US20220056557A1 - Method for recovery of metal-containing material from a composite material - Google Patents
Method for recovery of metal-containing material from a composite material Download PDFInfo
- Publication number
- US20220056557A1 US20220056557A1 US17/516,323 US202117516323A US2022056557A1 US 20220056557 A1 US20220056557 A1 US 20220056557A1 US 202117516323 A US202117516323 A US 202117516323A US 2022056557 A1 US2022056557 A1 US 2022056557A1
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- United States
- Prior art keywords
- metal
- product
- prod
- composite material
- matrix
- 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.)
- Abandoned
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 177
- 239000002184 metal Substances 0.000 title claims abstract description 164
- 239000002131 composite material Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000011084 recovery Methods 0.000 title abstract description 29
- 239000000463 material Substances 0.000 title description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 90
- 239000011159 matrix material Substances 0.000 claims abstract description 59
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 39
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims description 57
- 229910052719 titanium Inorganic materials 0.000 claims description 54
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 45
- 229910045601 alloy Inorganic materials 0.000 claims description 20
- 239000000956 alloy Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001788 irregular Effects 0.000 claims description 4
- 229910000883 Ti6Al4V Inorganic materials 0.000 claims 3
- 239000000047 product Substances 0.000 description 70
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 44
- 229910001629 magnesium chloride Inorganic materials 0.000 description 22
- 239000011777 magnesium Substances 0.000 description 21
- 238000002844 melting Methods 0.000 description 21
- 230000008018 melting Effects 0.000 description 21
- 229910052749 magnesium Inorganic materials 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 12
- 229910010068 TiCl2 Inorganic materials 0.000 description 11
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910010062 TiCl3 Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 229910001507 metal halide Inorganic materials 0.000 description 7
- 150000005309 metal halides Chemical class 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000007789 gas Substances 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
- 150000004820 halides Chemical class 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 208000020442 loss of weight Diseases 0.000 description 3
- 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 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 238000009694 cold isostatic pressing Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000010310 metallurgical process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- -1 titanium halide Chemical class 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001627 beryllium chloride Inorganic materials 0.000 description 1
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012063 pure reaction product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910021324 titanium aluminide Inorganic materials 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- B22F1/0011—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- 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
- C22B21/00—Obtaining aluminium
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/02—Obtaining aluminium with reducing
-
- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
-
- 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
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
- B22F2301/205—Titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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- 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 method for the recovery of metal-containing material from a composite material.
- the invention relates to a method for the recovery of a metal-containing product (M Prod ) from a novel composite material comprising a matrix of oxidised reductant (R o ), a product metal (M P ) dispersed in the matrix of oxidised reductant (R o ) and one or more metal compounds (M P C R ) of the product metal (M P ) in one or more oxidation states dispersed in the matrix of oxidised reductant (R o ).
- WO 2006/042360 provides a method for producing titanium by reaction of titanium tetrachloride with magnesium in a reactor, which may comprise a fluidised bed.
- the temperature in the reactor is above the melting point of magnesium, but below the melting point of magnesium chloride.
- the method produces particles comprising titanium which are removed from the reactor and processed in order to recover titanium particles generally having a particle size of greater than 500 ⁇ m.
- the method of WO 2006/042360 is operated under an excess of magnesium with unreacted magnesium optionally collected and recycled to the reactor. This is understood to achieve complete conversion of TiCl 4 to titanium metal, while avoiding the formation of sub-chlorides, TiCl 2 and TiCl 3 .
- the applicant has identified methods for producing composite materials from at least one metal compound in which an excess of oxidant is fed to the reactor during processing.
- the composite material will generally be in finely divided form and the method, generally, does not place significant weight on the exclusion of by-products in the composite material.
- the methods for the production of the composite material are described in detail in a co-pending international patent application with the title “METHOD FOR THE PRODUCTION OF A COMPOSITE MATERIAL USING EXCESS OXIDANT”, filed on the same date as the present application. The contents of the co-pending application are incorporated herein in their entirety.
- the present invention relates generally to a method for the recovery of a metal-containing product (M Prod ) from a composite material.
- M Prod metal-containing product
- a composite material comprising a matrix of oxidised reductant (R o ), a product metal (M P ) dispersed in the matrix of oxidised reductant (R o ), and one or more metal compounds (M P C R ) of the product metal (M P ) in one or more oxidation states dispersed in the matrix of oxidised reductant (R o ); and
- composite material will be used to describe a composite material that is a metal-salt composite, an alloy-salt composite or an inter-metallic-salt composite. That is, the term “composite material” as used herein is intended to include within its scope a composite comprising a salt and (i) a metallic element and a reduced metal compound of a metallic element, (ii) two or more metallic elements and reduced metal compounds of two or more metallic elements, and (iii) one or more metallic elements together with one or more non-metallic elements and one or more reduced metal compounds of one or more metallic elements.
- product metal will be used to describe a product that is a metal, an alloy or an inter-metallic. That is, the term “product metal” as used herein is intended to include within its scope product comprising (i) one metallic element, (ii) two or more metallic elements, or (iii) one or more metallic elements together with one or more non-metallic elements.
- the term “remove” will be used to describe physical removal of the one or more metal compounds (M P C R ) from the matrix of oxidised reductant (R o ), such as by distillation or other physical mechanisms. It will also be used to describe conversion of the metal compounds (M P C R ), for example by reduction.
- the treatment step comprises distilling the one or more metal compounds (M P C R ) from the matrix of oxidised reductant (R o ). The distillation may further at least partially remove the oxidised reductant (R o ).
- the treatment step comprises subjecting the composite material to conditions that result in volatilisation of the oxidised reductant (R o ). For example, the conditions may result in sublimation of the oxidised reductant (R o ).
- the treatment step may comprise at least one of (i) volatilisation of the one or more metal compounds (M P C R ), and (ii) reduction of the one or more metal compounds (M P C R ) to the product metal (M P ).
- the one or more metal compounds (M P C R ) and, optionally, the oxidised reductant (R o ), are removed from the composite material by vacuum distillation.
- the vacuum distillation may be carried out under inert conditions, such as under argon gas. If so, the inert (e.g. argon) gas is added, as a barrier gas, at a rate that is dependent on the scale of the operation and vacuum applied.
- the vacuum distillation may be conducted at a pressure of from 0.01 to 0.015 kPa.
- the vacuum distillation is preferably conducted at conditions at which sublimation of the oxidised reductant (R o ) occurs.
- the product metal (M P ) comprises titanium and the oxidised reductant (R o ) comprises magnesium chloride and the vacuum distillation is conducted at a temperature of from 700° C. to 950° C., and the product metal (M P ) optionally comprises at least titanium.
- treatment at relatively low pressures maintains the form of the product metal (M P ) recovered from the composite material.
- the composite material is particulate and comprises a plurality of small particles, as discussed in more detail below, treatment under these conditions may result in the recovery of product metal (M P ) in particulate form.
- the treatment step comprises reducing the one or more metal compounds (M P C R ) of the product metal (M P ) to the product metal (M P ) in the presence of a reductant (R).
- the reductant (R) may be included within the matrix of oxidised reductant (R o ), and/or the reductant (R) may be combined with the composite material prior to or during the distillation.
- the treatment step comprises melting at least the matrix of oxidised reductant of the composite material and recovering the metal-containing product (M Prod ) from the melt.
- the temperature at which melting is conducted will be somewhat predicated by the components of the matrix of oxidised reductant of the composite material.
- melting may be conducted at a temperature below the individual melting temperatures of each component of the matrix by formation of compositions inclusive of hypoeutectic and hypereutectic compositions.
- the composition of the components of the composite may form a eutectic composition.
- Melting may be conducted by introducing the composite material to a molten bath.
- the molten bath may be one of reduced melting point, for example a eutectic mixture.
- recovering the metal-containing product (M Prod ) from the melt may comprise subjecting the melt to conditions at which the product metal (M P ), the one or more metal compounds (M P C R ) and the oxidised reductant (R o ) form separate layers in the melt and recovering the product metal (M P ) layer.
- separation may comprise density separation, gravity separation or centrifugation.
- Recovery may also comprise dissolution of components of the composite material, such as the one or more metal compounds (M P C R ) and oxidised reductant (R o ).
- the form of the product metal (M P ) may not be maintained, but instead the (M P ) may be recovered and formed into, for example, ingots of the product metal (M P ).
- the reductant (R) may be a solid, solid particulate, liquid or vapour.
- the reductant (R) is selected from the group consisting of Mg, Na, K, Li, Ba, Ca, Be and Al, although it is envisaged other options may also be suitable.
- two or more reductants (R), which may include one or more metal reductant (M R ) may be present.
- the reductant (R) may suitably comprise a multi-component reductant, such as an alloy, for example an Mg—Al or Mg—Pd alloy.
- the composite material comprises up to 20 wt %, preferably up to 3 wt % of the reductant (R).
- the one or more metal compounds (M P C R ) of the product metal (M P ) in one or more oxidation states comprise one or more metal halides (M P X) of the product metal (M P ).
- the one or more metal compounds (M P C R ) of the product metal (M P ) in one or more oxidation states may comprise a metal halide selected from the group consisting of halides of titanium, aluminium, vanadium, chromium, niobium, molybdenum, zirconium, silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum, scandium, ruthenium and the rare earths or a combination of any two or more thereof.
- the one or more metal compounds (M P C R ) of the product metal (M P ) in one or more oxidation states may comprise at least two metal halides. If so, the metal halides may be preferably selected from the group consisting of halides of titanium, aluminium and vanadium.
- the oxidised reductant (R o ) comprises a metal halide (M R X).
- M R X metal halide
- the metal halide (M RX ) may be selected from the group consisting of MgCl 2 , NaCl, KCl, LiCl, BaCl 2 , CaCl 2 ), BeCl 2 AlCl 3 , and any combination thereof.
- the composite material may further comprise one or more metals (M).
- M metals
- an additional metal incorporated into the composite material during preparation of the composite material.
- the metal (M) may be selected from the group consisting of titanium, aluminium, vanadium, chromium, niobium, molybdenum, zirconium, silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum, scandium, ruthenium and the rare earths or a combination of any two or more thereof.
- the other metal, (i.e. metallic element) may be aluminium metal as a solid or liquid.
- the composite material is in the form of particles.
- the particles may be generally spherical. They may also be regular or irregular in shape.
- the particles have an average particle size of up to 500 ⁇ m, more preferably from 20-300 ⁇ m.
- the metal component (M P ) within the composite material generally has a particle size of up to about 1 micron.
- the surface area to volume ratio of the metal component (M P ) in the protective matrix is preferably greater than 6 m 2 /mL.
- the composite material is formed by contacting Mg with an excess of TiCl 4 in a fluidised bed reactor to form Ti metal dispersed in a MgCl 2 matrix
- TiCl 4 may react with one atom of Mg and produce MgCl 2 and TiCl 2 .
- Mg reacts with TiCl 2 and forms a second MgCl 2 and a single Ti atom. Therefore, at its limit, it is envisaged that the finely divided metal component (M P ) may be present in the protective matrix of MgCl 2 on an atomic scale. Such examples would represent true “primary particles” of the metal component (M P ).
- M P metal component
- metal component (M P ) of these preferred embodiments of the invention is the lack of a protective oxide layer.
- the metal component (M P ) particles of these embodiments do not have an activation barrier, which correlates with a lower activation energy (increase in reactivity) of the metal component (M P ).
- generally small particles are highly pyrophoric.
- the composite material of the preferred embodiments of the invention is, comparatively, not. For conventional metal powders of approximately ⁇ 10 ⁇ m, pyrophoricity becomes a major issue, but can be serious even at much larger sizes (>100 ⁇ m) under some conditions.
- the protective matrix of the composite material of the invention advantageously overcomes this issue.
- the method of the invention may further comprise combining the composite material with an additional component prior to or during the treating step.
- the additional component may be selected from the group consisting of (i) a composite material comprising a matrix of oxidised reductant (R o ), for example a metal halide, with one or more metallic elements dispersed in the matrix, (ii) a metallic element or compound; (iii) a non-metallic element or compound, (iv) a metalloid element or compound, and (v) any combination of two or more of these.
- the composite material may be combined with any one or more of the groups consisting of beryllium, boron, carbon, nitrogen, oxygen, aluminium, silicon, phosphorous, sulphur, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lead, bismuth, the Rare Earths and compounds thereof.
- the groups consisting of beryllium, boron, carbon, nitrogen, oxygen, aluminium, silicon, phosphorous, sulphur, scandium, vanadium, chromium, manganese, iron, cobalt, nickel
- the metal-containing product (M Prod ) may consist of the product metal (M P ) and the method may comprise recovering the product metal (M P ) from the composite material.
- the method may further comprise a post-treatment of the recovered product metal (M P ).
- the post-treatment comprises, milling, grinding, coating, pressing, heat treating (e.g. aging, annealing, quenching, tempering), rolling, forming, casting, hot or cold isostatic pressing (HIPing or CIP), moulding, melting, sintering, blending, extruding, drawing, forging, turning, welding, atomising and/or spraying.
- the method may further comprise pre-treating the composite material prior to the treatment step.
- the pre-treatment may comprise at least one of compacting, milling and grinding the composite material.
- metal-containing product (M Prod ) produced by a method as described above.
- the metal-containing product (M Prod ) formed according to the invention may comprise particulate metal having a particle size of less than 500 ⁇ m, preferably from 20-300 ⁇ m, or may comprise ingots of the product metal (M P ).
- the product metal (M P ) is an alloy, for example an alloy of two or more of titanium, vanadium and aluminium.
- the alloy may approximate Ti64.
- Ti64 alloy generally refers to an alloy having a chemical composition of 6% aluminium, 4% vanadium, 0.25% (maximum) iron, 0.2% (maximum) oxygen, and the remainder titanium. Ti64 is also commonly referred to as Grade 5 titanium.
- palladium may be incorporated into the composite material to facilitate recovery of Grade 7 titanium.
- Grade 7 titanium contains 0.12 to 0.25% palladium. The small quantity of palladium provides enhanced crevice corrosion resistance at low temperatures and high pH.
- the particulate metal may be suitable for use in many powder metallurgical processes.
- the form of the product metal (M P ) recovered be that in terms of desired shapes and particle sizes of the particles, may be predicted by manipulating the method of recovery, and also manipulating the method of production of the composite material. That is, the size and shape of the particles may be manipulated in order to achieve suitable particles for a particular powder metallurgical process.
- FIG. 1 illustrates a flow chart of a method for the recovery of metal-containing product (M Prod ) from a composite material, which also illustrates an exemplary method for obtaining a composite material.
- M Prod metal-containing product
- FIG. 2 illustrates weight loss of titanium composite rapidly heated to 500° C. and held at that temperature for a period of time according to example 4.
- FIG. 3 shows the total content of titanium and magnesium as determined by XRF of the feed material of Example 5 and several subsequent samples of the recovered material.
- FIG. 4 shows a similar plot to FIG. 3 , but separately shows the individual content of titanium and magnesium.
- a method 200 for the recovery of a metal-containing product (M Prod ) from a composite material is illustrated. Also illustrated for convenience and without any limitation to the method of recovery of the present invention, is an exemplary method 100 for the production of a suitable composite material that contains one or more metal compounds (M P C R ) of the product metal (M P ) in one or more oxidation states.
- M P C R metal compounds
- M P C R metal compounds
- metal compound (M P C) 110 of a product metal (M P ) and a reductant (R) 120 capable of reducing the metal compound (M P C) 110 of the product metal (M P ) are supplied to a reactor 130 .
- Composite material 150 is recovered from the reactor 130 .
- the composite material comprises a matrix of oxidised reductant (R o ), product metal (M P ) dispersed in the matrix of oxidised reductant (R o ), and one or more metal compounds (M P C R ) of the product metal (M P ) in one or more oxidation states dispersed in the matrix of oxidised reductant (R o ).
- the composite material may further comprise reductant (R).
- the reactor 130 which will be discussed in terms of a fluidised bed reactor with reference to FIG. 1 , is run at a temperature that is below the melting point of the oxidised reductant (R o ) and, generally, above the melting point of the reductant (R) 120 , which may form part of the composite material 150 .
- the temperature in the reactor 130 is between the melting point of the reductant (R) 120 and the melting point of the oxidised reductant (R o ), for example its oxidised salt
- the reaction of the reductant (R) 120 with oxidant results in the formation of a composite material 150 comprised of largely or entirely solid character. This ‘freezing’ reaction advantageously has the impact of creating finely divided and highly pure reaction products.
- the particle size of the composite material 150 is such that the finely divided elements comprised within are sufficiently small that they interact differently with visible light than their bulk counterparts. For example, they may appear black or dark in colour.
- the finely divided structure of the composite material 150 has advantages compared with composites of analogous nominal compositions that do not have the same finely divided structure. These advantages will be elucidated in more detail below.
- the prevailing conditions in the reactor 130 ensure, with sufficient time, the melting of the reductant 120 .
- the time required for melting of solid reductant 120 depends upon numerous factors, including the feed mechanism, whether the reductant 120 is fed with other materials, the temperature of the reactor 130 , the reaction intensity of the reactor 130 per unit volume, the particulate density of the reductant 120 feed at any single location and, if other reductant or reagent or inert streams are in or are entering into the reactor, the proximity to these components and their respective temperatures when impinging on particles of the reductant 120 .
- the interaction of the reductant (R) 120 upon contacting other surfaces in the reactor 130 will depend on its phase at that time. If the reductant 120 particle is solid, it is possible the reductant 120 particle will collide and rebound. It will then continue to interact with other surfaces and environments in the reactor 130 .
- the reductant 120 particle has a molten external surface and solid inner surface, it is possible the particle will adhere to any surface it impacts, creating a composite of the two objects. The particle will then continue to interact with other surfaces and environments in the reactor 130 .
- the reductant 120 particle is molten when it interacts with other surfaces, it may wet the surface. Depending upon the nature of the solid-liquid interaction the thickness of the layer formed will vary. It is considered that this may be manipulated through varying intensity of interactions, density of reductant 120 feed, temperature and time, etc.
- molten reductant in the reactor 130 is as a stand-alone mass, wetted on a surface or combined with other surfaces, at some point it will interact with oxidant and react. At this point the thickness or the wetted layer or size of the molten mass or particle is considered of some importance in determining the extent of reaction of the reductant (R) 120 and the morphology of the final composite material 150 .
- the freezing nature of the reaction as described previously can result in a proportion of the reductant (R) becoming encapsulated by the composite material 150 .
- the surface exposed to oxidant reacts to form a solid it may form a barrier (i.e. shell) that may restrict or eliminate the participation of the remaining reductant in further reduction.
- the process can consume the majority if not all of the reductant (R).
- the amount of oxidant in the reactor relative to reductant (R) will be an important factor in determining the probability of the above mentioned interactions.
- Weighting of one form of interaction over others can be manipulated by changing operating conditions, feed forms, etc.
- the nature of surfaces in the reactor available for interaction, potential for sequential ordering and forms in which the reductant and oxidant are brought into contact can result in composites being formed which have diverse characteristics. These may include, without limitation, excess or fully consumed reductant, layers of composite, layers of composite with magnesium interstitial layers. It is thought that novel structured materials may be formed by sequential layering of dissimilar layers of prescribed composition.
- the present invention relates to a method 200 for the recovery of a metal-containing product (M Prod ) from a composite material 150 .
- the method comprises the recovery of the product metal (M P ) directly from the composite material 210 , or may comprise recovery after combining the composite material with composite material of other product metal (M P′ ) 220 , and/or other compounding material (C M ) 230 .
- various products may be recovered, including without limitation a metal-containing product (M Prod ) 240 , an alloy or mixture of metal-containing product (M Prod /M Prod′ ) 250 , and a mixture or composite metal-containing product (M Prod /C M ) 260 .
- reductant (R) Once a desired composite material is formulated (i.e. with or without additional material), it is treated 270 to recover the metal-containing product 240 , 250 , 260 .
- Treatment 270 of the composite material aim to at least partially remove the one or more metal compounds (M P C R ) from the matrix of oxidised reductant (R o ) to form the metal-containing product (M Prod ).
- the aim of the treatment step 270 is to substantially completely remove the one or more metal compounds (M P C R ) from the matrix of oxidised reductant (R o ).
- two methods of treatment 270 are particularly useful for the removal of the one or more metal compounds (M P C R ) from the matrix of oxidised reductant (R o ). These include distillation, particularly vacuum distillation, and reduction of the one or more metal compounds (M P C R ) to product metal (M P ) in the presence of a reductant. These two options may be performed independently, or in combination. It will be appreciated, though, that other suitable options may be employed.
- the treatment step 270 may suitably comprise melting the composite material and subsequent separation of the one or more metal compounds (M P C R ).
- the treatment step 270 may also result in the removal of the matrix of oxidised reductant (R o ) from the composite material.
- the one or more metal compounds (M P C R ) and the oxidised reductant (R o ) may be removed from the composite material by vacuum distillation.
- the treatment 270 may further result in the removal of reductant (R), if present, which may be recycled to the reductant feed 120 , or be otherwise recovered.
- the metal-containing product 240 , 250 , 260 may consist of product metal (M P ) 240 , an alloy or mixture of product metals (M P /M P′ ) 250 , and a mixture or composite (M P /C M ) 260 .
- the finely divided nature of the product metal (M P ) in the composite material 150 is encased in materials chemically inert to itself by the nature of their generation.
- Product metal of similar compositional properties but without the same physical characteristics engendered by the encasement process will not respond to the same recovery process with analogous results. That is, the surface is free from any protective or passivation layer meaning that it will respond differently to physical interactions than its macroscopic bulk counterpart.
- the individual components of product metal encased in inert material provide for building blocks that may or may not combine to various extents and by different driving forces through the process of recovery to yield the product metal (M P ).
- the conditions under which the liberation of the product metal (M P ) from the composite matrix proceeds and the conditions throughout the recovery process have a significantly determinative impact on the way in which each divided product metal building block interacts with others, and ultimately on the manner in which they may or may not combine and the morphology and microstructure of the recovered product metal.
- Example 1 CP2 Titanium Recovery from a Predominantly MgCl 2 Matrix
- the vessel was purged with air and the remnant material was recovered from the vessel, comprising approximately 5 g of titanium metal.
- the metal was in the form of loosely sintered spheres with size approximately one half of the particulate size of the composite material fed into the vessel.
- the recovery process produced commercially pure grade 2 titanium.
- 15 g of composite material, black in colour, in spherical particulate form comprising a matrix of magnesium chloride, titanium metal, aluminium metal, magnesium and quantities of titanium sub-halides (TiCl 2 and TiCl 3 ) was combined with 15 g of composite material, black in colour, in spherical particulate form comprising a matrix of magnesium chloride, titanium metal, vanadium metal, magnesium and quantities of titanium sub-halides (TiCl 2 and TiCl 3 ) and possibly vanadium sub-halides.
- the total of 30 g of composite material was ground under inert conditions to form a homogeneous composition and then placed in a vessel made from stainless steel. The degree of milling could be altered for differing levels of uniformity.
- the vessel was placed under vacuum at a pressure of approximately 0.01 kPa.
- An argon purge was supplied at a rate of 10 mg/min.
- the vessel was then heated externally to a temperature of 900° C. at a heating rate of 31° C. per minute.
- the vessel was then left at a temperature of 900° C. for one hour before being cooled to room temperature.
- the vessel was purged with air and the remnant material was recovered from the vessel, comprising approximately 5 g of titanium, aluminium and vanadium containing metal in proportion with the sum of the product metal in the input composite material.
- the metal was in the form of closely packed sintered particles with irregular shape.
- the contents of the vessel was recovered and found to be a white and silver coloured mass comprised of titanium metal and magnesium chloride. There was no appearance of green or violet colouring to indicate presence of titanium sub-halides in the salt phase.
- the mass was broken up and milled to a powder and returned to the stainless steel vessel.
- the vessel was placed under vacuum at a pressure of approximately 0.01 kPa.
- An argon purge was supplied at a rate of 10 mg/min.
- the vessel was then heated externally to a temperature of 900° C. at a heating rate of 31° C. per minute.
- the vessel was then left at a temperature of 900° C. for one hour before being cooled to room temperature.
- the vessel was purged with air and the remnant material was recovered from the vessel, comprising approximately 5 g of titanium metal.
- the product metal was liberated from the protective matrix and enabled to consolidate to a degree by sintering.
- melting of the matrix provides the opportunity for partially reduced or oxidised compounds to be liberated from the matrix structure and a significantly enhanced opportunity to interact and react with other compounds in the matrix, or be removed by boiling.
- composite material black in colour, in angular particulate form comprising a matrix of magnesium chloride, titanium metal, magnesium and quantities of titanium sub-halides (TiCl 2 and TiCl 3 ) was placed in an open alumina cup.
- the cup was placed in a vacuum furnace at a pressure of approximately 0.01 kPa.
- An argon purge was supplied at a rate of 2 mg/min.
- the furnace was then heated to a temperature of 500° C. at a heating rate of 100° C. per minute, which under vacuum is sufficient for removing titanium and promoting the disproportionation of titanium sub-halides.
- the vessel was then left at a temperature of 500° C. for one hour before being cooled to room temperature.
- FIG. 2 shows the loss of weight of the material over time in the process. It can be seen the weight stabilises after a short period.
- the remnant material was recovered from the vessel, comprising approximately 30 mg of metal containing composite material with a substantially reduced sub-halide content.
- This composite could be put through further recovery processes, where the impact of the significant volatile sub-halide content would be reduced or eliminated. Such impacts could include significant increase in total volatile content, difficulty in controlling sub-halide conversion to metal or removal.
- a titanium composite containing significant sub-halide content was passed through vacuum at 600° C. with a residence time of 2 hours.
- the feed composite comprised uniform black spheres with particle size of ⁇ 2 mm.
- FIG. 3 shows the total content of titanium and magnesium as determined by XRF of the feed material and several subsequent samples of the recovered material.
- FIG. 4 shows a similar plot but separately shows the individual content of titanium and magnesium.
- FIG. 3 The increase in total metal ion content between the deed and the recovered material as shown in FIG. 3 indicates that the metal component of the composite has been concentrated in the process.
- FIG. 4 shows that the titanium content of the recovered material is reduced after processing, which when combined with the total metal content increasing suggests that a titanium halide phase has been removed by processing without impacting the remaining composite constituents.
- the process reduces the mass ration of titanium to magnesium from 1.12 substantially towards the theoretical ratio for a two-phase mixture of titanium metal and magnesium chloride of 0.985. As such the stability and predictability of the recovered composite to subsequent processing will be increased.
- composite material black in colour in angular particulate form comprising a matrix of magnesium chloride, titanium metal, magnesium and quantities of titanium sub-halides (TiCl 2 and TiCl 3 ), 7.83 g of lithium chloride and 10.01 g of potassium chloride were milled together to form a uniform grey powder.
- the cup was then placed in a vacuum furnace at a pressure of approximately 0.01 kPa.
- An argon purge was supplied at a rate of 2 mg/min.
- the furnace was then heated to a temperature of 1100° C. at a heating rate of 10° C. per minute.
- the sample was shown to melt again at approximately 350° C. Surprisingly all volatiles were removed below 700° C., leaving titanium metal behind. This represents a significant reduction in the temperature required to recover the metal component based on the original composite composition.
- Example 7 Recovery of Metal from a Composite with Containing Aluminium
- composite material black to grey in colour, in angular particulate form comprising a matrix of aluminium chloride, titanium metal, aluminium and quantities of titanium sub-halides (TiCl 2 and TiCl 3 ), was placed in an open alumina cup.
- the cup was placed in a furnace under an argon atmosphere. The furnace was then heated to a temperature of 900° C. at a heating rate of 10° C. per minute. The material was held at temperature for 20 minutes before cooling.
- the composite displayed an endotherm around 650° C. indicating the melting of aluminium metal.
- the composite also exhibited exotherms above and below 650° C. commensurate with the formation of titanium aluminides.
- In excess of 10% loss of weight of the sample was exhibited around 500° C. consistent with the removal of TiCl 3 . Greater than 10% loss of weight was exhibited above 850° C. commensurate with the removal of TiCl 2 .
Abstract
The invention provides a method for the recovery of a metal-containing product (MProd) comprising: providing a composite material comprising a matrix of oxidised reductant (Ro), a product metal (MP) dispersed in the matrix of oxidised reductant (Ro), and one or more metal compounds (MPCR) of the product metal (MP) in one or more oxidation states dispersed in the matrix of oxidised reductant (Ro); and treating the composite material to at least partially remove the one or more metal compounds (MPCR) from the matrix of oxidised reductant (Ro) to form the metal-containing product (MProd).
Description
- This application is a continuation of U.S. patent application Ser. No. 15/540,725, filed on Jun. 29, 2017, which is the national phase of PCT/AU2016/050745, which claims priority to AU 2015903278. The foregoing applications are incorporated herein by reference.
- The present invention relates to a method for the recovery of metal-containing material from a composite material. In particular, the invention relates to a method for the recovery of a metal-containing product (MProd) from a novel composite material comprising a matrix of oxidised reductant (Ro), a product metal (MP) dispersed in the matrix of oxidised reductant (Ro) and one or more metal compounds (MPCR) of the product metal (MP) in one or more oxidation states dispersed in the matrix of oxidised reductant (Ro).
- International Publication No. WO 2006/042360 provides a method for producing titanium by reaction of titanium tetrachloride with magnesium in a reactor, which may comprise a fluidised bed. The temperature in the reactor is above the melting point of magnesium, but below the melting point of magnesium chloride. The method produces particles comprising titanium which are removed from the reactor and processed in order to recover titanium particles generally having a particle size of greater than 500 μm. Compliant with conventional thinking, the method of WO 2006/042360 is operated under an excess of magnesium with unreacted magnesium optionally collected and recycled to the reactor. This is understood to achieve complete conversion of TiCl4 to titanium metal, while avoiding the formation of sub-chlorides, TiCl2 and TiCl3.
- The applicant has identified methods for producing composite materials from at least one metal compound in which an excess of oxidant is fed to the reactor during processing. The composite material will generally be in finely divided form and the method, generally, does not place significant weight on the exclusion of by-products in the composite material. The methods for the production of the composite material are described in detail in a co-pending international patent application with the title “METHOD FOR THE PRODUCTION OF A COMPOSITE MATERIAL USING EXCESS OXIDANT”, filed on the same date as the present application. The contents of the co-pending application are incorporated herein in their entirety.
- The subject matter claimed herein is not limited to embodiments that solve any disadvantages or that operate only in environments such as those described above. Rather, this background is only provided to illustrate one exemplary technology area where some embodiments described herein may be practiced.
- As mentioned above, the present invention relates generally to a method for the recovery of a metal-containing product (MProd) from a composite material.
- According to one aspect of the invention there is provided a method for the recovery of a metal-containing product (MProd) comprising:
- providing a composite material comprising a matrix of oxidised reductant (Ro), a product metal (MP) dispersed in the matrix of oxidised reductant (Ro), and one or more metal compounds (MPCR) of the product metal (MP) in one or more oxidation states dispersed in the matrix of oxidised reductant (Ro); and
- treating the composite material to at least partially remove the one or more metal compounds (MPCR) from the matrix of oxidised reductant (Ro) to form the metal-containing product (MProd).
- For convenience, the term “composite material” will be used to describe a composite material that is a metal-salt composite, an alloy-salt composite or an inter-metallic-salt composite. That is, the term “composite material” as used herein is intended to include within its scope a composite comprising a salt and (i) a metallic element and a reduced metal compound of a metallic element, (ii) two or more metallic elements and reduced metal compounds of two or more metallic elements, and (iii) one or more metallic elements together with one or more non-metallic elements and one or more reduced metal compounds of one or more metallic elements.
- In a similar way, the term “product metal” will be used to describe a product that is a metal, an alloy or an inter-metallic. That is, the term “product metal” as used herein is intended to include within its scope product comprising (i) one metallic element, (ii) two or more metallic elements, or (iii) one or more metallic elements together with one or more non-metallic elements.
- As used herein the term “remove” will be used to describe physical removal of the one or more metal compounds (MPCR) from the matrix of oxidised reductant (Ro), such as by distillation or other physical mechanisms. It will also be used to describe conversion of the metal compounds (MPCR), for example by reduction.
- Throughout this specification, unless the context requires otherwise, the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated step or element or integer or group of steps or elements or integers, but not the exclusion of any other step or element or integer or group of steps, elements or integers. Thus, in the context of this specification, the term “comprising” is used in an inclusive sense and thus should be understood as meaning “including principally, but not necessarily solely”.
- According to one embodiment of the invention, the treatment step comprises distilling the one or more metal compounds (MPCR) from the matrix of oxidised reductant (Ro). The distillation may further at least partially remove the oxidised reductant (Ro). In one embodiment, the treatment step comprises subjecting the composite material to conditions that result in volatilisation of the oxidised reductant (Ro). For example, the conditions may result in sublimation of the oxidised reductant (Ro).
- The treatment step may comprise at least one of (i) volatilisation of the one or more metal compounds (MPCR), and (ii) reduction of the one or more metal compounds (MPCR) to the product metal (MP).
- According to one embodiment, the one or more metal compounds (MPCR) and, optionally, the oxidised reductant (Ro), are removed from the composite material by vacuum distillation. For example, the vacuum distillation may be carried out under inert conditions, such as under argon gas. If so, the inert (e.g. argon) gas is added, as a barrier gas, at a rate that is dependent on the scale of the operation and vacuum applied. According to this embodiment, the vacuum distillation may be conducted at a pressure of from 0.01 to 0.015 kPa. The vacuum distillation is preferably conducted at conditions at which sublimation of the oxidised reductant (Ro) occurs.
- In one particular embodiment, the product metal (MP) comprises titanium and the oxidised reductant (Ro) comprises magnesium chloride and the vacuum distillation is conducted at a temperature of from 700° C. to 950° C., and the product metal (MP) optionally comprises at least titanium.
- It has been found that treatment at relatively low pressures maintains the form of the product metal (MP) recovered from the composite material. For example, if the composite material is particulate and comprises a plurality of small particles, as discussed in more detail below, treatment under these conditions may result in the recovery of product metal (MP) in particulate form.
- In another embodiment, the treatment step comprises reducing the one or more metal compounds (MPCR) of the product metal (MP) to the product metal (MP) in the presence of a reductant (R). The reductant (R) may be included within the matrix of oxidised reductant (Ro), and/or the reductant (R) may be combined with the composite material prior to or during the distillation.
- In an alternative embodiment, the treatment step comprises melting at least the matrix of oxidised reductant of the composite material and recovering the metal-containing product (MProd) from the melt. The temperature at which melting is conducted will be somewhat predicated by the components of the matrix of oxidised reductant of the composite material. In certain embodiments melting may be conducted at a temperature below the individual melting temperatures of each component of the matrix by formation of compositions inclusive of hypoeutectic and hypereutectic compositions. In a preferred embodiment the composition of the components of the composite may form a eutectic composition. Melting may be conducted by introducing the composite material to a molten bath. The molten bath may be one of reduced melting point, for example a eutectic mixture.
- In this embodiment, recovering the metal-containing product (MProd) from the melt may comprise subjecting the melt to conditions at which the product metal (MP), the one or more metal compounds (MPCR) and the oxidised reductant (Ro) form separate layers in the melt and recovering the product metal (MP) layer. For example, separation may comprise density separation, gravity separation or centrifugation. Recovery may also comprise dissolution of components of the composite material, such as the one or more metal compounds (MPCR) and oxidised reductant (Ro).
- According to this embodiment of the invention, the form of the product metal (MP) may not be maintained, but instead the (MP) may be recovered and formed into, for example, ingots of the product metal (MP).
- The reductant (R) may be a solid, solid particulate, liquid or vapour. In certain embodiments, the reductant (R) is selected from the group consisting of Mg, Na, K, Li, Ba, Ca, Be and Al, although it is envisaged other options may also be suitable. In certain embodiments two or more reductants (R), which may include one or more metal reductant (MR), may be present. In other embodiments, it is thought that the reductant (R) may suitably comprise a multi-component reductant, such as an alloy, for example an Mg—Al or Mg—Pd alloy. Generally, the composite material comprises up to 20 wt %, preferably up to 3 wt % of the reductant (R).
- In certain embodiments, the one or more metal compounds (MPCR) of the product metal (MP) in one or more oxidation states comprise one or more metal halides (MPX) of the product metal (MP). For example, the one or more metal compounds (MPCR) of the product metal (MP) in one or more oxidation states may comprise a metal halide selected from the group consisting of halides of titanium, aluminium, vanadium, chromium, niobium, molybdenum, zirconium, silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum, scandium, ruthenium and the rare earths or a combination of any two or more thereof. The one or more metal compounds (MPCR) of the product metal (MP) in one or more oxidation states may comprise at least two metal halides. If so, the metal halides may be preferably selected from the group consisting of halides of titanium, aluminium and vanadium.
- In certain embodiments, the oxidised reductant (Ro) comprises a metal halide (MRX). For example, the metal halide (MRX) may be selected from the group consisting of MgCl2, NaCl, KCl, LiCl, BaCl2, CaCl2), BeCl2 AlCl3, and any combination thereof.
- The composite material may further comprise one or more metals (M). For example, an additional metal incorporated into the composite material during preparation of the composite material. The metal (M) may be selected from the group consisting of titanium, aluminium, vanadium, chromium, niobium, molybdenum, zirconium, silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum, scandium, ruthenium and the rare earths or a combination of any two or more thereof. For example, the other metal, (i.e. metallic element) may be aluminium metal as a solid or liquid.
- In a preferred embodiment, the composite material is in the form of particles. The particles may be generally spherical. They may also be regular or irregular in shape. Preferably, the particles have an average particle size of up to 500 μm, more preferably from 20-300 μm.
- The metal component (MP) within the composite material generally has a particle size of up to about 1 micron. The surface area to volume ratio of the metal component (MP) in the protective matrix is preferably greater than 6 m2/mL.
- In that regard, taking as an example where the composite material is formed by contacting Mg with an excess of TiCl4 in a fluidised bed reactor to form Ti metal dispersed in a MgCl2 matrix, it is thought that at the extreme lower limit of particle size, one molecule of TiCl4 may react with one atom of Mg and produce MgCl2 and TiCl2. Thereafter, one more atom of Mg reacts with TiCl2 and forms a second MgCl2 and a single Ti atom. Therefore, at its limit, it is envisaged that the finely divided metal component (MP) may be present in the protective matrix of MgCl2 on an atomic scale. Such examples would represent true “primary particles” of the metal component (MP). In practice, there is the inherent desire on the part of the metal component (MP) to nucleate or agglomerate (and possibly sinter), especially at nascent sites and in the presence of some local heating, mixing, possible electronic transfer through partially melted salt, etc. As such, it is considered that there may be many atoms coalescing together to form the more realistically viable “primary particles” that would be observed under analysis. These particles may be extremely small, for example on the nano-scale. At some point, however, further aggregation is not possible because, according to this embodiment at least, of “freezing” of the MgCl2 to encapsulate the Ti in its current state of agglomeration, resulting in a frozen sea of MgCl2 with homogeneously dispersed titanium particles. Accordingly, in this particular embodiment, an ultrahigh surface area metal with no oxide barrier layer is completely protected from forming larger particles or otherwise reacting unless the MgCl2 is removed. However, when the protective matrix, in this case MgCl2 is removed (for example by melting), the titanium particles are free to move around and further aggregate and form larger structures, such as shells of Ti. These may be considered “secondary particles”. It will be appreciated that these comments are equally relevant to the extreme upper limit of the surface area to volume ratio of the metal component (MP) in the protective matrix.
- Another advantageous characteristic of the metal component (MP) of these preferred embodiments of the invention is the lack of a protective oxide layer. The metal component (MP) particles of these embodiments do not have an activation barrier, which correlates with a lower activation energy (increase in reactivity) of the metal component (MP). In addition to the above advantage, generally small particles are highly pyrophoric. The composite material of the preferred embodiments of the invention is, comparatively, not. For conventional metal powders of approximately <10 μm, pyrophoricity becomes a major issue, but can be serious even at much larger sizes (>100 μm) under some conditions.
- The protective matrix of the composite material of the invention advantageously overcomes this issue.
- The method of the invention may further comprise combining the composite material with an additional component prior to or during the treating step. The additional component may be selected from the group consisting of (i) a composite material comprising a matrix of oxidised reductant (Ro), for example a metal halide, with one or more metallic elements dispersed in the matrix, (ii) a metallic element or compound; (iii) a non-metallic element or compound, (iv) a metalloid element or compound, and (v) any combination of two or more of these. For example, the composite material may be combined with any one or more of the groups consisting of beryllium, boron, carbon, nitrogen, oxygen, aluminium, silicon, phosphorous, sulphur, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lead, bismuth, the Rare Earths and compounds thereof.
- The metal-containing product (MProd) may consist of the product metal (MP) and the method may comprise recovering the product metal (MP) from the composite material. The method may further comprise a post-treatment of the recovered product metal (MP). For example, the post-treatment comprises, milling, grinding, coating, pressing, heat treating (e.g. aging, annealing, quenching, tempering), rolling, forming, casting, hot or cold isostatic pressing (HIPing or CIP), moulding, melting, sintering, blending, extruding, drawing, forging, turning, welding, atomising and/or spraying.
- The method may further comprise pre-treating the composite material prior to the treatment step. For example, the pre-treatment may comprise at least one of compacting, milling and grinding the composite material.
- According to another aspect of the invention there is provided metal-containing product (MProd) produced by a method as described above.
- The metal-containing product (MProd) formed according to the invention may comprise particulate metal having a particle size of less than 500 μm, preferably from 20-300 μm, or may comprise ingots of the product metal (MP).
- In certain embodiments, the product metal (MP) is an alloy, for example an alloy of two or more of titanium, vanadium and aluminium. For example, the alloy may approximate Ti64.
- In that regard, it will be appreciated that Ti64 alloy generally refers to an alloy having a chemical composition of 6% aluminium, 4% vanadium, 0.25% (maximum) iron, 0.2% (maximum) oxygen, and the remainder titanium. Ti64 is also commonly referred to as
Grade 5 titanium. - In another embodiment, palladium may be incorporated into the composite material to facilitate recovery of Grade 7 titanium. In that regard, Grade 7 titanium contains 0.12 to 0.25% palladium. The small quantity of palladium provides enhanced crevice corrosion resistance at low temperatures and high pH.
- It is believed that the particulate metal may be suitable for use in many powder metallurgical processes. In that regard, as mentioned above, it is envisaged that the form of the product metal (MP) recovered, be that in terms of desired shapes and particle sizes of the particles, may be predicted by manipulating the method of recovery, and also manipulating the method of production of the composite material. That is, the size and shape of the particles may be manipulated in order to achieve suitable particles for a particular powder metallurgical process.
- The present invention consists of features and a combination of parts hereinafter fully described and illustrated in the accompanying drawings, it being understood that various changes in the details may be made without departing from the scope of the invention or sacrificing any of the advantages of the present invention.
- To further clarify various aspects of some embodiments of the present invention, a more particular description of the invention will be rendered by references to specific embodiments thereof, which are illustrated in the appended drawings. It should be appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting on its scope. The invention will be described and explained with additional specificity and detail through the accompanying drawings in which:
-
FIG. 1 illustrates a flow chart of a method for the recovery of metal-containing product (MProd) from a composite material, which also illustrates an exemplary method for obtaining a composite material. -
FIG. 2 illustrates weight loss of titanium composite rapidly heated to 500° C. and held at that temperature for a period of time according to example 4. -
FIG. 3 shows the total content of titanium and magnesium as determined by XRF of the feed material of Example 5 and several subsequent samples of the recovered material. -
FIG. 4 shows a similar plot toFIG. 3 , but separately shows the individual content of titanium and magnesium. - Hereinafter, this specification will describe the present invention according to the preferred embodiments. It is to be understood that limiting the description to the preferred embodiments of the invention is merely to facilitate discussion of the present invention and it is envisioned without departing from the scope of the appended claims.
- Referring to
FIG. 1 , amethod 200 for the recovery of a metal-containing product (MProd) from a composite material is illustrated. Also illustrated for convenience and without any limitation to the method of recovery of the present invention, is anexemplary method 100 for the production of a suitable composite material that contains one or more metal compounds (MPCR) of the product metal (MP) in one or more oxidation states. We provide the following non-limiting discussion of theexemplary method 100, followed by a more detailed discussion of themethod 200 of the present invention. - According to the
method 100 for the recovery of a composite material, metal compound (MPC) 110 of a product metal (MP) and a reductant (R) 120 capable of reducing the metal compound (MPC) 110 of the product metal (MP) are supplied to areactor 130. The amount of metal compound (MPC) 110 supplied to thereactor 130, including any recycled metal compound (MPC) 140, is in excess relative to the amount ofreductant 120 supplied to thereactor 130.Composite material 150 is recovered from thereactor 130. The composite material comprises a matrix of oxidised reductant (Ro), product metal (MP) dispersed in the matrix of oxidised reductant (Ro), and one or more metal compounds (MPCR) of the product metal (MP) in one or more oxidation states dispersed in the matrix of oxidised reductant (Ro). The composite material may further comprise reductant (R). - The
reactor 130, which will be discussed in terms of a fluidised bed reactor with reference toFIG. 1 , is run at a temperature that is below the melting point of the oxidised reductant (Ro) and, generally, above the melting point of the reductant (R) 120, which may form part of thecomposite material 150. Where the temperature in thereactor 130 is between the melting point of the reductant (R) 120 and the melting point of the oxidised reductant (Ro), for example its oxidised salt, the reaction of the reductant (R) 120 with oxidant results in the formation of acomposite material 150 comprised of largely or entirely solid character. This ‘freezing’ reaction advantageously has the impact of creating finely divided and highly pure reaction products. Without seeking to be bound by theory, it is thought that the particle size of thecomposite material 150 is such that the finely divided elements comprised within are sufficiently small that they interact differently with visible light than their bulk counterparts. For example, they may appear black or dark in colour. The finely divided structure of thecomposite material 150 has advantages compared with composites of analogous nominal compositions that do not have the same finely divided structure. These advantages will be elucidated in more detail below. - Where the reductant (R) 120 is fed into the
reactor 130 as a solid or solid particulate, the prevailing conditions in thereactor 130 ensure, with sufficient time, the melting of thereductant 120. The time required for melting ofsolid reductant 120 depends upon numerous factors, including the feed mechanism, whether thereductant 120 is fed with other materials, the temperature of thereactor 130, the reaction intensity of thereactor 130 per unit volume, the particulate density of thereductant 120 feed at any single location and, if other reductant or reagent or inert streams are in or are entering into the reactor, the proximity to these components and their respective temperatures when impinging on particles of thereductant 120. - The interaction of the reductant (R) 120 upon contacting other surfaces in the
reactor 130 will depend on its phase at that time. If thereductant 120 particle is solid, it is possible thereductant 120 particle will collide and rebound. It will then continue to interact with other surfaces and environments in thereactor 130. - If the
reductant 120 particle has a molten external surface and solid inner surface, it is possible the particle will adhere to any surface it impacts, creating a composite of the two objects. The particle will then continue to interact with other surfaces and environments in thereactor 130. - If the
reductant 120 particle is molten when it interacts with other surfaces, it may wet the surface. Depending upon the nature of the solid-liquid interaction the thickness of the layer formed will vary. It is considered that this may be manipulated through varying intensity of interactions, density ofreductant 120 feed, temperature and time, etc. - Whether the end location of molten reductant in the
reactor 130 is as a stand-alone mass, wetted on a surface or combined with other surfaces, at some point it will interact with oxidant and react. At this point the thickness or the wetted layer or size of the molten mass or particle is considered of some importance in determining the extent of reaction of the reductant (R) 120 and the morphology of the finalcomposite material 150. - If the particle or wetted layer is sufficiently large or not completely molten at this time, the freezing nature of the reaction as described previously can result in a proportion of the reductant (R) becoming encapsulated by the
composite material 150. Where the surface exposed to oxidant reacts to form a solid it may form a barrier (i.e. shell) that may restrict or eliminate the participation of the remaining reductant in further reduction. If the particle is sufficiently small or the wetted layer sufficiently thin, for example if the thickness of the reaction layer is equivalent to the radius of the particle or the thickness of the wetted layer, the process can consume the majority if not all of the reductant (R). - The amount of oxidant in the reactor relative to reductant (R) will be an important factor in determining the probability of the above mentioned interactions.
- Weighting of one form of interaction over others can be manipulated by changing operating conditions, feed forms, etc. The nature of surfaces in the reactor available for interaction, potential for sequential ordering and forms in which the reductant and oxidant are brought into contact can result in composites being formed which have diverse characteristics. These may include, without limitation, excess or fully consumed reductant, layers of composite, layers of composite with magnesium interstitial layers. It is thought that novel structured materials may be formed by sequential layering of dissimilar layers of prescribed composition.
- Once the Composite Material is Recovered 150, it May be Stored Under Suitable Conditions for Later Use
- The present invention relates to a
method 200 for the recovery of a metal-containing product (MProd) from acomposite material 150. In certain embodiments, the method comprises the recovery of the product metal (MP) directly from thecomposite material 210, or may comprise recovery after combining the composite material with composite material of other product metal (MP′) 220, and/or other compounding material (CM) 230. As such, it is envisaged that various products may be recovered, including without limitation a metal-containing product (MProd) 240, an alloy or mixture of metal-containing product (MProd/MProd′) 250, and a mixture or composite metal-containing product (MProd/CM) 260. In any of these recovery processes, it may also be desirable to recover reductant (R). Once a desired composite material is formulated (i.e. with or without additional material), it is treated 270 to recover the metal-containingproduct -
Treatment 270 of the composite material aim to at least partially remove the one or more metal compounds (MPCR) from the matrix of oxidised reductant (Ro) to form the metal-containing product (MProd). Generally, the aim of thetreatment step 270 is to substantially completely remove the one or more metal compounds (MPCR) from the matrix of oxidised reductant (Ro). - It is currently envisaged that two methods of
treatment 270 are particularly useful for the removal of the one or more metal compounds (MPCR) from the matrix of oxidised reductant (Ro). These include distillation, particularly vacuum distillation, and reduction of the one or more metal compounds (MPCR) to product metal (MP) in the presence of a reductant. These two options may be performed independently, or in combination. It will be appreciated, though, that other suitable options may be employed. For example, thetreatment step 270 may suitably comprise melting the composite material and subsequent separation of the one or more metal compounds (MPCR). - The
treatment step 270 may also result in the removal of the matrix of oxidised reductant (Ro) from the composite material. As an example, the one or more metal compounds (MPCR) and the oxidised reductant (Ro) may be removed from the composite material by vacuum distillation. Thetreatment 270 may further result in the removal of reductant (R), if present, which may be recycled to thereductant feed 120, or be otherwise recovered. In such cases, the metal-containingproduct - Aside from the different compositional inputs into the recovery process as described above, the finely divided nature of the product metal (MP) in the
composite material 150, is encased in materials chemically inert to itself by the nature of their generation. Product metal of similar compositional properties but without the same physical characteristics engendered by the encasement process will not respond to the same recovery process with analogous results. That is, the surface is free from any protective or passivation layer meaning that it will respond differently to physical interactions than its macroscopic bulk counterpart. - The individual components of product metal encased in inert material provide for building blocks that may or may not combine to various extents and by different driving forces through the process of recovery to yield the product metal (MP). As such, the conditions under which the liberation of the product metal (MP) from the composite matrix proceeds and the conditions throughout the recovery process have a significantly determinative impact on the way in which each divided product metal building block interacts with others, and ultimately on the manner in which they may or may not combine and the morphology and microstructure of the recovered product metal.
- The following examples are provided for exemplification only and should not be construed as limiting on the invention in any way.
- 30 g of composite material, black in colour, in spherical particulate form comprising a matrix of magnesium chloride, titanium metal, magnesium and quantities of titanium sub-halides (TiCl2 and TiCl3) was placed in a vessel made from stainless steel. The vessel was placed under vacuum at a pressure of approximately 0.01 kPa. An argon purge was supplied at a rate of 10 mg/min. The vessel was then heated externally to a temperature of 900° C. at a heating rate of 31° C. per minute. The vessel was then left at a temperature of 900° C. for one hour before being cooled to room temperature.
- The vessel was purged with air and the remnant material was recovered from the vessel, comprising approximately 5 g of titanium metal. The metal was in the form of loosely sintered spheres with size approximately one half of the particulate size of the composite material fed into the vessel.
- The recovery process produced commercially
pure grade 2 titanium. - 15 g of composite material, black in colour, in spherical particulate form comprising a matrix of magnesium chloride, titanium metal, aluminium metal, magnesium and quantities of titanium sub-halides (TiCl2 and TiCl3) was combined with 15 g of composite material, black in colour, in spherical particulate form comprising a matrix of magnesium chloride, titanium metal, vanadium metal, magnesium and quantities of titanium sub-halides (TiCl2 and TiCl3) and possibly vanadium sub-halides.
- The total of 30 g of composite material was ground under inert conditions to form a homogeneous composition and then placed in a vessel made from stainless steel. The degree of milling could be altered for differing levels of uniformity. The vessel was placed under vacuum at a pressure of approximately 0.01 kPa. An argon purge was supplied at a rate of 10 mg/min. The vessel was then heated externally to a temperature of 900° C. at a heating rate of 31° C. per minute. The vessel was then left at a temperature of 900° C. for one hour before being cooled to room temperature.
- The vessel was purged with air and the remnant material was recovered from the vessel, comprising approximately 5 g of titanium, aluminium and vanadium containing metal in proportion with the sum of the product metal in the input composite material. The metal was in the form of closely packed sintered particles with irregular shape.
- 30 g of composite material, black in colour, in spherical particulate form comprising a matrix of magnesium chloride, titanium metal, magnesium and quantities of titanium sub-halides (TiCl2 and TiCl3) was ground under inert conditions and then placed in a vessel made from stainless steel. The degree of milling and or sieving could be altered for differing sizing and morphology of initial particulate size of composite material. The vessel was purged with argon at atmospheric pressure and then then heated externally to a temperature of 900° C. at a heating rate of 31° C. per minute. The vessel was then left at a temperature of 900° C. for one hour before being cooled to room temperature.
- The contents of the vessel was recovered and found to be a white and silver coloured mass comprised of titanium metal and magnesium chloride. There was no appearance of green or violet colouring to indicate presence of titanium sub-halides in the salt phase.
- The mass was broken up and milled to a powder and returned to the stainless steel vessel. The vessel was placed under vacuum at a pressure of approximately 0.01 kPa. An argon purge was supplied at a rate of 10 mg/min. The vessel was then heated externally to a temperature of 900° C. at a heating rate of 31° C. per minute. The vessel was then left at a temperature of 900° C. for one hour before being cooled to room temperature.
- The vessel was purged with air and the remnant material was recovered from the vessel, comprising approximately 5 g of titanium metal.
- Under the atmospheric process the product metal was liberated from the protective matrix and enabled to consolidate to a degree by sintering. Similarly, melting of the matrix provides the opportunity for partially reduced or oxidised compounds to be liberated from the matrix structure and a significantly enhanced opportunity to interact and react with other compounds in the matrix, or be removed by boiling.
- 50 mg of composite material, black in colour, in angular particulate form comprising a matrix of magnesium chloride, titanium metal, magnesium and quantities of titanium sub-halides (TiCl2 and TiCl3) was placed in an open alumina cup. The cup was placed in a vacuum furnace at a pressure of approximately 0.01 kPa. An argon purge was supplied at a rate of 2 mg/min. The furnace was then heated to a temperature of 500° C. at a heating rate of 100° C. per minute, which under vacuum is sufficient for removing titanium and promoting the disproportionation of titanium sub-halides. The vessel was then left at a temperature of 500° C. for one hour before being cooled to room temperature.
-
FIG. 2 shows the loss of weight of the material over time in the process. It can be seen the weight stabilises after a short period. - The remnant material was recovered from the vessel, comprising approximately 30 mg of metal containing composite material with a substantially reduced sub-halide content. This composite could be put through further recovery processes, where the impact of the significant volatile sub-halide content would be reduced or eliminated. Such impacts could include significant increase in total volatile content, difficulty in controlling sub-halide conversion to metal or removal.
- A titanium composite containing significant sub-halide content was passed through vacuum at 600° C. with a residence time of 2 hours. The feed composite comprised uniform black spheres with particle size of <2 mm.
- Upon exiting the heated zone the composite material had become lighter in colour indicating some form of chemical process has occurred.
-
FIG. 3 shows the total content of titanium and magnesium as determined by XRF of the feed material and several subsequent samples of the recovered material.FIG. 4 shows a similar plot but separately shows the individual content of titanium and magnesium. - The increase in total metal ion content between the deed and the recovered material as shown in
FIG. 3 indicates that the metal component of the composite has been concentrated in the process.FIG. 4 shows that the titanium content of the recovered material is reduced after processing, which when combined with the total metal content increasing suggests that a titanium halide phase has been removed by processing without impacting the remaining composite constituents. - It is noted that the process reduces the mass ration of titanium to magnesium from 1.12 substantially towards the theoretical ratio for a two-phase mixture of titanium metal and magnesium chloride of 0.985. As such the stability and predictability of the recovered composite to subsequent processing will be increased.
- 2 g of composite material black in colour, in angular particulate form comprising a matrix of magnesium chloride, titanium metal, magnesium and quantities of titanium sub-halides (TiCl2 and TiCl3), 7.83 g of lithium chloride and 10.01 g of potassium chloride were milled together to form a uniform grey powder.
- 50 mg of the grey composite material was placed in an open alumina cup. The cup was placed in a furnace under an argon atmosphere. The furnace was then heated to a temperature of 500° C. at a heating rate of 10° C. per minute. The material was held at temperature for 20 minutes before cooling. The composite displayed an endotherm around 350° C. indicating the composite had melted. This is in contrast to the melting point of the original composite of around 715° C.
- The cup was then placed in a vacuum furnace at a pressure of approximately 0.01 kPa. An argon purge was supplied at a rate of 2 mg/min. The furnace was then heated to a temperature of 1100° C. at a heating rate of 10° C. per minute. The sample was shown to melt again at approximately 350° C. Surprisingly all volatiles were removed below 700° C., leaving titanium metal behind. This represents a significant reduction in the temperature required to recover the metal component based on the original composite composition.
- 50 mg of composite material black to grey in colour, in angular particulate form comprising a matrix of aluminium chloride, titanium metal, aluminium and quantities of titanium sub-halides (TiCl2 and TiCl3), was placed in an open alumina cup. The cup was placed in a furnace under an argon atmosphere. The furnace was then heated to a temperature of 900° C. at a heating rate of 10° C. per minute. The material was held at temperature for 20 minutes before cooling. The composite displayed an endotherm around 650° C. indicating the melting of aluminium metal. The composite also exhibited exotherms above and below 650° C. commensurate with the formation of titanium aluminides. In excess of 10% loss of weight of the sample was exhibited around 500° C. consistent with the removal of TiCl3. Greater than 10% loss of weight was exhibited above 850° C. commensurate with the removal of TiCl2.
- Inspection by SEM indicated that the recovered metal comprised titanium-aluminium composition with low residual chloride content.
- While the above examples primarily employ magnesium chloride as the matrix of oxidised reductant (Ro), those in the art will appreciate that other metals, including but not limited to other magnesium halides and halides of sodium, potassium, lithium and barium, would be expected to achieve similar results given their similar properties.
- Unless the context requires otherwise or specifically stated to the contrary, integers, steps or elements of the invention recited herein as singular integers, steps or elements clearly encompass both singular and plural forms of the recited integers, steps or elements.
- It will be appreciated that the foregoing description has been given by way of illustrative example of the invention and that all such modifications and variations thereto as would be apparent to persons of skill in the art are deemed to fall within the broad scope and ambit of the invention as herein set forth.
Claims (15)
1. Metal-containing product (MProd) comprising a particulate product metal (MP) having a particle size of less than 500 μm, the metal-containing product produced by a method comprising:
providing a composite material comprising a matrix of oxidized reductant (Ro), the product metal (MP) dispersed in the matrix of oxidized reductant (Ro), and one or more metal compounds (MPCR) of said product metal (MP) in one or more oxidation states dispersed in said matrix of oxidized reductant (Ro); and
treating said composite material to at least partially remove said one or more metal compounds (MPCR) from said matrix of oxidized reductant (Ro) to form a metal-containing product (MProd).
2. Metal-containing product according to claim 1 , wherein said (MProd) metal-containing product (MProd) is an alloy.
3. Metal-containing product according to claim 2 , wherein said (MProd) alloy approximates Ti-6Al-4V.
4. Metal-containing product (MProd) according to claim 1 , comprises particulate product metal (MP) having a particle size of from 20-300 μm.
5. Metal-containing product (MProd) according to claim 2 , wherein said metal-containing product (MProd) is an alloy of two or more of titanium, vanadium and aluminum.
6. Metal-containing product (MProd) comprising a particulate product metal (MP), with the particulate product metal (MP) being an alloy that approximates Ti64, with the particulate product metal (MP) being in the form of closely packed sintered particles with irregular shape, and with the particles having a particle size of less than 500 μm, the metal-containing product produced by a method comprising:
providing a composite material comprising a matrix of oxidized reductant (Ro), the product metal (MP) dispersed in the matrix of oxidized reductant (Ro), and one or more metal compounds (MPCR) of said product metal (MP) in one or more oxidation states dispersed in said matrix of oxidized reductant (Ro); and
treating said composite material to at least partially remove said one or more metal compounds (MPCR) from said matrix of oxidized reductant (Ro) to form a metal-containing product (MProd).
7. Metal-containing product according to claim 6 , wherein said (MProd) metal-containing product (MProd) is an alloy.
8. Metal-containing product according to claim 7 , wherein said (MProd) alloy approximates Ti-6Al-4V.
9. Metal-containing product (MProd) according to claim 6 , comprises particulate product metal (MP) having a particle size of from 20-300 μm.
10. Metal-containing product (MProd) according to claim 7 , wherein said metal-containing product (MProd) is an alloy of two or more of titanium, vanadium and aluminum.
11. Metal-containing product (MProd) comprising a particulate product metal (MP), with the particulate product metal (MP) being an alloy that approximates Ti64, with the particulate product metal (MP) being in the form of closely packed sintered particles having an irregular shape that is not generally spherical in shape and is not regular in shape, and with the particles having a particle size of less than 500 μm, the metal-containing product produced by a method comprising:
providing a composite material comprising a matrix of oxidized reductant (Ro), the product metal (MP) dispersed in the matrix of oxidized reductant (Ro), and one or more metal compounds (MPCR) of said product metal (MP) in one or more oxidation states dispersed in said matrix of oxidized reductant (Ro); and
treating said composite material to at least partially remove said one or more metal compounds (MPCR) from said matrix of oxidized reductant (Ro) to form a metal-containing product (MProd).
12. Metal-containing product (MProd) according to claim 11 , wherein said metal-containing product (MProd) is an alloy.
13. Metal-containing product (MProd) according to claim 12 , wherein said alloy approximates Ti-6Al-4V.
14. Metal-containing product (MProd) according to claim 11 , comprises particulate product metal (MP) having a particle size of from 20-300 μm.
15. Metal-containing product (MProd) according to claim 12 , wherein said metal-containing product (MProd) is an alloy of two or more of titanium, vanadium and aluminum.
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PCT/AU2016/050745 WO2017027914A1 (en) | 2015-08-14 | 2016-08-12 | Method for recovery of metal-containing material from a composite material |
US201715540725A | 2017-06-29 | 2017-06-29 | |
US17/516,323 US20220056557A1 (en) | 2015-08-14 | 2021-11-01 | Method for recovery of metal-containing material from a composite material |
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AU2016309952B2 (en) * | 2015-08-14 | 2022-01-27 | Coogee Titanium Pty Ltd | Method for recovery of metal-containing material from a composite material |
CN111876617B (en) * | 2020-08-03 | 2022-02-22 | 国家地质实验测试中心 | Extraction of molybdenum, rhenium and radioactive origin187Methods for Os |
CN111876597B (en) * | 2020-08-03 | 2022-02-22 | 国家地质实验测试中心 | Extraction of radioactive cause from molybdenite187Methods for Os |
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