy-conservation purpose of inert anode electrolyzer.While Al
2O
3In ionogen, also easily melted, be difficult to reach running balance.
Summary of the invention
The present invention seeks to the deficiency for above-mentioned prior art existence, provide a kind of corrosion resistance good, can Effective Raise electrolytic efficiency, reduce and pollute, can satisfy the ferronickel base non-corrosive metal inert anode material that is applicable to inert anode of metal fused-salt electrolysis cell that industrial application requires.
The objective of the invention is to be achieved through the following technical solutions.
A kind of ferronickel base non-corrosive metal inert anode material is characterized in that the quality percentage composition of this ferronickel base non-corrosive metal inert anode material comprises: the Ni of 35%-65%, the Fe of 20%-50%, the Cu of 3%-15%, the Co of 3%-10%.
A kind of ferronickel base non-corrosive metal inert anode material of the present invention, in aluminium electrolysis process, this ferronickel non-corrosive metal inert anode generates the spinel structure oxide films such as nickel ferrite based magnetic loaded, cobalt ferrite, coppeferrite by original position, this even film layer is fine and close, can stop the further corrosion of inert anode fully.
A kind of ferronickel base non-corrosive metal inert anode material of the present invention, the quality percentage composition that it is characterized in that this ferronickel base non-corrosive metal inert anode material also comprises the active element of 0.1%-3%, and active element is one or more the mixing among Y, La, Ce, Sc, the Hf.
Oxide film is thicker in this alloy inert anode electrolysis process, is about 0.5-1.0mm, and in order to increase the adhesivity of oxide film, minimizing is peeled off, and also need add the active element of 0.1-3% in the alloy material, and active element comprises Y, La, Ce, Sc, Hf etc.Passivation phenomenon can occur in the active element anode above 3%, and resistance increases, and voltage sharply raises.The adding of active element, all right crystal grain thinning, the homogeneity of increase Fine Texture of Material.
A kind of ferronickel base non-corrosive metal inert anode material of the present invention, the quality percentage composition that it is characterized in that this ferronickel base non-corrosive metal inert anode material also comprises the alloy element of 0-10%; Alloy element is a kind of alloying element among Ti, V, Mn, Zn, Sn, Zr, Nb, Ag, W, Mo, the Ta or two or more combinations.Its main purpose of above-mentioned element is to improve plasticity and the physical strength of rete.
A kind of ferronickel base non-corrosive metal inert anode material of the present invention is characterized in that adopting thin brilliant casting, rapid solidification, powder metallurgy process preparation.
A kind of ferronickel base non-corrosive metal inert anode material of the present invention, it is characterized in that also can further adopting repeatedly thermal treatment and viscous deformation, such as forging, extruding, rolling, to optimize Fine Texture of Material, crystal grain thinning is put forward heavy alloyed high-temperature oxidation resistance and electrolyte-resistant corrosive nature.
A kind of ferronickel base non-corrosive metal inert anode material of the present invention is characterized in that the average crystal grain of its alloy less than 300 microns, adopts thin brilliant casting, rapid solidification, powder metallurgy process preparation.
The corrosion resistance of alloy inert anode can be provided by the ferronickel corrosion resistant alloy material that is applicable to inert anode of metal fused-salt electrolysis cell that provides a kind of ferronickel base non-corrosive metal inert anode material of the present invention, improves electrolytic efficiency, reduces and pollutes.
Embodiment
A kind of ferronickel base non-corrosive metal inert anode material, the quality percentage composition of its alloy material comprises: the Ni of 35-65%, the Fe of 20-50%, the Cu of 3-15%, the Co of 3-10%.
Oxide film is mainly the spinel structure oxide films such as nickel ferrite based magnetic loaded, cobalt ferrite, coppeferrite in this alloy inert anode electrolysis process, and this even film layer is fine and close, but rete is thicker, is about 0.5-1.0mm.In order to increase the adhesivity of oxide film, improve thermal shock resistance, minimizing is peeled off, and also need add the active element of 0.1-3% in the alloy material, and active element comprises Y, La, Ce, Sc, Hf etc.Passivation phenomenon can occur in the active element anode above 3%, and resistance increases, and voltage sharply raises.The adding of active element, all right crystal grain thinning, the homogeneity of increase Fine Texture of Material.
Also comprise suitable alloy element in the composition of this alloy material, element comprises: a kind of alloying element among Ti, V, Mn, Zn, Sn, Zr, Nb, Ag, W, Mo, the Ta or two or more combinations, the quality percentage composition summation of above-mentioned element is 0-10%, and its main purpose is to improve plasticity and the physical strength of rete.
Form oxide film for quick in electrolytic process, and can carry out self-regeneration, need homogeneous microstructure, average crystal grain can adopt the methods preparations such as thin brilliant casting, rapid solidification, powder metallurgy less than 300 microns.
This alloy also can further adopt repeatedly thermal treatment and viscous deformation, such as forging, extruding, rolling etc., to optimize Fine Texture of Material, puies forward heavy alloyed high-temperature oxidation resistance and electrolyte-resistant corrosive nature.
This alloy material has good conductivity, and good switching performance, is suitable for brazing, mechanical connection and bonding etc.This alloy has good high-temperature oxidation resistance under atmospheric environment He in the molten salt electrolyte, good electrochemically resistant is learned the anti-grain boundary corrosion performance of burn into, and the temperature fluctuation of electrolyzer is had good robust and interference free performance.
The metal alloy anode that the embodiment of the invention provides is applicable in low temperature (700-850 ℃) electrolyte system; anode is polarized in the surface by electrochemical in-situ and forms oxide compound and fluorochemical mixed protection layer; to prevent further corrosion and the oxidation of anode interior, the holding anode inner base is the electrochemistry inertia.
The metal alloy that the embodiment of the invention provides is suitable in low temperature (700-850 ℃) electrolyte system, and its electrolyte ingredient is KF-NaF-AlF
3-Al
2O
3, its KF+NaF and AlF
3Mol ratio is between 1.2-1.7.Test shows, is 0.5-0.8A/cm in anodic current density
2The time, adopt alloy inert anode of the present invention can obtain foreign matter content and be less than 0.5% electrolysis primary aluminum.
The further feature of the metal alloy that the embodiment of the invention provides is done with the following Examples further to replenish and is described.
Embodiment 1
A kind of ferronickel corrosion resistant alloy material that is applicable to inert anode of metal fused-salt electrolysis cell, the mass component of alloy is: 65% nickel, 20% iron, 4.5% copper, 10% cobalt, 0.5% scandium.Alloy is the melting casting in medium-frequency induction furnace, forms the anode product after the ingot casting processing.At KF-NaF-AlF
3-Al
2O
3In the system 20A electrolytic trial, electrolysis temperature is 850 ℃, and anodic current density is 0.8A/cm
2, electrolysis voltage is in 5.2 ~ 5.8V fluctuation, and electrolysis can obtain quality in 24 hours and reach 99.7% primary aluminum.
Embodiment 2
A kind of ferronickel corrosion resistant alloy material that is applicable to inert anode of metal fused-salt electrolysis cell, the mass component of alloy is: 35% nickel, 50% iron, 9% copper, 3% cobalt, 3% lanthanum.Alloy is the argon-filled protection melting in vacuum induction furnace, and tapping casting in 1400-1500 ℃ of temperature range forms the anode product after the ingot casting processing.At KF-NaF-AlF
3-Al
2O
3In the system 20A electrolytic trial, electrolysis temperature is 800 ℃, and anodic current density is 0.5A/cm
2, average electrolysis voltage is 3.4 ~ 3.7V fluctuation, electrolysis can obtain quality in 24 hours and reach primary aluminum more than 99.5%.
Embodiment 3
A kind of ferronickel corrosion resistant alloy material that is applicable to inert anode of metal fused-salt electrolysis cell, the mass component of alloy is: 54% nickel, 30% iron, 3% copper, 10% cobalt, 1% cerium, 2% tin.Alloy is melting in 1450-1550 ℃ of temperature range in vacuum induction furnace, again through water cooled mo(u)ld cooling casting.Ingot casting cuts into diameter after Overheating Treatment be that 25mm, thickness are the sequin of 3mm.Carry out the high-temperature oxidation resistant property testing at 850 ℃, oxidization time is 200 hours, and the result shows, the oxidation weight gain speed of this alloy is 0.002 mg/cm
2H, the furnace cooling oxide film does not have peeling phenomenon.
Embodiment 4
A kind of ferronickel corrosion resistant alloy material that is applicable to inert anode of metal fused-salt electrolysis cell, the alloy mass composition is: 45% nickel, 26.5% iron, 15% copper, 10% cobalt, 0.5% hafnium, 3% silver.Alloy adopts the thin brilliant casting of induction stirring in process of setting, main grain size is 120 ~ 200um.At KF-NaF-AlF
3-Al
2O
3In the system 20A electrolytic trial, electrolysis temperature is 800 ℃, and anodic current density is 0.6A/cm
2, electrolysis voltage is in the fluctuation of 3.6-4.0 scope, and electrolysis shows after 24 hours that the oxide film adhesive ability of this alloy is strong, and oxide film does not have peeling phenomenon, and is excellent to robust and the interference free performance of temperature fluctuation.
Embodiment 5
A kind of ferronickel corrosion resistant alloy material that is applicable to inert anode of metal fused-salt electrolysis cell, the alloy mass composition is: 40% nickel, 30% iron, 15% copper, 10% cobalt, 1% yttrium, 2% niobium, 2% manganese.Be polarized in outer oxide compound and the fluorochemical mixed protection layer of forming of anode surface by electrochemical in-situ, internal layer forms oxide compound and spinel structure protective membrane, at KF-NaF-AlF
3-Al
2O
3In the system 200A electrolytic trial, electrolysis temperature is 800 ℃, and anodic current density is 0.5A/cm
2, electrolysis voltage is in 4.2-4.7 scope fluctuation, and electrolysis can obtain quality in 300 hours and reach primary aluminum more than 99.7%, and anodic corrosion speed is 8mm/a.
Embodiment 6
Adopt the identical electrolytic condition of embodiment 5, take out alloy anode after electrolysis 300h finishes, the scanning electron microscope analysis electrolytic oxide film shows: oxide film is outer to be NiO, FeO
x, CuO
xDeng oxide compound and FeF
x, the fluorochemical such as AlF3, NaF, KF mixolimnion, this layer thickness is the 300-600 micron; Internal layer is fine and close mixed oxide, and its main component is NiFe
2O
4, CoFe
2O
4, CuFe
2O
4, and a small amount of NiO, thickness is the 200-500 micron.
Embodiment 7
The alloy employing simple substance powder of embodiment 1 to embodiment 5 such as nickel powder, iron powder, copper powder, cobalt powder etc. obtain highdensity alloy through batch mixing, coldmoulding, sintering, obtain having the alloy material of even tiny microstructure after the thermal treatment.The alloy that this technique prepares has good high-temperature oxidation resistance and resistance to electrochemical corrosion energy equally.
Embodiment 8
The alloy of embodiment 1 to embodiment 5 adopts alloy atomization powder process, forms the powdered alloy of 20 ~ 150 microns rational gradation compositions, obtains highdensity alloy through isostatic cool pressing, degassed sintering and hot isostatic pressing.The anode that this technique prepares is compared the casting alloy anode, has more excellent high-temperature oxidation resistance and resistance to electrochemical corrosion energy, and the primary aluminum purity that electrolysis in 24 hours obtains reaches as high as more than 99.9%.
Embodiment 9
Embodiment 1 to embodiment 5 alloy adopts repeatedly thermal treatment and viscous deformation, such as extruding, forging, rolling etc., obtains the tiny microtexture of crystal grain, reduces grain boundary corrosion, avoids spot corrosion.With respect to casting alloy, high-temperature oxidation resistance and the resistance to electrochemical corrosion of alloy can improve more than 20% after the distortion thermal treatment, and the primary aluminum foreign matter content reduces 10%-20%.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. a ferronickel base non-corrosive metal inert anode material is characterized in that the quality percentage composition of this ferronickel base non-corrosive metal inert anode material comprises: the Ni of 35%-65%, the Fe of 20%-50%, the Cu of 3%-15%, the Co of 3%-10%.
2. a kind of ferronickel base non-corrosive metal inert anode material according to claim 1, the quality percentage composition that it is characterized in that this ferronickel base non-corrosive metal inert anode material also comprises the active element of 0.1%-3%, and active element is one or more the mixing among Y, La, Ce, Sc, the Hf.
3. a kind of ferronickel base non-corrosive metal inert anode material according to claim 1, the quality percentage composition that it is characterized in that this ferronickel base non-corrosive metal inert anode material also comprises the alloy element of 0-10%; Alloy element is a kind of alloying element among Ti, V, Mn, Zn, Sn, Zr, Nb, Ag, W, Mo, the Ta or two or more combinations; Its main purpose of above-mentioned element is to improve plasticity and the physical strength of rete.
4. a kind of ferronickel base non-corrosive metal inert anode material according to claim 1 is characterized in that the average crystal grain of its alloy less than 300 microns, adopts thin brilliant casting, rapid solidification, powder metallurgy process preparation.
5. a kind of ferronickel base non-corrosive metal inert anode material according to claim 1, it is characterized in that also can further adopting repeatedly thermal treatment and viscous deformation, such as forging, extruding, rolling, to optimize Fine Texture of Material, crystal grain thinning is put forward heavy alloyed high-temperature oxidation resistance and electrolyte-resistant corrosive nature.
6. the described ferronickel corrosion resistant alloy material that is applicable to inert anode of metal fused-salt electrolysis cell according to claim 1; in aluminium electrolysis process; generate the oxide film of even compact by original position, this alloy protecting oxide film is comprised of the spinel structure oxide film of nickel ferrite based magnetic loaded, cobalt ferrite, coppeferrite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201310262234 CN103305870A (en) | 2013-06-27 | 2013-06-27 | Ferro-nickel anticorrosion alloy material for inert anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201310262234 CN103305870A (en) | 2013-06-27 | 2013-06-27 | Ferro-nickel anticorrosion alloy material for inert anode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103305870A true CN103305870A (en) | 2013-09-18 |
Family
ID=49131576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201310262234 Pending CN103305870A (en) | 2013-06-27 | 2013-06-27 | Ferro-nickel anticorrosion alloy material for inert anode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103305870A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105024041A (en) * | 2015-07-14 | 2015-11-04 | 北京航空航天大学 | Activated metal electrode based on oxygen-metal battery |
| CN106906491A (en) * | 2017-04-06 | 2017-06-30 | 东北大学 | A kind of ferronickel base is anti-oxidant and corrosion resisting alloy inert anode material |
-
2013
- 2013-06-27 CN CN 201310262234 patent/CN103305870A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105024041A (en) * | 2015-07-14 | 2015-11-04 | 北京航空航天大学 | Activated metal electrode based on oxygen-metal battery |
| CN106906491A (en) * | 2017-04-06 | 2017-06-30 | 东北大学 | A kind of ferronickel base is anti-oxidant and corrosion resisting alloy inert anode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pawlek | Inert anodes: an update | |
| CN102011144A (en) | Nickel-based alloy material suitable for inert anode of metal molten salt electrolyzer | |
| CN101717969A (en) | Alloy material suitable for inert anode of metal fused-salt electrolysis cell | |
| CN102994801A (en) | Alloy material applicable to inert anode of metal molten salt electrolytic cell | |
| CN101688285B (en) | Material for covering surface of hot dip galvanizing bath member, process for producing the material, and hot dip galvanizing bath member | |
| CN107937879A (en) | A kind of method of neodymium iron boron magnetic body and neodymium iron boron magnetic body overlay coating | |
| EP0396586A1 (en) | Cermet anode compositions with high content alloy phase | |
| CN109457164A (en) | A kind of AlNbMoVTi high-entropy alloy powder and application | |
| CN110714156A (en) | Light high-strength corrosion-resistant high-entropy alloy and preparation method thereof | |
| EP0378584A1 (en) | Cermet anode with continuously dispersed alloy phase and process for making | |
| CN106906491A (en) | A kind of ferronickel base is anti-oxidant and corrosion resisting alloy inert anode material | |
| CN108359866A (en) | A kind of fire resistant aluminum alloy sacrificial anode material and the preparation method and application thereof | |
| CN103305870A (en) | Ferro-nickel anticorrosion alloy material for inert anode | |
| El Ghallali et al. | Electrochemical synthesis of Ni–Sn alloys in molten LiCl–KCl | |
| Petrova et al. | Electrochemical behaviour of lead alloys as anodes in zinc electrowinning | |
| CN115287529B (en) | Nickel-iron-based alloy coating and preparation method and application thereof | |
| CN104561620A (en) | Preparation method of titanium alloy and use of titanium alloy | |
| CN114672755B (en) | Non-wetting coating suitable for resisting high-temperature aluminum permeation and preparation method thereof | |
| CN106514039B (en) | A kind of copper and tin titanium solder and preparation method thereof | |
| CA2545865A1 (en) | Stable anodes including iron oxide and use of such anodes in metal production cells | |
| CN109402422B (en) | Aluminum-magnesium-zirconium alloy wire and manufacturing method thereof | |
| CN102677099A (en) | Ni-w gradient material and preparation method thereof | |
| CN102400082B (en) | Magnesium alloy surface conduction anticorrosive paint and preparation method thereof | |
| CN106591626B (en) | A kind of TA18 titanium alloy composite material and its preparation method and application | |
| CN109338375A (en) | A kind of high-performance Al-Zn-In series sacrificial anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130918 |