US20090255372A1 - Recycling of superalloys with the aid of an alkali metal salt bath - Google Patents
Recycling of superalloys with the aid of an alkali metal salt bath Download PDFInfo
- Publication number
- US20090255372A1 US20090255372A1 US12/306,853 US30685307A US2009255372A1 US 20090255372 A1 US20090255372 A1 US 20090255372A1 US 30685307 A US30685307 A US 30685307A US 2009255372 A1 US2009255372 A1 US 2009255372A1
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- United States
- Prior art keywords
- melt
- process according
- metals
- weight
- superalloy
- Prior art date
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- Abandoned
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- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 64
- 229910052783 alkali metal Inorganic materials 0.000 title claims description 7
- 238000004064 recycling Methods 0.000 title description 4
- -1 alkali metal salt Chemical class 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 150000002739 metals Chemical class 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 16
- 230000029087 digestion Effects 0.000 claims description 44
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 229910052702 rhenium Inorganic materials 0.000 claims description 25
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000000737 periodic effect Effects 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 239000012223 aqueous fraction Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910020814 NaAl(OH)4 Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 150000003388 sodium compounds Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 239000011651 chromium Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910000691 Re alloy Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910002065 alloy metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- 229910004882 Na2S2O8 Inorganic materials 0.000 description 1
- 229910019075 NaOH—Na2SO4 Inorganic materials 0.000 description 1
- 229910019660 Nb(OH)5 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000289 melt material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G47/00—Compounds of rhenium
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- 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
- C22B23/00—Obtaining nickel or cobalt
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/026—Obtaining nickel or cobalt by dry processes from spent catalysts
-
- 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
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a process for the digestion of superalloys, in particular superalloy scrap, in a salt melt and subsequent recovery of the valuable metals.
- Superalloys are alloys which have a complex composition, are stable at high temperatures and are based on nickel and cobalt, with additions of other metals, such as, for example, aluminium, chromium, molybdenum, tungsten, tantalum, niobium, manganese, rhenium, platinum, titanium, zirconium and hafnium, and nonmetals, such as boron and/or carbon.
- the superalloys are high-strength and particularly hard-wearing alloys which are used in motor and engine construction, in energy technology and in aviation and space flight. The particular properties of these alloys are achieved in particular by the addition of rare and noble metals, such as rhenium, tantalum, niobium or even platinum.
- the superalloys differ from the customary high-melting alloys, e.g. W—Re alloys or Mo—Re alloys, in their particular resistance to oxidation or corrosion.
- W—Re alloys or Mo—Re alloys e.g. W—Re alloys or Mo—Re alloys
- components comprising superalloys are used in the production of blades in aircraft turbines. After elapse of the duration of use, such parts are an important raw material source for recovering rare metals, in particular rhenium, tantalum, niobium, tungsten, molybdenum and platinum.
- the recovery of the alloy metals of the superalloys is commercially very interesting owing to the high proportion of expensive metals.
- special superalloys contain the metals rhenium in up to 12% by weight, tantalum in up to 12% by weight, niobium in up to 5% by weight and tungsten and molybdenum in up to 12% by weight.
- Further metals which serve as base metals in the superalloys are nickel and cobalt.
- the superalloys are a raw material source from which the recovery of these metals is commercially expedient.
- the high-melting metals present in scraps of an Fe/Ni/Co/Cu base alloy e.g. tungsten, molybdenum and chromium
- scraps of an Fe/Ni/Co/Cu base alloy e.g. tungsten, molybdenum and chromium
- tungsten, molybdenum and chromium are first converted into borides, carbides, nitrides, silicides or phosphides via a melting process by addition of non-metallic compounds of group III, IV or V, melted to give anodes and then subjected to an anodic oxidation.
- Those metals such as Co, Ni and Cu initially go into solution and are deposited from this at the cathode, while the high-melting metals, remain behind in the anode sludge, for example as borides, carbides, etc.
- the metals Ni, Co, Cu are separated from the high-melting metals, such as W, Mo or chromium, but there is no information at all about whether complete separation of these metals takes place.
- the document furthermore provides no information about the cost-efficiency of the process.
- WO 96/14440 describes a process for the electrochemical digestion of superalloys by anodic oxidation of the alloy in an electrolysis bath with an organic solvent component.
- the document discloses that up to 10% of water can be added to the electrolyte solution so that the process can still be carried out according to the invention. Otherwise, passivation of the anode occurs through formation of a gel or a firmly adhering oxide layer, which can lead to termination of the electrolysis.
- the working-up and separation of the valuable substances from the suspension forming as a result of the electrolysis are initially effected by filtration.
- the filtration residue separated off and containing a part of the alloy metals is then worked up thermally by calcination and subsequently by the customary hydrometallurgical processes.
- DE 10155791C1 likewise discloses an electrochemical digestion process for superalloys.
- the superalloys are first cast into sheets and then electrolytically digested in an oxygen-free inorganic acid.
- the problem of anodic passivation is counteracted by reversal of the polarity of the electrodes.
- the two last-mentioned processes can be implemented economically only under certain general conditions, in particular very high rhenium contents in superalloys.
- DE 19521333 C1 discloses a pyrometallurgical digestion of tungsten-containing hard metal and heavy metal scraps. The digestion takes place at temperatures between 800 and 1000° C. in a salt melt which consists of NaOH and Na 2 SO 4 . In these processes, a sodium tungstate melt is produced, which is dissolved in water after subsequent cooling.
- tungsten hard metal scrap is virtually completely digested there in alkaline, sulphate-containing melt under oxidizing conditions by formation of sodium tungstate. This is not surprising since the metallate is distinguished by high stability and dissolves in the NaOH melt under the reaction conditions. Thus, a complete dissolution process of the hard metal scrap is ensured.
- the object was achieved by a process for the recovery of valuable metals from superalloys, the superalloys being digested in a salt melt consisting of 60-95% by weight of NaOH and 5-40% by weight of Na 2 SO 4 and the melt digestion product formed thereby then being worked up hydrometallurgically with the aim of simple separation of the individual valuable metals.
- the digestion is preferably carried out in a salt melt consisting of 65-85% by weight of NaOH and 15-35% by weight of Na 2 SO 4 , particularly preferably of 70-80% by weight of NaOH and 20-30% by weight of Na 2 SO 4 .
- Superalloys according to the present invention are alloys which contain, as main components, 50 to 80% of nickel, 3 to 15% by weight of at least one or more of the elements cobalt, chromium and optionally aluminium, and 1 to 12% by weight of one or more of the elements rhenium, tantalum, niobium, tungsten, molybdenum, hafnium and platinum.
- the process according to the invention is suitable in particular for rhenium-containing superalloys which contain up to 12% by weight of rhenium.
- the digestion according to the invention of superalloys is advantageously carried out in such a way that up to 10% by weight, preferably up to 8% by weight and particularly preferably up to 5% by weight of sodium carbonate (Na 2 CO 3 ), based on the weight of the salt melt, are added to the salt melt.
- compositions of the salt melt are listed in Table 1.
- the superalloys may be present both in lump form and in pulverulent form (grindings or grinding dusts).
- the superalloy digestion can be carried out both in directly heated furnaces, e.g. in furnaces with gas or oil firing, and in indirectly heated furnaces, continuously or batchwise.
- the furnaces suitable for this purpose are, for example, rotary furnaces and rotary tubular kilns.
- the digestion of superalloys is preferably carried out in a moving alkaline melt in a directly fired rotary tubular kiln operated batchwise.
- the digestion according to the invention is carried out in such a way that at least 1 kg of salt melt, preferably at least 1.5 kg and particularly preferably at least 2 kg are used per 1 kg of superalloy. In the case of certain superalloys which have rhenium contents greater than 8%, up to 5 kg of salt melt are used per kilogram of superalloy.
- the digestion according to the invention of superalloys takes place particularly advantageously with regard to the space-time yield if air and/or oxygen, or a mixture thereof, is passed into the salt melt.
- a mixture of air and oxygen consisting of 25 to 95% by volume of air and 5 to 75% by volume of oxygen, preferably of 35 to 80% by volume of air and 20 to 65% by volume of oxygen, is preferably passed into the salt melt.
- the digestion according to the invention of superalloys is carried out at temperatures of 800 to 1200° C.
- the digestion is carried out in the temperature range of 850 to 1100° C., particularly preferably at 900 to 1050° C.
- Good digestion conditions are present if oxidizing agents are additionally introduced into the melt.
- oxidizing agents for example, nitrates, peroxodisulphates, peroxides of the alkali metals and/or mixtures thereof can serve as such.
- Potassium nitrate, sodium nitrate, sodium peroxide, potassium peroxide, sodium peroxodisulphate, potassium peroxodisulphate and/or mixtures thereof are advantageously used as oxidizing agents.
- Particularly good digestion rates are achieved if 5 to 25% by weight of the oxidizing component, based on the weight of the melt, are added to the melt.
- compositions of the salt melt are shown in Table 2.
- the melt digestion is particularly advantageously carried out in such a way that a partial oxidation of the superalloy takes place or, after virtually complete oxidation, reducing conditions are established for a certain time.
- three fractions are pre-formed in the melt itself, consisting of:
- the present invention therefore relates to a process for working up the superalloy melt digestion product, comprising the following steps:
- the process according to the invention is shown schematically in the attached FIG. 1 .
- the superalloy melt digestion product ( 2 ) is crushed after cooling to room temperature, then comminuted in a mill and then leached in water.
- the leaching is carried out at temperatures of less than 60° C. and particularly preferably at less than 40° C.
- the particular feature of the melt digestion comprises the three fractions which are formed therein beforehand and are present during the water leaching as fractions which can be easily separated:
- the rhenium can be separated off after the filtration from the filtrate ( 4 ) over strongly basic ion exchangers, as described in DE 10155791.
- the rhenium-free solution containing substantially sodium molybdate and sodium tungstate can be added to the process for obtaining molybdenum and tungsten.
- the nonmagnetic residue which contains up to 15% of tantalum, can be used as raw material in tantalum-metallurgy.
- the magnetic residue is advantageously used for the production of cobalt and nickel.
- the process according to the invention is suitable in particular for recovering rhenium from superalloys.
- the present invention furthermore relates to a process for obtaining rhenium from superalloys, comprising the following steps:
- the process according to the invention for obtaining rhenium from superalloys is advantageously carried out in a manner such that up to 10% by weight, preferably up to 8% by weight and particularly preferably up to 5% by weight of sodium carbonate (Na 2 CO 3 ), based on the weight of the salt melt, are added to the salt melt.
- Na 2 CO 3 sodium carbonate
- the removal of the rhenium from the aqueous suspension by means of strongly basic ion exchange resins is preferred.
- An advantage of the process according to the invention is that the superalloy digestion in an NaOH—Na 2 SO 4 melt is exothermic. By passing in air or an air/oxygen mixture, the process is readily controllable. A further advantage is that the valuable substances can be virtually completely recovered.
- the filter cake was suspended again in water, and the metallic, magnetic fractions were separated from the oxidic and hydroxidic fractions by circulating the suspension through a magnetic separator by means of a pump.
- the substantially metal-free suspension was then separated again by means of a filter press, and the filtrates were initially introduced for the next leaching run. 1.46 t of metal sludge ( 5 ) and 0.56 t of hydroxide sludge ( 6 ) were obtained.
- the hydroxide sludge ( 6 ) was sent to a tantalum facility for recovering the tantalum, and the metal sludge ( 5 ) was sent to a nickel facility for further working-up.
- the rhenium-containing filtrate ( 3 ) was passed over ion exchange columns with strongly basic ion exchangers for recovering the rhenium.
- the further enrichment and purification of the rhenium were effected by standard methods according to the prior art.
- the rhenium-free outflow of the ion exchange columns was used in a tungsten facility as an initially taken material for the leaching of WO 3 .
- the rhenium yield was 94%.
Abstract
The invention relates to a process for recovering valuable metals from a superalloy which has the steps of digesting the superalloy in a salt melt. The salt melt contains 60-95% by weight of NaOH and 5-40% by weight of Na2SO4.
Description
- The present invention relates to a process for the digestion of superalloys, in particular superalloy scrap, in a salt melt and subsequent recovery of the valuable metals.
- Superalloys are alloys which have a complex composition, are stable at high temperatures and are based on nickel and cobalt, with additions of other metals, such as, for example, aluminium, chromium, molybdenum, tungsten, tantalum, niobium, manganese, rhenium, platinum, titanium, zirconium and hafnium, and nonmetals, such as boron and/or carbon. The superalloys are high-strength and particularly hard-wearing alloys which are used in motor and engine construction, in energy technology and in aviation and space flight. The particular properties of these alloys are achieved in particular by the addition of rare and noble metals, such as rhenium, tantalum, niobium or even platinum. A good overview of the composition, properties and fields of use of the superalloys is to be found in Ullmann's Encyclopedia of Industrial Chemistry, Volume A13, Fifth Edition, 1989, pages 55-65, and in Kirk-Othmer Encyclopedia of Technology, Volume 12, Forth Edition, pages 417-458.
- The superalloys differ from the customary high-melting alloys, e.g. W—Re alloys or Mo—Re alloys, in their particular resistance to oxidation or corrosion. Thus, owing to their excellent oxidation stability, components comprising superalloys are used in the production of blades in aircraft turbines. After elapse of the duration of use, such parts are an important raw material source for recovering rare metals, in particular rhenium, tantalum, niobium, tungsten, molybdenum and platinum.
- The recovery of the alloy metals of the superalloys is commercially very interesting owing to the high proportion of expensive metals. Thus, special superalloys contain the metals rhenium in up to 12% by weight, tantalum in up to 12% by weight, niobium in up to 5% by weight and tungsten and molybdenum in up to 12% by weight. Further metals which serve as base metals in the superalloys are nickel and cobalt. For the last-mentioned metals, too, the superalloys are a raw material source from which the recovery of these metals is commercially expedient.
- For the recovery of the metallic components from superalloys, a large number of hydrometallurgical or pyrometallurgical and electrochemical processes are known which, owing to their complex embodiments and high energy demand, are not processes which are not carried out on a large scale from commercial points of view, especially owing to the constantly increasing energy prices.
- According to the prior art, for the recovery of the metallic components from the superalloys, the latter are melted kept under an inert gas atmosphere and then atomized to give a finely divided powder. In this procedure, a disadvantage is that the superalloys melt only at high temperatures between 1200 and 1500° C. The actual digestion of the superalloy takes place only in a second step by treatment of the powder obtained with acids. Experience has shown that several days are required for this purpose. According to another process, clump-like superalloy scrap is first comminuted by energy-intensive milling processes after prior embrittlement, for example at low temperatures, and then digested by a wet-chemical method at elevated temperatures in mineral acids of a certain concentration and composition, Potter et al., Eff. Technol. Recycling Metal 1971, page 35 et seq.
- Furthermore, some processes which envisage the digestion of the superalloy scrap via electrochemical processes are known.
- According to U.S. Pat. No. 3,649,487, the high-melting metals present in scraps of an Fe/Ni/Co/Cu base alloy, e.g. tungsten, molybdenum and chromium, are first converted into borides, carbides, nitrides, silicides or phosphides via a melting process by addition of non-metallic compounds of group III, IV or V, melted to give anodes and then subjected to an anodic oxidation. Those metals such as Co, Ni and Cu initially go into solution and are deposited from this at the cathode, while the high-melting metals, remain behind in the anode sludge, for example as borides, carbides, etc. It is disclosed here that the metals Ni, Co, Cu are separated from the high-melting metals, such as W, Mo or chromium, but there is no information at all about whether complete separation of these metals takes place. The document furthermore provides no information about the cost-efficiency of the process.
- WO 96/14440 describes a process for the electrochemical digestion of superalloys by anodic oxidation of the alloy in an electrolysis bath with an organic solvent component. The document discloses that up to 10% of water can be added to the electrolyte solution so that the process can still be carried out according to the invention. Otherwise, passivation of the anode occurs through formation of a gel or a firmly adhering oxide layer, which can lead to termination of the electrolysis. The working-up and separation of the valuable substances from the suspension forming as a result of the electrolysis are initially effected by filtration. The filtration residue separated off and containing a part of the alloy metals is then worked up thermally by calcination and subsequently by the customary hydrometallurgical processes.
- DE 10155791C1 likewise discloses an electrochemical digestion process for superalloys. In this process, the superalloys are first cast into sheets and then electrolytically digested in an oxygen-free inorganic acid. Here, the problem of anodic passivation is counteracted by reversal of the polarity of the electrodes. The two last-mentioned processes can be implemented economically only under certain general conditions, in particular very high rhenium contents in superalloys.
- DE 19521333 C1 discloses a pyrometallurgical digestion of tungsten-containing hard metal and heavy metal scraps. The digestion takes place at temperatures between 800 and 1000° C. in a salt melt which consists of NaOH and Na2SO4. In these processes, a sodium tungstate melt is produced, which is dissolved in water after subsequent cooling.
- As in the present invention, tungsten hard metal scrap is virtually completely digested there in alkaline, sulphate-containing melt under oxidizing conditions by formation of sodium tungstate. This is not surprising since the metallate is distinguished by high stability and dissolves in the NaOH melt under the reaction conditions. Thus, a complete dissolution process of the hard metal scrap is ensured.
- It was an object of this invention to provide a process for the digestion and recycling of superalloys, in particular rhenium-containing superalloy scraps, and working-up for recovery of the valuable materials present therein as a more economical alternative to recycling by anodic oxidation or acid digestion.
- The object was achieved by a process for the recovery of valuable metals from superalloys, the superalloys being digested in a salt melt consisting of 60-95% by weight of NaOH and 5-40% by weight of Na2SO4 and the melt digestion product formed thereby then being worked up hydrometallurgically with the aim of simple separation of the individual valuable metals.
- The digestion is preferably carried out in a salt melt consisting of 65-85% by weight of NaOH and 15-35% by weight of Na2SO4, particularly preferably of 70-80% by weight of NaOH and 20-30% by weight of Na2SO4.
- In the case of superalloys with the digestion of which the present invention is concerned, more than over 50% of the metallic constituents, e.g. nickel or cobalt, do not form metallates under the reaction conditions of DE 19521333 C1, and it was surprising that a corresponding digestion could take place at all. Furthermore, it was surprising that virtually all the nickel and cobalt was present in metallic form after digestion and hence particularly advantageous working-up of the melt digestion product where the use of magnetic separation was possible. At least, this results in a substantial economic advantage over the electrochemical digestion processes cited for superalloys. Superalloys according to the present invention are alloys which contain, as main components, 50 to 80% of nickel, 3 to 15% by weight of at least one or more of the elements cobalt, chromium and optionally aluminium, and 1 to 12% by weight of one or more of the elements rhenium, tantalum, niobium, tungsten, molybdenum, hafnium and platinum.
- The process according to the invention is suitable in particular for rhenium-containing superalloys which contain up to 12% by weight of rhenium. The digestion according to the invention of superalloys is advantageously carried out in such a way that up to 10% by weight, preferably up to 8% by weight and particularly preferably up to 5% by weight of sodium carbonate (Na2CO3), based on the weight of the salt melt, are added to the salt melt.
- Advantageous compositions of the salt melt are listed in Table 1.
-
TABLE 1 % by weight of % by weight of % by weight of NaOH Na2SO4 Na2CO3 85 5 10 80 10 10 70 25 5 80 15 5 75 20 5 72 20 8 - The superalloys may be present both in lump form and in pulverulent form (grindings or grinding dusts).
- The superalloy digestion can be carried out both in directly heated furnaces, e.g. in furnaces with gas or oil firing, and in indirectly heated furnaces, continuously or batchwise. The furnaces suitable for this purpose are, for example, rotary furnaces and rotary tubular kilns.
- The digestion of superalloys is preferably carried out in a moving alkaline melt in a directly fired rotary tubular kiln operated batchwise.
- The digestion according to the invention is carried out in such a way that at least 1 kg of salt melt, preferably at least 1.5 kg and particularly preferably at least 2 kg are used per 1 kg of superalloy. In the case of certain superalloys which have rhenium contents greater than 8%, up to 5 kg of salt melt are used per kilogram of superalloy.
- The digestion according to the invention of superalloys takes place particularly advantageously with regard to the space-time yield if air and/or oxygen, or a mixture thereof, is passed into the salt melt. A mixture of air and oxygen consisting of 25 to 95% by volume of air and 5 to 75% by volume of oxygen, preferably of 35 to 80% by volume of air and 20 to 65% by volume of oxygen, is preferably passed into the salt melt.
- The digestion according to the invention of superalloys is carried out at temperatures of 800 to 1200° C.
- Preferably, the digestion is carried out in the temperature range of 850 to 1100° C., particularly preferably at 900 to 1050° C. Good digestion conditions are present if oxidizing agents are additionally introduced into the melt. For example, nitrates, peroxodisulphates, peroxides of the alkali metals and/or mixtures thereof can serve as such. Potassium nitrate, sodium nitrate, sodium peroxide, potassium peroxide, sodium peroxodisulphate, potassium peroxodisulphate and/or mixtures thereof are advantageously used as oxidizing agents. Particularly good digestion rates are achieved if 5 to 25% by weight of the oxidizing component, based on the weight of the melt, are added to the melt.
- Advantageous compositions of the salt melt are shown in Table 2.
-
TABLE 2 % by weight % by weight of % by weight of % by weight of of oxidizing NaOH Na2SO4 Na2CO3 agent 70 10 — 20 (NaNO3) 77 5 — 18 (K2S2O8) 80 5 5 10 (Na2O2) 60 20 8 6 (NaNO3) 6 (Na2S2O8) 85 10 — 5 (Na2O2) - The melt digestion is particularly advantageously carried out in such a way that a partial oxidation of the superalloy takes place or, after virtually complete oxidation, reducing conditions are established for a certain time. In the digestion process according to the invention, three fractions are pre-formed in the melt itself, consisting of:
-
- water-soluble alkali metal oxometallates of the metals of the 6th and/or 7th subgroup and/or of the 3rd main group of the Periodic Table of the Elements and/or mixtures thereof;
- water-insoluble components from the group consisting of the metals Co, Ni, Fe, Mn or Cr and/or mixtures thereof,
- oxides and/or water-insoluble alkali metal oxometallates of the metals of the 4th or 5th subgroup of the Periodic Table of the Elements and/or mixtures thereof.
- These three fractions are then worked up hydrometallurgically. The present invention therefore relates to a process for working up the superalloy melt digestion product, comprising the following steps:
- a) conversion of the melt digestion product into the solid phase by cooling to room temperature,
b) commination of the solidified melt digestion product,
c) reaction of the comminuted melt digestion product in water at temperatures of less than 80° C. and production of an aqueous suspension containing -
- a solution consisting of a mixture of sodium compounds from the group consisting of NaOH, Na2SO4, NaAl(OH)4 and/or Na2CO3 and alkali metallates of the elements of the 6th and/or 7th subgroups of the Periodic Table of the Elements;
- a solid metallic phase consisting of the group of metals Co, Ni, Fe, Mn and Cr;
- a solid phase consisting of hydroxides and/or hydrated oxides of the metals of the 3rd main group and of metals of the 4th and/or 5th subgroup of the Periodic Table of the Elements,
d) removal of the aqueous fraction by filtration,
e) separation of the water-insoluble fraction by magnetic deposition of metallic components,
f) removal of the oxidic fraction.
- The process according to the invention is shown schematically in the attached
FIG. 1 . According toFIG. 1 , the superalloy melt digestion product (2) is crushed after cooling to room temperature, then comminuted in a mill and then leached in water. Preferably, the leaching is carried out at temperatures of less than 60° C. and particularly preferably at less than 40° C. The particular feature of the melt digestion comprises the three fractions which are formed therein beforehand and are present during the water leaching as fractions which can be easily separated: -
- the filtrate (4) which substantially contains the elements molybdenum, tungsten and rhenium in the form of their alkali metallates,
- the water-insoluble residue (3) which consists of a magnetic fraction which contains practically the total nickel and cobalt fractions of the alloy and about ⅓ of the chromium used, in metallic form, while all other elements are present only as secondary constituents or in the trace range, and
- a nonmagnetic fraction (5) which contains the elements aluminium, chromium, titanium, zirconium, hafnium, niobium and tantalum in the form of their oxides (e.g. Al2O3, Cr2O3, TiO2, ZrO2, HfO2, Ta2O5, Nb2O5), or hydroxides (e.g. Al(OH)3, Cr(OH)3, Ti(OH)4, Zr(OH)4, Hf(OH)4, Ta(OH)5, Nb(OH)5 or nitrides (e.g. AlN, CrN, TiN, HfN, NbN and TaN) or carbides (e.g. AlC, Cr2C3, TiC, ZrC, HfC, NbC and TaC).
- The further working-up of these fractions can be effected by the known methods. Thus, the rhenium can be separated off after the filtration from the filtrate (4) over strongly basic ion exchangers, as described in DE 10155791. The rhenium-free solution containing substantially sodium molybdate and sodium tungstate can be added to the process for obtaining molybdenum and tungsten.
- The nonmagnetic residue, which contains up to 15% of tantalum, can be used as raw material in tantalum-metallurgy.
- The magnetic residue is advantageously used for the production of cobalt and nickel.
- The process according to the invention is suitable in particular for recovering rhenium from superalloys. The present invention furthermore relates to a process for obtaining rhenium from superalloys, comprising the following steps:
- a) digestion of superalloys in a salt melt consisting of 60-95% by weight of NaOH and 5-40% by weight of Na2SO4,
b) cooling of the melt to room temperature,
c) commination of the melt digestion product,
d) reaction of the comminuted melt digestion product in water at temperatures of less than 80° C. and production of an aqueous suspension containing -
- a solution consisting of a mixture of sodium compounds from the group consisting of NaOH, Na2SO4, NaAl(OH)4 and/or Na2CO3 and alkali metallates of the elements of the 6th and/or 7th subgroup of the Periodic Table of the Elements;
- a solid metallic phase consisting of the group of metals Co, Ni, Fe, Mn and Cr;
- a solid phase consisting of hydroxides and/or hydrated oxides of the metals of the 3rd main group and of metals of the 4th and/or 5th subgroup of the Periodic Table of the Elements,
e) removal of the aqueous fraction by filtration,
f) removal of the rhenium from the aqueous fraction according to DE 10155791.
- The process according to the invention for obtaining rhenium from superalloys is advantageously carried out in a manner such that up to 10% by weight, preferably up to 8% by weight and particularly preferably up to 5% by weight of sodium carbonate (Na2CO3), based on the weight of the salt melt, are added to the salt melt. The removal of the rhenium from the aqueous suspension by means of strongly basic ion exchange resins is preferred.
- An advantage of the process according to the invention is that the superalloy digestion in an NaOH—Na2SO4 melt is exothermic. By passing in air or an air/oxygen mixture, the process is readily controllable. A further advantage is that the valuable substances can be virtually completely recovered.
- The invention is explained in more detail with reference to the following example.
- 1.97 t of superalloy grinding dust (1) were heated together with 2.50 t of NaOH and 0.45 t of Na2SO4 to 1110° C. in the course of 4 hours in a rotary furnace directly fired with natural gas and left at this temperature for a further hour. The composition of the superalloy grinding dust is shown in Table 1.
- Thereafter, the resulting viscous superalloy melt digestion product was completely poured out of the furnace. The cooled melt was first coarsely crushed and then melted to <2 mm. 5.26 t of pulverulent melt material (2) were obtained, which material was stirred into 7.5 m3 of water for leaching. After the end of the addition, stirring was continued for a further 2 hours, followed by filtration over a filter press and rinsing with 0.5 m3 of water. 2.10 t of filter residue (3) and 9.3 m3 of filtrate (4) were obtained. The filter cake was suspended again in water, and the metallic, magnetic fractions were separated from the oxidic and hydroxidic fractions by circulating the suspension through a magnetic separator by means of a pump. The substantially metal-free suspension was then separated again by means of a filter press, and the filtrates were initially introduced for the next leaching run. 1.46 t of metal sludge (5) and 0.56 t of hydroxide sludge (6) were obtained. The hydroxide sludge (6) was sent to a tantalum facility for recovering the tantalum, and the metal sludge (5) was sent to a nickel facility for further working-up. The rhenium-containing filtrate (3) was passed over ion exchange columns with strongly basic ion exchangers for recovering the rhenium. The further enrichment and purification of the rhenium were effected by standard methods according to the prior art. The rhenium-free outflow of the ion exchange columns was used in a tungsten facility as an initially taken material for the leaching of WO3. The rhenium yield was 94%.
- The composition of the superalloy grinding dust and of the most important intermediates is shown in Table 3.
-
TABLE 3 % kg % kg % kg g/L kg % kg % kg Al 9.28 183 4.47 235 1.46 30.5 21.9 204 0.12 1.7 5.05 28.4 Co 7.09 140 2.59 136 6.73 141 0.0 0.0 9.46 138 0.37 2.1 Cr 7.17 141 2.62 138 6.69 140 0.0 0.0 3.16 46.2 16.4 92.7 Hf 0.22 4.4 0.08 4.3 0.21 4.3 0.0 0.0 0.09 1.4 0.52 2.9 Mo 1.05 20.6 0.39 20.4 0.01 0.1 2.21 20.5 0.01 0.1 0.0 0.0 Ni 51.3 1001 19.0 999 47.9 1000 0.0 0.0 68.8 1006 3.14 17.7 Re 1.53 30.1 0.58 30.5 0.09 1.9 3.12 29.0 0.13 1.8 0.01 0.0 Ta 4.20 82.8 1.55 81.3 3.93 82.0 0.0 0.0 1.94 28.4 9.55 53.8 Ti 1.53 30.2 0.58 30.5 1.47 30.6 0.0 0.0 0.68 10.0 3.59 20.2 W 4.38 86.2 1.64 86.1 0.04 0.9 9.16 85.3 0.06 0.9 0.0 0.0 Zr 2.33 45.9 0.87 45.5 2.15 45 0.0 0.0 0.97 14.3 5.5 31.0 Non-metallic constituents 9.92 Total of metals 90.08 1775 1807 1476 339 1249 249
Claims (22)
1-21. (canceled)
22. A process for recovering valuable metals from a superalloy which comprises digesting the superalloy in a salt melt containing 60-95% by weight of NaOH and 5-40% by weight of Na2SO4.
23. The process according to claim 22 , which further comprises adding sodium carbonate in an amount not to exceed 10% by weight of the salt melt.
24. The process according to claim 23 , wherein the salt melt contains 75-90% by weight of NaOH, 5-20% by weight of Na2SO4 and 5-10% by weight of sodium carbonate.
25. The process according to claim 22 , wherein the superalloy contains one or more of the metals from the group consisting of Ni, Co, Cr or Al as a main component and one or more of the elements from the group consisting of Re, Mo, Ta, Nb, W, Hf or Pt as secondary component.
26. The process according to claim 25 , wherein the superalloy contains 0.5 to 12% by weight of rhenium.
27. The process according to claim 22 , wherein at least 1 kg of the salt melt is used per 1 kg of superalloy.
28. The process according to claim 22 , wherein the digesting is carried out in a moving melt.
29. The process according to claim 23 , wherein the digesting is carried out in a rotary tubular kiln operated batchwise or continuously.
30. The process according to claim 22 , which further comprises passing air and/or oxygen or a mixture thereof into the melt.
31. The process according to claim 22 , which further comprises adding oxidizing component to the melt, wherein the oxidizing component is a nitrate, peroxodisulphate, peroxide of the alkali metal and/or mixtures thereof.
32. The process according to claim 31 , wherein 5 to 25% by weight of the oxidizing component, based on the salt melt, are added to the melt.
33. The process according to claim 30 , wherein the mixture of air and oxygen consisting of 25 to 95% by volume of air and 5 to 75% by volume of oxygen is passed into the melt.
34. The process according to claim 32 , wherein the digesting is carried out at temperatures of 800 to 1200° C.
35. The process according to claim 32 , wherein the superalloy is partly oxidized.
36. The process according to claim 22 , wherein three fractions consisting of:
water-soluble alkali metal oxometallate of the metals of the 6th and/or 7th subgroup and/or of the 3rd main group of the Periodic Table of the Elements and/or mixtures thereof;
water-insolble components from the group consisting of the metals Co, Ni, Fe, Mn or Cr and/or mixtures thereof,
oxide and/or water-insoluble alkali metal oxometallate of the metals of the 4th or 5th subgroup of the Periodic Table of the Elements and/or mixtures thereof are pre-formed in the melt.
37. A process for recovering valuable metals from a superalloy comprising the following steps:
a) converting of the melt digestion product according to claim 36 into the solid phase by cooling to room temperature,
b) commination of the solidified melt digestion product,
c) reacting of the comminuted melt digestion product in water at temperatures of less than 80° C. and production of an aqueous suspension containing
a solution consisting of a mixture of sodium compounds from the group consisting of NaOH, Na2SO4, NaAl(OH)4 and/or Na2CO3 and alkali metallates of the elements of the 6th and/or 7th subgroups of the Periodic Table of the Elements;
a solid metallic phase consisting of the group of metals Co, Ni, Fe, Mn and Cr;
a solid phase consisting of hydroxides and/or hydrated oxides of the metals of the 3rd main group and of metals of the 4th and/or 5th subgroup of the Periodic Table of the Elements,
d) removing of the aqueous fraction by filtration,
e) separating of the water-insoluble fraction by magnetic deposition of metallic components, and
f) removing the oxidic fraction.
38. The process according to claim 37 , wherein the reaction of the melt digestion product in water is carried out at temperatures of less than 60° C.
39. The process according to claim 37 , wherein the reaction of the melt digestion product in water is carried out at temperatures of less than 40° C.
40. A process for obtaining rhenium from a superalloy consisting of the following steps:
a) digesting the superalloy in a salt melt consisting essentially of 60-95% by weight of NaOH and 5-40% by weight of Na2SO4,
b) cooling of the melt to room temperature,
c) commination of the melt digestion product,
d) reacting of the comminuted melt digestion product in water at temperatures of less than 80° C. and production of an aqueous suspension containing
a solution consisting of a mixture of sodium compounds from the group consisting of NaOH, Na2SO4, NaAl(OH)4 and/or Na2CO3 and alkali metallates of the elements of the 6th and/or 7th subgroup of the Periodic Table of the Elements;
a solid metallic phase consisting of the group of metals Co, Ni, Fe, Mn and Cr;
a solid phase consisting of hydroxides and/or hydrated oxides of the metals of the 3rd main group and of metals of the 4th and/or 5th subgroup of the Periodic Table of the Elements,
e) removing of the aqueous fraction by filtration, and
f) removing of the rhenium from the aqueous fraction.
41. The process according to claim 40 , which further comprises adding sodium carbonate in an amount not to exceed 10% by weight of the salt melt.
42. The process according to claim 22 , wherein the superalloy is a superalloy scrap.
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PCT/EP2007/056527 WO2008000810A1 (en) | 2006-06-30 | 2007-06-29 | Recycling of superalloys with the aid of an alkali metal salt bath |
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CA (1) | CA2654516C (en) |
DE (1) | DE102006030731A1 (en) |
MX (1) | MX2008015447A (en) |
PL (1) | PL2038438T3 (en) |
RU (1) | RU2447165C2 (en) |
WO (1) | WO2008000810A1 (en) |
Cited By (7)
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US20110229366A1 (en) * | 2010-03-16 | 2011-09-22 | Luederitz Eberhard | Method for recovering rhenium and other metals from rhenium-bearing materials |
US20120058029A1 (en) * | 2009-03-13 | 2012-03-08 | Neo Performance Materials Limited | Rhenium recovery |
US8632747B2 (en) | 2009-03-11 | 2014-01-21 | A.L.M.T. Corp. | Method for producing sodium tungstate, method for collecting tungsten, apparatus for producing sodium tungstate, and method for producing sodium tungstate aqueous solution |
US9322081B2 (en) | 2011-07-05 | 2016-04-26 | Orchard Material Technology, Llc | Retrieval of high value refractory metals from alloys and mixtures |
WO2017075015A1 (en) | 2015-10-26 | 2017-05-04 | Techemet, Llc | A method for platinum recovery from materials containing rhenium and platinum metals |
US10011890B2 (en) | 2013-03-15 | 2018-07-03 | A.L.M.T. Corp. | Sodium tungstate production method |
CN111876620A (en) * | 2020-07-21 | 2020-11-03 | 浙江今飞凯达轮毂股份有限公司 | Titanium element additive and preparation method thereof |
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CN108342583B (en) * | 2018-02-08 | 2020-01-14 | 河南科技大学 | Method for recovering rhenium and molybdenum from molybdenum concentrate roasting dust |
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- 2007-06-29 CN CN2007800245331A patent/CN101479394B/en not_active Expired - Fee Related
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US9512504B2 (en) | 2009-03-11 | 2016-12-06 | A.L.M.T Corp. | Method for producing sodium tungstate, method for collecting tungsten, apparatus for producing sodium tungstate, and method for producing sodium tungstate aqueous solution |
US9249479B2 (en) | 2009-03-11 | 2016-02-02 | A.L.M.T. Corp. | Method for producing sodium tungstate, method for collecting tungsten, apparatus for producing sodium tungstate, and method for producing sodium tungstate aqueous solution |
US8632747B2 (en) | 2009-03-11 | 2014-01-21 | A.L.M.T. Corp. | Method for producing sodium tungstate, method for collecting tungsten, apparatus for producing sodium tungstate, and method for producing sodium tungstate aqueous solution |
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DE112016004897T5 (en) | 2015-10-26 | 2018-07-05 | Techemet, Llc | Process for platinum recovery from materials containing rhenium and platinum metals |
CN111876620A (en) * | 2020-07-21 | 2020-11-03 | 浙江今飞凯达轮毂股份有限公司 | Titanium element additive and preparation method thereof |
Also Published As
Publication number | Publication date |
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KR101457713B1 (en) | 2014-11-03 |
ATE528415T1 (en) | 2011-10-15 |
CA2654516C (en) | 2014-12-23 |
WO2008000810A1 (en) | 2008-01-03 |
JP2009541596A (en) | 2009-11-26 |
EP2038438B1 (en) | 2011-10-12 |
MX2008015447A (en) | 2008-12-12 |
PL2038438T3 (en) | 2012-04-30 |
JP5550336B2 (en) | 2014-07-16 |
RU2447165C2 (en) | 2012-04-10 |
RU2009102948A (en) | 2010-08-10 |
CN101479394A (en) | 2009-07-08 |
KR20090023692A (en) | 2009-03-05 |
CN101479394B (en) | 2012-09-26 |
EP2038438A1 (en) | 2009-03-25 |
CA2654516A1 (en) | 2008-01-03 |
DE102006030731A1 (en) | 2008-01-03 |
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