US20160122846A1 - Sustainable process for reclaiming precious metals and base metals from e-waste - Google Patents
Sustainable process for reclaiming precious metals and base metals from e-waste Download PDFInfo
- Publication number
- US20160122846A1 US20160122846A1 US14/993,614 US201614993614A US2016122846A1 US 20160122846 A1 US20160122846 A1 US 20160122846A1 US 201614993614 A US201614993614 A US 201614993614A US 2016122846 A1 US2016122846 A1 US 2016122846A1
- Authority
- US
- United States
- Prior art keywords
- acid
- ether
- metal
- glycol
- extraction
- 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
- 238000000034 method Methods 0.000 title claims abstract description 90
- 239000010793 electronic waste Substances 0.000 title claims description 83
- 230000008569 process Effects 0.000 title abstract description 19
- 239000010970 precious metal Substances 0.000 title abstract description 15
- 239000010953 base metal Substances 0.000 title abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 189
- 239000002184 metal Substances 0.000 claims abstract description 189
- 239000000203 mixture Substances 0.000 claims abstract description 185
- 239000010931 gold Substances 0.000 claims abstract description 83
- 229910052737 gold Inorganic materials 0.000 claims abstract description 40
- 229910052709 silver Inorganic materials 0.000 claims abstract description 37
- 150000002739 metals Chemical class 0.000 claims abstract description 32
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims description 237
- 239000007787 solid Substances 0.000 claims description 150
- 239000007788 liquid Substances 0.000 claims description 124
- 229910021645 metal ion Inorganic materials 0.000 claims description 108
- 230000029087 digestion Effects 0.000 claims description 85
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- 239000010949 copper Substances 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 28
- 239000007800 oxidant agent Substances 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 23
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 23
- 239000008139 complexing agent Substances 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- -1 Dequest 2060s Chemical compound 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 239000003002 pH adjusting agent Substances 0.000 claims description 14
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 claims description 6
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 4
- UNUKEKVIHNLAMU-UHFFFAOYSA-N 2,3,4,6-tetrahydroxybenzenesulfonic acid Chemical compound OC1=CC(O)=C(S(O)(=O)=O)C(O)=C1O UNUKEKVIHNLAMU-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- ZCLXQTGLKVQKFD-UHFFFAOYSA-N 3-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1 ZCLXQTGLKVQKFD-UHFFFAOYSA-N 0.000 claims description 4
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 4
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 3
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 3
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 claims description 3
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 3
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 3
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 claims description 3
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 3
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 3
- FYYLCPPEQLPTIQ-UHFFFAOYSA-N 2-[2-(2-propoxypropoxy)propoxy]propan-1-ol Chemical compound CCCOC(C)COC(C)COC(C)CO FYYLCPPEQLPTIQ-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 claims description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 3
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims description 2
- SNUSZUYTMHKCPM-UHFFFAOYSA-N 1-hydroxypyridin-2-one Chemical compound ON1C=CC=CC1=O SNUSZUYTMHKCPM-UHFFFAOYSA-N 0.000 claims description 2
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 claims description 2
- RLIDQZXQFBZZRI-UHFFFAOYSA-N 2,3,4,5-tetrahydroxybenzenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=C(O)C(O)=C1O RLIDQZXQFBZZRI-UHFFFAOYSA-N 0.000 claims description 2
- RUESGWAQQFPVIF-UHFFFAOYSA-N 2,3,4-trihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C(O)=C1O RUESGWAQQFPVIF-UHFFFAOYSA-N 0.000 claims description 2
- IQSNOBRLEUDOAF-UHFFFAOYSA-N 2,3,5,6-tetrahydroxybenzenesulfonic acid Chemical compound OC1=CC(O)=C(O)C(S(O)(=O)=O)=C1O IQSNOBRLEUDOAF-UHFFFAOYSA-N 0.000 claims description 2
- NIRNCHUTYHSUSR-UHFFFAOYSA-N 2,3,5-trihydroxybenzenesulfonic acid Chemical compound OC1=CC(O)=C(O)C(S(O)(=O)=O)=C1 NIRNCHUTYHSUSR-UHFFFAOYSA-N 0.000 claims description 2
- APFTZGWMGKJYBL-UHFFFAOYSA-N 2,3,6-trihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(O)C(S(O)(=O)=O)=C1O APFTZGWMGKJYBL-UHFFFAOYSA-N 0.000 claims description 2
- UGEHFOSBNBEWMP-UHFFFAOYSA-N 2,3-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1N UGEHFOSBNBEWMP-UHFFFAOYSA-N 0.000 claims description 2
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 claims description 2
- XJLCMPSREKXGAK-UHFFFAOYSA-N 2,3-dimethoxybenzenesulfonic acid Chemical compound COC1=CC=CC(S(O)(=O)=O)=C1OC XJLCMPSREKXGAK-UHFFFAOYSA-N 0.000 claims description 2
- IORISFYTXJVNFE-UHFFFAOYSA-N 2,3-dinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O IORISFYTXJVNFE-UHFFFAOYSA-N 0.000 claims description 2
- UTONEBGRZQYUKQ-UHFFFAOYSA-N 2,4,5-trihydroxybenzenesulfonic acid Chemical compound OC1=CC(O)=C(S(O)(=O)=O)C=C1O UTONEBGRZQYUKQ-UHFFFAOYSA-N 0.000 claims description 2
- MGRLXPDNBRDFQX-UHFFFAOYSA-N 2,4,6-triaminobenzenesulfonic acid Chemical compound NC1=CC(N)=C(S(O)(=O)=O)C(N)=C1 MGRLXPDNBRDFQX-UHFFFAOYSA-N 0.000 claims description 2
- JLYIGXJCYFBIJB-UHFFFAOYSA-N 2,4,6-trihydroxybenzenesulfonic acid Chemical compound OC1=CC(O)=C(S(O)(=O)=O)C(O)=C1 JLYIGXJCYFBIJB-UHFFFAOYSA-N 0.000 claims description 2
- RTBNEJHMNWQEBM-UHFFFAOYSA-N 2,4,6-trimethoxybenzenesulfonic acid Chemical compound COC1=CC(OC)=C(S(O)(=O)=O)C(OC)=C1 RTBNEJHMNWQEBM-UHFFFAOYSA-N 0.000 claims description 2
- NHJVRSWLHSJWIN-UHFFFAOYSA-N 2,4,6-trinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O NHJVRSWLHSJWIN-UHFFFAOYSA-N 0.000 claims description 2
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 2
- GPULXEIKKFAUAW-UHFFFAOYSA-N 2,4-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C(O)=C1 GPULXEIKKFAUAW-UHFFFAOYSA-N 0.000 claims description 2
- ZPHMCVPMYLSOJH-UHFFFAOYSA-N 2,4-dimethoxybenzenesulfonic acid Chemical compound COC1=CC=C(S(O)(=O)=O)C(OC)=C1 ZPHMCVPMYLSOJH-UHFFFAOYSA-N 0.000 claims description 2
- GWGBNENHEGYJSN-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O GWGBNENHEGYJSN-UHFFFAOYSA-N 0.000 claims description 2
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims description 2
- IKQCSJBQLWJEPU-UHFFFAOYSA-N 2,5-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(O)C(S(O)(=O)=O)=C1 IKQCSJBQLWJEPU-UHFFFAOYSA-N 0.000 claims description 2
- YKPVMVVSUJOBHF-UHFFFAOYSA-N 2,5-dimethoxybenzenesulfonic acid Chemical compound COC1=CC=C(OC)C(S(O)(=O)=O)=C1 YKPVMVVSUJOBHF-UHFFFAOYSA-N 0.000 claims description 2
- DHEZBDZMYYAOKR-UHFFFAOYSA-N 2,5-dinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC([N+]([O-])=O)=CC=C1[N+]([O-])=O DHEZBDZMYYAOKR-UHFFFAOYSA-N 0.000 claims description 2
- HSZGXYFZPBCFSP-UHFFFAOYSA-N 2,6-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(N)=C1S(O)(=O)=O HSZGXYFZPBCFSP-UHFFFAOYSA-N 0.000 claims description 2
- ZZJVDYQPZOHNIK-UHFFFAOYSA-N 2,6-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(O)=C1S(O)(=O)=O ZZJVDYQPZOHNIK-UHFFFAOYSA-N 0.000 claims description 2
- YVBBSZGKRJZXOY-UHFFFAOYSA-N 2,6-dimethoxybenzenesulfonic acid Chemical compound COC1=CC=CC(OC)=C1S(O)(=O)=O YVBBSZGKRJZXOY-UHFFFAOYSA-N 0.000 claims description 2
- JIBYVYTYCPNJJO-UHFFFAOYSA-N 2,6-dinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O JIBYVYTYCPNJJO-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- 235000010323 ascorbic acid Nutrition 0.000 description 15
- 229960005070 ascorbic acid Drugs 0.000 description 15
- 239000011668 ascorbic acid Substances 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 15
- 229940001584 sodium metabisulfite Drugs 0.000 description 15
- 235000010262 sodium metabisulphite Nutrition 0.000 description 15
- 239000003638 chemical reducing agent Substances 0.000 description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 11
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 150000005324 oxide salts Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000003841 chloride salts Chemical class 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229930184207 Polyphenon Natural products 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 231100001261 hazardous Toxicity 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 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 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
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- 239000012086 standard solution Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000430525 Aurinia saxatilis Species 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- 241001337814 Erysiphe glycines Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012223 aqueous fraction Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229940094952 green tea extract Drugs 0.000 description 1
- 235000020688 green tea extract Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000003313 weakening effect Effects 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
- C22B11/00—Obtaining noble metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0006—Preliminary treatment without modification of the copper constituent by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0073—Leaching or slurrying with acids or salts thereof containing nitrogen
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Definitions
- the present invention relates generally to environmentally friendly processes for recycling printed wire boards, more specifically environmentally friendly processes for extracting the precious metals and base metals from IC chips and other materials comprising said metals.
- PWB's are a common component of many electronic systems. PWB's are typically manufactured by laminating dry film on clean copper foil, which is supported on a fiberglass plate matrix. The film is exposed with a film negative of the circuit board design, and an etcher is used to remove unmasked copper foil from the plate. Solder is then applied over the unetched copper on the board. Depending upon the use and design of the particular PWB, various other metals may be used in the manufacturing process, including lead, tin, nickel, iron, zinc, aluminum, silver, gold, platinum, and mercury.
- the PWB's include many additional components, for example, transistors, capacitors, heat sinks, IC's, resistors, integrated switches, processors, etc.
- PWB's are potentially a difficult waste material to process since they generally have little usefulness once they are removed from the electrical component in which they were installed. In addition, they typically consist of materials that classify them as a hazardous or “special” waste stream. They must be segregated and handled separately from other nonhazardous solid waste streams. PWB's that are handled as waste materials must be processed using any one of several available disposal options. Not only are these options expensive, they require a significant amount of effort and handling by the generator. Furthermore, since some of these disposal options do not include destruction of the waste circuit boards, the generator also retains much of the liability associated with improper handling or disposal.
- the PWB's or pieces thereof are burnt in metallurgy works.
- the base material made up of glass fibre and plastic or similar such materials, is also burnt.
- the melting down process of the PWB's causes the energy requirement to be high. Refining the melted down metals also requires further high energy and environmentally unfriendly processes such as smelting.
- the processes described herein are useful for recycling electronic waste and for recovering valuable and/or hazardous metals therefrom.
- the processes provide an alternative to smelting for the recovery of valuable and/or hazardous metals present in electronic waste.
- a method of removing more than one metal from e-waste comprising:
- the first extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst.
- the second extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst. It should be appreciated by the skilled artisan that the first extraction liquid can be the same as or different from the second extraction liquid.
- the first metal comprises gold
- the second metal comprises silver
- the third metal comprises copper.
- a method of removing more than one metal from e-waste comprising:
- the first extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst.
- the second extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst.
- the first extraction liquid can be the same as or different from the second extraction liquid.
- the first metal comprises gold
- the second metal comprises silver
- the third metal comprises copper.
- a method of removing more than one metal from e-waste comprising:
- the first extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst.
- the second extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst.
- the first extraction liquid can be the same as or different from the second extraction liquid.
- the first metal comprises gold
- the second metal comprises silver
- the third metal comprises copper.
- a method of removing metals from e-waste comprising:
- FIG. 1 illustrates the generic separation process described herein.
- FIG. 2 illustrates schematically the separation process wherein the additive is a pH adjusting agent.
- FIG. 3 illustrates schematically the separation process wherein the additive is an organic component.
- FIG. 4 illustrates the percentage of Ag. Al, Au, Cu, Fe, Mn, Ni, Pb, Sb, Sn and Zn extracted in small scale serial extractions using Formulation D as a function of the total mass of metal extracted.
- FIG. 5 illustrates the percentage of Ag. Al, Au, Cu, Fe, Mn, Ni, Pb, Sb, Sn and Zn extracted in large scale serial extractions using Formulation D as a function of the total mass of metal extracted.
- the present invention relates generally to environmentally friendly processes to recycle printed wire boards, more specifically, environmentally friendly processes to recycle components removed from the printed wire boards.
- Electronic waste corresponds to computers, computer monitors, television receivers, cellular telephones, video cameras, digital cameras, DVD players, video game consoles, facsimile machines, copiers, MP3 players, and similar products that have reached the end of their useful life or otherwise have been disposed of Electronic waste or e-waste includes the components contained within these well known items such as printed wire boards and the components contained thereon (e.g., transistors, capacitors, heat sinks, integrated circuits (IC's), resistors, integrated switches, chips, and processors).
- IC integrated circuits
- metal correspond to precious metals and base metals that are preferably extracted from the components removed from the printed wire boards.
- precious metals include the metals such as gold, silver, platinum, palladium, alloys comprising same, and combinations thereof.
- base metals corresponds to iron, nickel, lead, zinc, alloys comprising same, and combinations thereof. Although not base metals per se, for the purposes of the present invention, the base metals further include copper, manganese, tin, antimony, aluminum, as well as alloys comprising same, and combinations thereof.
- Substantially devoid is defined herein as less than 2 wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt. %, and most preferably less than 0.1 wt. %. “Devoid” corresponds to 0 wt. %.
- complexing agent includes those compounds that are understood by one skilled in the art to be complexing agents, chelating agents, sequestering agents, and combinations thereof. Complexing agents will chemically combine with or physically hold the metal atom and/or metal ion to be removed using the compositions described herein.
- printed wire boards and “printed circuit boards” are synonymous and may be used interchangeably.
- PWB components include, but are not limited to, transistors, capacitors, heat sinks, IC's, resistors, integrated switches, chips, and processors.
- releases corresponds to the complete removal of the component(s) from the PWB component or the partial release of the component(s) from the PWB component, wherein the partial release of the component from the PWB corresponds to the weakening of the solder holding the component(s) to the PWB and the remainder of the release may be carried out by another method.
- substantially separate corresponds to the separation of a first metal from a material or composition comprising at least two metals, wherein at least 75 wt % of the first metal is separated from the material or composition, preferably at least 85 wt %, even more preferably at least 90 wt %, and most preferably at least 95 wt % of the first metal is separated from the material or composition.
- compositions may be embodied in a wide variety of specific formulations, as hereinafter more fully described.
- specific components of the composition are discussed in reference to weight percentage ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such components are employed.
- the present disclosure relates to the reclamation of materials from PWB components regardless of how they are obtained (e.g., de-soldering, planing down, chiselling off, grinding down, wet chemical processing or using some other method known in the art).
- FIG. 1 a method of removing metals from e-waste is described and illustrated generally in FIG. 1 , said method comprising:
- a method of removing more than one metal from e-waste is described and illustrated in FIGS. 2 and 3 , said method comprising:
- FIGS. 2 and 3 a method of removing more than one metal from e-waste is described and illustrated in FIGS. 2 and 3 , said method comprising:
- the e-waste can be pulverized into a powder, shredded into pieces, crushed, or in any other form so long as the metals contained in the e-waste are readily exposed for extraction from the e-waste.
- crushed e-waste corresponds to any method that substantially exposes the gold and other precious metals of the e-waste (e.g., PWB component) to the extraction composition, e.g., cracking, pulverizing or shredding the e-waste.
- the e-waste is cracked, thereby minimizing the amount of gold or other precious metals lost as a result of the pulverizing or shredding.
- Precious metals can be lost if scrap is pulverized wherein gold dust adheres to the separated stream and is lost in the magnetic fraction. Accordingly, crushing is further defined as a process whereby no more than 10% of the gold or other precious metals are lost to processes such as pulverizing or shredding, preferably no more than 5%, even more preferably no more than 2%. Moreover, crushing the e-waste minimizes the risk to human health by minimizing the release of dusts containing hazardous metals and brominated flame retardants.
- the first metal digestion composition comprises, consists of, or consists essentially of at least one oxidizing agent and at least one complexing agent. In another embodiment, the first metal digestion composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst.
- the first metal digestion composition is preferably more environmentally friendly than aqua regia or cyanide-containing compositions. Further, the first metal digestion composition preferably is formulated to substantially separate a first metal or metal ion from the e-waste into a fraction that can be further processed to reclaim said metal.
- the first metal digestion composition can be used to separate gold from other precious and base metals, wherein the gold is present in the solid and the other precious and base metals are dissolved in the first metal digestion composition.
- the gold and polymeric material can be present in the first extraction solid while the first extraction liquid comprises precious metals other than gold and other base metals.
- the first metal digestion composition as described herein is contacted in any suitable manner to the e-waste, e.g., by spraying the composition on the e-waste, by dipping (in a volume of the composition) of the e-waste, by contacting the e-waste with another material, e.g., a pad, or fibrous sorbent applicator element, that has the composition absorbed thereon, or by any other suitable means, manner or technique, by which a composition is brought into contact with the e-waste.
- the first extraction process using the first metal digestion composition may be static or dynamic.
- the process is dynamic whereby agitation and/or ultrasonics occurs.
- the composition typically is contacted with the e-waste for a time of from about 10 minutes to about 200 minutes, preferably about 30 min to 135 min, at temperature in a range of from about 20° C. to about 70° C., preferably in a range from about 20° C. to about 50° C.
- Such contacting times and temperatures are illustrative, and any other suitable time and temperature conditions may be employed that are efficacious to separate a first metal or metal ion from the e-waste into a fraction that can be further processed to reclaim said metal.
- Oxidizing agents are included in the composition to oxidize the metals to be removed into an ionic form.
- Oxidizing agents contemplated herein include, but are not limited to, methanesulfonic acid (MSA), ethanesulfonic acid, benzenesulfonic acid, 2-hydroxyethanesulfonic acid, cyclohexylaminosulfonic acid, n-propanesulfonic acid, n-butanesulfonic acid, or n-octanesulfonic acid, hydrogen peroxide (H 2 O 2 ), FeCl 3 (both hydrated and unhydrated), oxone (2KHSO 5 .KHSO 4 .K 2 SO 4 ), ammonium polyatomic salts (e.g., ammonium peroxomonosulfate, ammonium chlorite (NH 4 ClO 2 ), ammonium chlorate (NH 4 ClO 3 ), ammonium iodate (NH 4 IO 3 ),
- the oxidizing agent may be introduced to the first composition at the manufacturer, prior to introduction of the first composition to the PWB, or alternatively at the PWB, i.e., in situ.
- the oxidizing agent comprises a peroxide compound such as hydrogen peroxide.
- the complexing agents are included to complex the ions produced by the oxidizing agent.
- Complexing agents contemplated herein include, but are not limited to: ⁇ -diketonate compounds such as acetylacetonate, 1,1,1-trifluoro-2,4-pentanedione, and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; carboxylates such as formate and acetate and other long chain carboxylates; and amides (and amines), such as bis(trimethylsilylamide) tetramer.
- Additional chelating agents include amines and amino acids (i.e.
- glycine serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine
- citric acid acetic acid, maleic acid, oxalic acid, malonic acid, succinic acid, phosphonic acid, phosphonic acid derivatives such as hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1,1-diphosphonic acid, nitrilo-tris(methylenephosphonic acid), nitrilotriacetic acid, iminodiacetic acid, etidronic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), and (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyme, pentamethyldiethylenetriamine (PMDETA), 1,3,5-triazine-2,4,6-thithiol trisodium salt solution, 1,
- the catalyst is added to enhance the removal rate of the metal(s) from the e-waste.
- the catalyst comprises a glycol or a glycol ether selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (DEGBE), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl
- the catalyst comprises diethylene glycol monobutyl ether, propylene glycol, dipropylene glycol n-butyl ether, and combinations thereof. Most preferably, the catalyst comprises DEGBE.
- the amount of catalyst is in a range from about 0.01 wt % to about 10 wt %, preferably about 0.1 wt % to about 5 wt %, and most preferably about 0.5 wt % to about 1 wt %.
- chain length of the catalyst e.g., methyl versus butyl
- the first metal digestion composition comprises, consists of, or consists essentially of hydrochloric acid and hydrogen peroxide.
- the first metal digestion composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether.
- the first metal digestion composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether.
- the first metal digestion composition is substantially devoid of nitric acid and cyanide-containing components.
- the first metal digestion compositions are water soluble, non-corrosive, non-flammable and of low toxicity.
- the first metal digestion composition preferably is formulated to substantially separate a first metal or metal ion from the e-waste into a fraction that can be further processed to reclaim said first metal.
- the first metal digestion composition can be used to separate gold from other precious and base metals.
- the first extraction solid can comprise gold
- the first extraction liquid can comprise ions of other precious and base metals (e.g., silver and copper).
- the first extraction solid can be separated from the first extraction liquid using methods well known in the art (e.g., filtration means, centrifugation and decanting, etc.).
- a second extraction can commence, wherein a second metal digestion composition is combined with the first extraction solid which comprises a first metal (e.g., gold).
- the second metal digestion composition can be the same as or different from the first metal digestion composition.
- the second metal digestion composition is the same as the first metal digestion composition, wherein the time and/or temperature of contacting of the first metal digestion composition with the e-waste is different than the time and/or temperature of contacting of the second metal digestion composition with the first extraction solid, as will be clarified in the examples herein.
- the second metal digestion composition as described herein is contacted in any suitable manner to the first extraction solid, e.g., by spraying the composition on the first extraction solid, by dipping (in a volume of the composition) of the first extraction solid, by contacting the first extraction solid with another material, e.g., a pad, or fibrous sorbent applicator element, that has the composition absorbed thereon, or by any other suitable means, manner or technique, by which a composition is brought into contact with the first extraction solid.
- the second extraction process using the second metal digestion composition may be static or dynamic.
- the process is dynamic whereby agitation and/or ultrasonics occurs.
- the composition typically is contacted with the first extraction solid for a time of from about 10 minutes to about 200 minutes, preferably about 30 min to 135 min, at temperature in a range of from about 20° C. to about 70° C., preferably in a range from about 20° C. to about 50° C.
- contacting times and temperatures are illustrative, and any other suitable time and temperature conditions may be employed that are efficacious to separate a first metal ion from the first extraction solid into a fraction that can be further processed to reclaim said metal.
- the second metal digestion composition comprises, consists of, or consists essentially of at least one oxidizing agent and at least one complexing agent. In another embodiment, the second metal digestion composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst.
- the second metal digestion composition is preferably more environmentally friendly than, and is substantially devoid of, nitric acid and cyanide-containing compositions. Further, the second metal digestion composition preferably is formulated to substantially separate the first metal ion from the first extraction solid into a fraction (e.g., an aqueous fraction) that can be further processed to reclaim said metal.
- the second metal digestion composition can be used to separate gold ions from the first extraction solid, wherein the second extraction solid comprises polymeric material.
- the oxidizing agents, complexing agents and catalysts are the same as described hereinabove.
- the second metal digestion composition preferably is formulated to substantially separate the first metal ion (e.g., gold) from the first extraction solid into a fraction (e.g., the second extraction liquid) that can be further processed to reclaim said metal.
- the second metal digestion composition can be used to separate gold ions from the first extraction solid.
- the second extraction liquid can comprise gold ions
- the second extraction solid can comprise residual plastics. It should be appreciated by the skilled artisan that the residual plastics may be disposed of or alternatively, recycled or reclaimed for reuse.
- the metal can be obtained by reducing the metal ions, as will be discussed at length hereinbelow.
- an additive can be added to further separate metals that are present in the first extraction liquid.
- the additive can be a pH adjusting agent or an organic phase such that upon addition of the additive to the first extraction liquid, a second metal ion is separated from a third metal ion based using precipitation or separation.
- the temperature of the contacting conditions can be varied.
- the additive is a pH adjusting agent wherein the pH of the first extraction liquid is raised to a pH in a range from about 6 to about 12, preferably about 9 to about 11, to separate a second metal ion from the first extraction liquid.
- pH adjusting agents contemplated herein preferably include hydroxide ions such as alkali and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, or barium hydroxide.
- the pH adjusting agents can include quaternary ammonium bases having the formula [NR 1 R 2 R 3 R 4 ] + OH ⁇ , wherein R 1 , R 2 , R 3 and R 4 can be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained or branched C 1 -C 6 alkyls (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), C 6 -C 10 aryls (e.g., benzyl), and combinations thereof.
- C 1 , R 2 , R 3 and R 4 can be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained or branched C 1 -C 6 alkyls (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), C 6 -C 10 aryls (e.g.
- the addition of the pH adjusting agent to the first extraction liquid preferably substantially separates a second metal ion from the first extraction liquid into a fraction that can be further processed to reclaim said metal.
- a precipitate comprising metal hydroxides will form, said precipitate being readily separable from the remaining liquid comprising the second metal ion (the “pH ramp liquid”).
- the pH ramp solid can be separated from the pH ramp liquid using methods well known in the art (e.g., filtration means, centrifugation and decanting, etc.).
- the second metal ions in the pH ramp liquid can comprise silver ions, which are substantially separable from other metals in the first extraction liquid which readily formed hydroxide solids in the presence of a pH adjusting agent.
- the pH ramp liquid comprising silver ions can be reduced to silver metal in a subsequent step to be discussed below.
- the pH ramp solid remaining subsequent to separation from the pH ramp liquid can comprise several metals, most notably copper, in the form of metal hydroxide salts.
- the copper ions can subsequently be extracted from the pH ramp solid into an aqueous phase, followed by reduction to copper metal.
- the copper ions can be extracted from the solid using a dilute sulfuric acid solution.
- Another embodiment relates to a method of removing more than one metal from e-waste as illustrated in FIG. 2 , said method comprising:
- Still another embodiment relates to a method of removing more than one metal from e-waste as illustrated in FIG. 2 , said method comprising:
- the additive is an organic component which is added to the first extraction liquid to separate a metal ion (e.g., the second metal ions) from another metal ion (e.g., the third metal ions).
- a metal ion e.g., the second metal ions
- another metal ion e.g., the third metal ions
- the organic component is added to the first extraction liquid and two phases will form (the organic component is substantially immiscible with the first extraction liquid, which is aqueous), one phase comprising the second metal ions and the other phase comprising the third metal ions.
- Organic components contemplated herein include hydroxyoximes such as ACORGA® M5774 metal extraction reagent (Cytec Industries, Inc.) or the equivalent thereof.
- the addition of the organic component to the first extraction liquid preferably substantially separates a second metal ion from the first extraction liquid into a fraction that can be further processed to reclaim said metal.
- the aqueous phase can comprise the silver ions and the organic phase can comprise copper ions.
- the pH of the aqueous phase comprising the silver ions can be ramped to a range from about 6 to about 12, preferably about 9 to about 11, as described hereinabove, wherein the silver ions are substantially separable from other metals in the aqueous phase which readily formed hydroxide solids in the presence of a pH adjusting agent. Following separation of the pH ramp solid from the pH ramp liquid, the silver ions in the pH ramp liquid can be reduced to obtain silver metal.
- the third metal ions can be extracted out of the organic phase into an aqueous phase and the aqueous phase comprising the third metal ions can be reduced to obtain the copper metal.
- the extraction of the copper ions from the organic phase can be effectuated using dilute sulfuric acid.
- the reducing agent is a so-called environmentally friendly chemical. Moreover, preferably the reduction occurs rapidly with minimal heating requirements.
- preferred reducing agents include, but are not limited to, ascorbic acid, diethyl malonate, sodium metabisulfite, polyphenon 60, glucose and sodium citrate.
- Another embodiment relates to a method of removing more than one metal from e-waste as illustrated in FIG. 3 , said method comprising:
- Yet another embodiment relates to a method of removing more than one metal from e-waste as illustrated in FIG. 3 , said method comprising:
- compositions described herein are easily formulated by simple addition of the respective ingredients and mixing to homogeneous condition. Furthermore, the compositions may be readily formulated as single-package formulations or multi-part formulations that are mixed at or before the point of use, e.g., the individual parts of the multi-part formulation may be mixed at the tool or in a storage tank upstream of the tool.
- concentrations of the respective ingredients may be widely varied in specific multiples of the composition, i.e., more dilute or more concentrated, and it will be appreciated that the compositions described herein can variously and alternatively comprise, consist or consist essentially of any combination of ingredients consistent with the disclosure herein.
- the methods described herein can be used in the mining industry to separate metals from ores.
- the original material to be extracted using the first metal digestion composition is an ore or some other product of the mining industry.
- a method of removing a metal from e-waste comprising contacting the e-waste with a composition under conditions to extract a metal ion from said e-waste into an extraction composition, wherein said composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. Suitable oxidizing agent(s), complexing agent(s) and catalyst(s) have been described herein.
- the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether.
- the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether.
- the method further comprises separating the extraction composition comprising the metal ion from the solid e-waste.
- Solid metal can be obtained by reducing the metal ion in the extraction composition (e.g., with a reducing agent suitable for such purpose).
- the e-waste treated with the extraction compositions described herein may contain two or more different metals.
- a method of removing a metal from e-waste comprising: (a) contacting the e-waste with a composition under conditions to extract a metal ion from said e-waste into an extraction composition; (b) separating the extraction composition comprising the metal ion from the solid e-waste; and (c) obtaining solid metal from the extraction composition comprising the metal ion, wherein said composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. Suitable oxidizing agent(s), complexing agent(s) and catalyst(s) have been described herein.
- the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether. In another embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether.
- Solid metal can be obtained by reducing the metal ion in the extraction composition (e.g., with a reducing agent suitable for such purpose).
- the e-waste treated with the extraction compositions described herein may contain two or more different metals.
- a method of separating a first metal from at least a second metal comprising contacting a material comprising the first and second metal with a composition under conditions to extract a first metal ion from said material into an extraction composition, wherein said composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. Suitable oxidizing agent(s), complexing agent(s) and catalyst(s) have been described herein.
- the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether.
- the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether.
- the method further comprises separating the extraction composition comprising the first metal ion from the material. Solid first metal can be obtained by reducing the first metal ion in the extraction composition (e.g., with a reducing agent suitable for such purpose).
- a method of separating a first metal from at least a second metal comprising: (a) contacting a material comprising the first and second metal with a composition under conditions to extract a first metal ion from said material into an extraction composition; (b) separating the extraction composition comprising the first metal ion from the material; and (c) obtaining a solid first metal from the first metal ion, wherein said composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. Suitable oxidizing agent(s), complexing agent(s) and catalyst(s) have been described herein.
- the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether. In another embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether.
- Solid first metal can be obtained by reducing the first metal ion in the extraction composition (e.g., with a reducing agent suitable for such purpose).
- the first extraction of e-waste using variations of the first metal digestion composition described herein was performed.
- the e-waste was ground into a course powder.
- Single and multiple digestions of the powder were performed in duplicate and the first extraction compositions and the first extraction solids were analyzed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). All digestions were performed using 500 mg-10 g powder in 10 mL-200 mL of first metal digestion composition. Agitation occurred throughout the digestions. Digestion times ranged from about 30 minutes to about 135 minutes at temperatures in a range from about room temperature to about 50° C.
- the first metal digestion compositions tested were as follows:
- Formulation A Aqua regia (Control, 3:1 HCl:HNO3)
- Formulation B 37% HCl:30% H2O2 (90%: 10% by vol.)
- Formulation C 37% HCl:30% H2O2 (90%:10% by vol.) with NH 4 Cl or NH 4 SCN
- Formulation D 37% HCl:30% H2O2 (90%:10% by vol.+0.75 vol. % DEGBE)
- Formulation E 37% HCl:30% H2O2 (90%:10% by vol.+0.75 vol. % propylene glycol)
- Formulation F 37% HCl:30% H2O2 (90%:10% by vol.+0.75 vol. % DPGBE)
- Formulation G Etidronic acid+DEGBE (99%:1% by vol.)
- Formulation I 37% HCl:30% H2O2 (90%: 10% by vol.+0.5 vol. % DEGBE)
- Formulation K 95% H 2 SO 4 :30% H 2 O 2 (90%:10% by vol.)
- Formulation L 95% H 2 SO 4 :30% H 2 O 2 (90%:10% by vol.+0.75 vol. % DEGBE
- Formulation M 37% HCl:30% H2O2 (90%:10% by vol.+25 vol. % DEGBE)
- Formulation N 75 vol. % Etidronic acid+25 vol. % DEGBE
- formulations and reaction conditions can be selected to ensure the selective extraction of silver and copper ions relative to gold.
- the first extraction can be carried out using formulation J as the first metal digestion composition at 50° C. for 30 minutes and silver ions and copper ions are extracted with 79% and 95% efficiency, respectively (relative to aqua regia), while no gold is extracted. Clean formulation J can then be used as the second metal digestion composition at room temperature for 30 minutes and gold ions can be readily extracted from the e-waste.
- the first metal digestion composition can be formulation F at 50° C. for 30 minutes while the second metal digestion composition can be clean formulation F at room temperature for 30 minutes. It should be appreciated that these are just examples to demonstrate that it is possible to formulate a digestion composition and select the appropriate temperature and time to selectively extract metal ions relative to gold for the first extraction step described herein.
- An alternative way to determine the efficiency of metal extraction is to determine the total mass of a single metal extracted into the liquid relative to the total mass of that metal in the e-waste powder.
- the e-waste powder is digested and then the liquid is separated from the solid, the liquid and solid are both analyzed to determine their metal contact, and the percent metal in the liquid relative to the total amount of metal in the e-waste calculated. If the extraction is highly efficient, the metals of interest should be found in the liquid, having been extracted from the solid. Results are shown in Table 2.
- serial extractions could be used to separated Ag and Cu from Au.
- an organic component can be combined with the first extraction liquid to enable selective precipitation of desired metal ions (see, e.g., FIG. 3 , add additive).
- An organic component of interest is M-5774, which is a proprietary mixture of oximes and aldoximes which is selective for Cu ions and phase separates from aqueous solutions. The organic layer extracts Cu ions from aqueous solutions comprising same. Following extraction into M-5774, copper ions can be recovered from the organic M-5774 layer using a dilute sulfuric acid wash.
- the metal ions are preferably reduced to metal solid.
- the reducing agent is a so-called environmentally friendly chemical.
- the reduction occurs rapidly with minimal heating requirements.
- Ascorbic acid (AA) was added to each of the Au 3+ , Ag + and Cu 2+ solutions at the conditions disclosed in Table 6 and room temperature for less than 1 hour and the solids recovered were analyzed using ICP-MS to test for purity. The results are shown in Table 6.
- Diethyl malonate is not miscible with aqueous solutions and Au can be selectively extracted into the organic layer, forming the CH 2 (COOC 2 H 5 )Au(H 2 O) 4 Cl 3 complex at low pH. Thereafter, the organic extract containing the Au can be washed by mixing with HNO 3 to remove impurities and then FeSO 4 at 80° C. can be used to reduce to Au metal.
- Au +3 Au 3+ in soln at pH 1 No solid formed N/A Au move to DEM layer
- Au Au(s) formed may contain oxide or chloride salts Au +3 Au 3+ in soln at pH 10
- Light yellow solid 93% Au Au(s) formed may 50° C. for 20 min formed, 94% contain oxide or chloride salts Au +3 Au 3+ in soln at pH 10
- Yellow solid formed, 56% Au Likely contains 50° C.
- diethyl malonate was more effective for Au reduction, relative to either Ag or Cu.
- Polyphenon 60 (P60) was added to each of the Au 3+ , Ag + and Cu 2+ solutions at the conditions disclosed in Table 9 and room temperature and the solids recovered were analyzed using ICP-MS to test for purity. The results are shown in Table 9.
Abstract
Processes for recycling electronic components removed from printed wire boards, whereby precious metals and base metals are extracted from the electronic components using environmentally friendly compositions. At least gold, silver and copper ions can be extracted from the electronic components and reduced to their respective metals using the processes and compositions described herein.
Description
- The present invention relates generally to environmentally friendly processes for recycling printed wire boards, more specifically environmentally friendly processes for extracting the precious metals and base metals from IC chips and other materials comprising said metals.
- Disposal of used electronic equipment, parts, and components, including obsolete or damaged computers, computer monitors, television receivers, cellular telephones, MP3 players, and similar products, is increasing at a rapid rate. It is recognized that there are significant hazards to living things and to the environment generally when electronic equipment is dumped in landfills. Equally, it is understood that improper disassembly poses appreciable risks to the health and safety of people performing disassembly manually.
- Printed wire boards (PWB's) are a common component of many electronic systems. PWB's are typically manufactured by laminating dry film on clean copper foil, which is supported on a fiberglass plate matrix. The film is exposed with a film negative of the circuit board design, and an etcher is used to remove unmasked copper foil from the plate. Solder is then applied over the unetched copper on the board. Depending upon the use and design of the particular PWB, various other metals may be used in the manufacturing process, including lead, tin, nickel, iron, zinc, aluminum, silver, gold, platinum, and mercury. The PWB's include many additional components, for example, transistors, capacitors, heat sinks, IC's, resistors, integrated switches, processors, etc.
- PWB's are potentially a difficult waste material to process since they generally have little usefulness once they are removed from the electrical component in which they were installed. In addition, they typically consist of materials that classify them as a hazardous or “special” waste stream. They must be segregated and handled separately from other nonhazardous solid waste streams. PWB's that are handled as waste materials must be processed using any one of several available disposal options. Not only are these options expensive, they require a significant amount of effort and handling by the generator. Furthermore, since some of these disposal options do not include destruction of the waste circuit boards, the generator also retains much of the liability associated with improper handling or disposal.
- Different methods have been suggested to try to combat the waste of raw materials and environmental pollution through the ever increasing load of scrap electronic waste. As far as PWB's are concerned the main problem remains in the fact that different materials are either glued, soldered or stuck together. Methods requiring a high energy demand are needed to separate the materials so that they can be recycled. Presently, these methods involve shredding the PWB's into an equipped, partly equipped and unequipped state. With regards to shredding, the first two cases are a cause of concern when considering the environment. In the last case the components can be removed by de-soldering, planing down, chiselling off, grinding down, wet chemical processing (e.g., aqua regia, cyanide, etc.) or other similar processes. After this, the PWB's or pieces thereof are burnt in metallurgy works. In this process the base material, made up of glass fibre and plastic or similar such materials, is also burnt. The melting down process of the PWB's causes the energy requirement to be high. Refining the melted down metals also requires further high energy and environmentally unfriendly processes such as smelting.
- The processes described herein are useful for recycling electronic waste and for recovering valuable and/or hazardous metals therefrom. The processes provide an alternative to smelting for the recovery of valuable and/or hazardous metals present in electronic waste.
- In one aspect, a method of removing more than one metal from e-waste is described, said method comprising:
- (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions; and
(e) contacting the first extraction liquid with an additive to separate second metal ions from third metal ions.
Preferably, the first extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst. Preferably, the second extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst. It should be appreciated by the skilled artisan that the first extraction liquid can be the same as or different from the second extraction liquid. In a preferred embodiment, the first metal comprises gold, the second metal comprises silver and the third metal comprises copper. - In another aspect, a method of removing more than one metal from e-waste is described, said method comprising:
- (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions; and
(e) contacting the first extraction liquid with a pH adjusting agent to separate second metal ions from third metal ions.
Preferably, the first extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst. Preferably, the second extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst. It should be appreciated by the skilled artisan that the first extraction liquid can be the same as or different from the second extraction liquid. In a preferred embodiment, the first metal comprises gold, the second metal comprises silver and the third metal comprises copper. - In still another aspect, a method of removing more than one metal from e-waste is described, said method comprising:
- (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions; and
(e) contacting the first extraction liquid with an organic component that is immiscible with the first extraction liquid to separate second metal ions from third metal ions.
Preferably, the first extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst. Preferably, the second extraction liquid comprises at least one chelating agent, at least one oxidizing agent, and at least one catalyst. It should be appreciated by the skilled artisan that the first extraction liquid can be the same as or different from the second extraction liquid. In a preferred embodiment, the first metal comprises gold, the second metal comprises silver and the third metal comprises copper. - In yet another embodiment, a method of removing metals from e-waste, said method comprising:
- (a) contacting the e-waste with a composition to extract at least two metal ions from said e-waste;
(b) separating the at least two metal ions extracted from the e-waste into individual metal ion fractions; and
(c) reducing each fraction of metal ions to solid metals. - Other aspects, features and advantages will be more fully apparent from the ensuing disclosure and appended claims.
-
FIG. 1 illustrates the generic separation process described herein. -
FIG. 2 illustrates schematically the separation process wherein the additive is a pH adjusting agent. -
FIG. 3 illustrates schematically the separation process wherein the additive is an organic component. -
FIG. 4 illustrates the percentage of Ag. Al, Au, Cu, Fe, Mn, Ni, Pb, Sb, Sn and Zn extracted in small scale serial extractions using Formulation D as a function of the total mass of metal extracted. -
FIG. 5 illustrates the percentage of Ag. Al, Au, Cu, Fe, Mn, Ni, Pb, Sb, Sn and Zn extracted in large scale serial extractions using Formulation D as a function of the total mass of metal extracted. - The present invention relates generally to environmentally friendly processes to recycle printed wire boards, more specifically, environmentally friendly processes to recycle components removed from the printed wire boards.
- For the purposes of the present disclosure, “electronic waste” or “e-waste” corresponds to computers, computer monitors, television receivers, cellular telephones, video cameras, digital cameras, DVD players, video game consoles, facsimile machines, copiers, MP3 players, and similar products that have reached the end of their useful life or otherwise have been disposed of Electronic waste or e-waste includes the components contained within these well known items such as printed wire boards and the components contained thereon (e.g., transistors, capacitors, heat sinks, integrated circuits (IC's), resistors, integrated switches, chips, and processors).
- As used herein, “metals” correspond to precious metals and base metals that are preferably extracted from the components removed from the printed wire boards.
- As used herein, “precious metals” include the metals such as gold, silver, platinum, palladium, alloys comprising same, and combinations thereof.
- As used herein, “base metals” corresponds to iron, nickel, lead, zinc, alloys comprising same, and combinations thereof. Although not base metals per se, for the purposes of the present invention, the base metals further include copper, manganese, tin, antimony, aluminum, as well as alloys comprising same, and combinations thereof.
- “Substantially devoid” is defined herein as less than 2 wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt. %, and most preferably less than 0.1 wt. %. “Devoid” corresponds to 0 wt. %.
- As used herein, “about” is intended to correspond to ±5% of the stated value.
- As defined herein, “complexing agent” includes those compounds that are understood by one skilled in the art to be complexing agents, chelating agents, sequestering agents, and combinations thereof. Complexing agents will chemically combine with or physically hold the metal atom and/or metal ion to be removed using the compositions described herein.
- For the purposes of the present description, “printed wire boards” and “printed circuit boards” are synonymous and may be used interchangeably.
- For the purposes of the present description, “PWB components” include, but are not limited to, transistors, capacitors, heat sinks, IC's, resistors, integrated switches, chips, and processors.
- As used herein, the term “releases” corresponds to the complete removal of the component(s) from the PWB component or the partial release of the component(s) from the PWB component, wherein the partial release of the component from the PWB corresponds to the weakening of the solder holding the component(s) to the PWB and the remainder of the release may be carried out by another method.
- As used herein, “substantially separate” corresponds to the separation of a first metal from a material or composition comprising at least two metals, wherein at least 75 wt % of the first metal is separated from the material or composition, preferably at least 85 wt %, even more preferably at least 90 wt %, and most preferably at least 95 wt % of the first metal is separated from the material or composition.
- Compositions may be embodied in a wide variety of specific formulations, as hereinafter more fully described. In all such compositions, wherein specific components of the composition are discussed in reference to weight percentage ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such components are employed.
- In co-pending provisional patent applications 61/362,118 filed on Jul. 7, 2010 and 61/368,360 filed on Jul. 28, 2010, both entitled “Processes for Reclaiming Precious Metals and Copper From Printed Wire Boards,” both of which are incorporated by reference herein in their entireties, a method of removing solder from a surface was described (e.g., a method of removing lead and/or tin-containing solder from a printed wire board (PWB)). With the removal of the solder, the components on the PWB are released and said components may be separated into those that are recyclable and those that may be further processed for disposal, reclamation of useful materials, etc. The present disclosure relates to the reclamation of materials from the PWB components that must be further processed. It should be appreciated that the present disclosure relates to the reclamation of materials from PWB components regardless of how they are obtained (e.g., de-soldering, planing down, chiselling off, grinding down, wet chemical processing or using some other method known in the art).
- In a first aspect, a method of removing metals from e-waste is described and illustrated generally in
FIG. 1 , said method comprising: - (a) contacting the e-waste with a composition to extract at least two metal ions from said e-waste;
(b) separating the at least two metal ions extracted from the e-waste into individual metal ion fractions; and
(c) reducing each fraction of metal ions to individual solid metals. - In one embodiment, a method of removing more than one metal from e-waste is described and illustrated in
FIGS. 2 and 3 , said method comprising: - (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions; and
(e) contacting the first extraction liquid with an additive to separate second metal ions from third metal ions. - In another embodiment, a method of removing more than one metal from e-waste is described and illustrated in
FIGS. 2 and 3 , said method comprising: - (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions;
(e) contacting the first extraction liquid with an additive to separate second metal ions from third metal ions; and
(f) reducing the first metal ions to a first metal, the second metal ions to a second metal, and the third metal ions to a third metal. - The e-waste can be pulverized into a powder, shredded into pieces, crushed, or in any other form so long as the metals contained in the e-waste are readily exposed for extraction from the e-waste. As defined herein, “crushed” e-waste corresponds to any method that substantially exposes the gold and other precious metals of the e-waste (e.g., PWB component) to the extraction composition, e.g., cracking, pulverizing or shredding the e-waste. Preferably, the e-waste is cracked, thereby minimizing the amount of gold or other precious metals lost as a result of the pulverizing or shredding. Precious metals can be lost if scrap is pulverized wherein gold dust adheres to the separated stream and is lost in the magnetic fraction. Accordingly, crushing is further defined as a process whereby no more than 10% of the gold or other precious metals are lost to processes such as pulverizing or shredding, preferably no more than 5%, even more preferably no more than 2%. Moreover, crushing the e-waste minimizes the risk to human health by minimizing the release of dusts containing hazardous metals and brominated flame retardants.
- In one embodiment, the first metal digestion composition comprises, consists of, or consists essentially of at least one oxidizing agent and at least one complexing agent. In another embodiment, the first metal digestion composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. The first metal digestion composition is preferably more environmentally friendly than aqua regia or cyanide-containing compositions. Further, the first metal digestion composition preferably is formulated to substantially separate a first metal or metal ion from the e-waste into a fraction that can be further processed to reclaim said metal. For example, in one embodiment, the first metal digestion composition can be used to separate gold from other precious and base metals, wherein the gold is present in the solid and the other precious and base metals are dissolved in the first metal digestion composition. For example, the gold and polymeric material can be present in the first extraction solid while the first extraction liquid comprises precious metals other than gold and other base metals.
- In first extraction application, the first metal digestion composition as described herein is contacted in any suitable manner to the e-waste, e.g., by spraying the composition on the e-waste, by dipping (in a volume of the composition) of the e-waste, by contacting the e-waste with another material, e.g., a pad, or fibrous sorbent applicator element, that has the composition absorbed thereon, or by any other suitable means, manner or technique, by which a composition is brought into contact with the e-waste. The first extraction process using the first metal digestion composition may be static or dynamic. Preferably, the process is dynamic whereby agitation and/or ultrasonics occurs.
- In use of the first metal digestion composition, the composition typically is contacted with the e-waste for a time of from about 10 minutes to about 200 minutes, preferably about 30 min to 135 min, at temperature in a range of from about 20° C. to about 70° C., preferably in a range from about 20° C. to about 50° C. Such contacting times and temperatures are illustrative, and any other suitable time and temperature conditions may be employed that are efficacious to separate a first metal or metal ion from the e-waste into a fraction that can be further processed to reclaim said metal.
- Oxidizing agents are included in the composition to oxidize the metals to be removed into an ionic form. Oxidizing agents contemplated herein include, but are not limited to, methanesulfonic acid (MSA), ethanesulfonic acid, benzenesulfonic acid, 2-hydroxyethanesulfonic acid, cyclohexylaminosulfonic acid, n-propanesulfonic acid, n-butanesulfonic acid, or n-octanesulfonic acid, hydrogen peroxide (H2O2), FeCl3 (both hydrated and unhydrated), oxone (2KHSO5.KHSO4.K2SO4), ammonium polyatomic salts (e.g., ammonium peroxomonosulfate, ammonium chlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4ClO4), ammonium periodate (NH4IO3), ammonium persulfate ((NH4)2S2O8), ammonium hypochlorite (NH4ClO)), sodium polyatomic salts (e.g., sodium persulfate (Na2S2O8), sodium hypochlorite (NaClO)), potassium polyatomic salts (e.g., potassium iodate (KIO3), potassium permanganate (KMnO4), potassium persulfate, nitric acid (HNO3), potassium persulfate (K2S2O8), potassium hypochlorite (KClO)), tetramethylammonium polyatomic salts (e.g., tetramethylammonium chlorite ((N(CH3)4)ClO2), tetramethylammonium chlorate ((N(CH3)4)ClO3), tetramethylammonium iodate ((N(CH3)4)IO3), tetramethylammonium perborate ((N(CH3)4)BO3), tetramethylammonium perchlorate ((N(CH3)4)ClO4), tetramethylammonium periodate ((N(CH3)4IO4), tetramethylammonium persulfate ((N(CH3)4)S2O8)), tetrabutylammonium polyatomic salts (e.g., tetrabutylammonium peroxomonosulfate), peroxomonosulfuric acid, ferric nitrate (Fe(NO3)3), urea hydrogen peroxide ((CO(NH2)2)H2O2), peracetic acid (CH3(CO)OOH), sodium nitrate, potassium nitrate, ammonium nitrate, 4-methoxybenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, 4-nitrobenzenesulfonic acid, toluenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, 3-nitrobenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-nitronaphthalenesulfonic acid, 3-nitronaphthalenesulfonic acid, 2,3-dinitrobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 2,5-dinitrobenzenesulfonic acid, 2,6-dinitrobenzenesulfonic acid, 3,5-dinitrobenzenesulfonic acid, 2,4,6-trinitrobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 2-aminonaphthalenesulfonic acid, 3-aminonaphthalenesulfonic acid, 2,3-diaminobenzenesulfonic acid, 2,4-diaminobenzenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 2,6-diaminobenzenesulfonic acid, 3,5-diaminobenzenesulfonic acid, 2,4,6-triaminobenzenesulfonic acid, 3-hydroxybenzenesulfonic acid, 2-hydroxybenzenesulfonic acid, 2-hydroxynaphthalenesulfonic acid, 3-hydroxynaphthalenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,4-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 2,6-dihydroxybenzenesulfonic acid, 3,5-dihydroxybenzenesulfonic acid, 2,3,4-trihydroxybenzenesulfonic acid, 2,3,5-trihydroxybenzenesulfonic acid, 2,3,6-trihydroxybenzenesulfonic acid, 2,4,5-trihydroxybenzenesulfonic acid, 2,4,6-trihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid, 2,3,4,5-tetrahydroxybenzenesulfonic acid, 2,3,4,6-tetrahydroxybenzenesulfonic acid, 2,3,5,6-tetrahydroxybenzenesulfonic acid, 2,4,5,6-tetrahydroxybenzenesulfonic acid, 3-methoxybenzenesulfonic acid, 2-methoxybenzenesulfonic acid, 2,3-dimethoxybenzenesulfonic acid, 2,4-dimethoxybenzenesulfonic acid, 2,5-dimethoxybenzenesulfonic acid, 2,6-dimethoxybenzenesulfonic acid, 3,5-dimethoxybenzenesulfonic acid, 2,4,6-trimethoxybenzenesulfonic acid, and combinations thereof. The oxidizing agent may be introduced to the first composition at the manufacturer, prior to introduction of the first composition to the PWB, or alternatively at the PWB, i.e., in situ. Preferably, the oxidizing agent comprises a peroxide compound such as hydrogen peroxide.
- The complexing agents are included to complex the ions produced by the oxidizing agent. Complexing agents contemplated herein include, but are not limited to: β-diketonate compounds such as acetylacetonate, 1,1,1-trifluoro-2,4-pentanedione, and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; carboxylates such as formate and acetate and other long chain carboxylates; and amides (and amines), such as bis(trimethylsilylamide) tetramer. Additional chelating agents include amines and amino acids (i.e. glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine), citric acid, acetic acid, maleic acid, oxalic acid, malonic acid, succinic acid, phosphonic acid, phosphonic acid derivatives such as hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1,1-diphosphonic acid, nitrilo-tris(methylenephosphonic acid), nitrilotriacetic acid, iminodiacetic acid, etidronic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), and (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyme, pentamethyldiethylenetriamine (PMDETA), 1,3,5-triazine-2,4,6-thithiol trisodium salt solution, 1,3,5-triazine-2,4,6-thithiol triammonium salt solution, sodium diethyldithiocarbamate, disubstituted dithiocarbamates (R1(CH2CH2O)2NR2CS2Na) with one alkyl group (R2=hexyl, octyl, deceyl or dodecyl) and one oligoether (R1(CH2CH2O)2, where R1=ethyl or butyl), ammonium sulfate, monoethanolamine (MEA), Dequest 2000, Dequest 2010, Dequest 2060s, diethylenetriamine pentaacetic acid, propylenediamine tetraacetic acid, 2-hydroxypyridine 1-oxide, ethylendiamine disuccinic acid (EDDS), N-(2-hydroxyethyl)iminodiacetic acid (HEIDA), sodium triphosphate penta basic, sodium and ammonium salts thereof, ammonium chloride, ammonium sulfate, hydrochloric acid, sulfuric acid, and combinations thereof. Preferably, the complexing agent comprises hydrochloric acid or sulfuric acid.
- The catalyst is added to enhance the removal rate of the metal(s) from the e-waste. Preferably, the catalyst comprises a glycol or a glycol ether selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (DEGBE), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof. Most preferably, the catalyst comprises diethylene glycol monobutyl ether, propylene glycol, dipropylene glycol n-butyl ether, and combinations thereof. Most preferably, the catalyst comprises DEGBE. When included, the amount of catalyst is in a range from about 0.01 wt % to about 10 wt %, preferably about 0.1 wt % to about 5 wt %, and most preferably about 0.5 wt % to about 1 wt %. Although not wishing to be bound by theory, it is thought that by changing the chain length of the catalyst (e.g., methyl versus butyl), that the selectivity of the first extraction composition for certain metals can be varied.
- Preferably, in one embodiment, the first metal digestion composition comprises, consists of, or consists essentially of hydrochloric acid and hydrogen peroxide. In another embodiment, the first metal digestion composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether. In yet another embodiment, the first metal digestion composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether. The first metal digestion composition is substantially devoid of nitric acid and cyanide-containing components. Preferably, the first metal digestion compositions are water soluble, non-corrosive, non-flammable and of low toxicity.
- As illustrated in
FIGS. 2 and 3 , following the first extraction with the first metal digestion composition, there can be a first extraction solid and a first extraction liquid. As introduced hereinabove, the first metal digestion composition preferably is formulated to substantially separate a first metal or metal ion from the e-waste into a fraction that can be further processed to reclaim said first metal. For example, in one embodiment, the first metal digestion composition can be used to separate gold from other precious and base metals. As illustrated inFIGS. 2 and 3 , the first extraction solid can comprise gold, while the first extraction liquid can comprise ions of other precious and base metals (e.g., silver and copper). - Following the first extraction, the first extraction solid can be separated from the first extraction liquid using methods well known in the art (e.g., filtration means, centrifugation and decanting, etc.).
- As illustrated in
FIGS. 2 and 3 , once the first extraction solid is obtained, a second extraction can commence, wherein a second metal digestion composition is combined with the first extraction solid which comprises a first metal (e.g., gold). The second metal digestion composition can be the same as or different from the first metal digestion composition. Preferably, the second metal digestion composition is the same as the first metal digestion composition, wherein the time and/or temperature of contacting of the first metal digestion composition with the e-waste is different than the time and/or temperature of contacting of the second metal digestion composition with the first extraction solid, as will be clarified in the examples herein. - In second extraction application, the second metal digestion composition as described herein is contacted in any suitable manner to the first extraction solid, e.g., by spraying the composition on the first extraction solid, by dipping (in a volume of the composition) of the first extraction solid, by contacting the first extraction solid with another material, e.g., a pad, or fibrous sorbent applicator element, that has the composition absorbed thereon, or by any other suitable means, manner or technique, by which a composition is brought into contact with the first extraction solid. The second extraction process using the second metal digestion composition may be static or dynamic. Preferably, the process is dynamic whereby agitation and/or ultrasonics occurs.
- In use of the second metal digestion composition, the composition typically is contacted with the first extraction solid for a time of from about 10 minutes to about 200 minutes, preferably about 30 min to 135 min, at temperature in a range of from about 20° C. to about 70° C., preferably in a range from about 20° C. to about 50° C. Such contacting times and temperatures are illustrative, and any other suitable time and temperature conditions may be employed that are efficacious to separate a first metal ion from the first extraction solid into a fraction that can be further processed to reclaim said metal.
- In one embodiment, the second metal digestion composition comprises, consists of, or consists essentially of at least one oxidizing agent and at least one complexing agent. In another embodiment, the second metal digestion composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. The second metal digestion composition is preferably more environmentally friendly than, and is substantially devoid of, nitric acid and cyanide-containing compositions. Further, the second metal digestion composition preferably is formulated to substantially separate the first metal ion from the first extraction solid into a fraction (e.g., an aqueous fraction) that can be further processed to reclaim said metal. For example, in one embodiment, the second metal digestion composition can be used to separate gold ions from the first extraction solid, wherein the second extraction solid comprises polymeric material. The oxidizing agents, complexing agents and catalysts are the same as described hereinabove.
- As illustrated in
FIGS. 2 and 3 , following the second extraction with the second metal digestion composition, there can be a second extraction solid and a second extraction liquid. As introduced hereinabove, the second metal digestion composition preferably is formulated to substantially separate the first metal ion (e.g., gold) from the first extraction solid into a fraction (e.g., the second extraction liquid) that can be further processed to reclaim said metal. For example, in one embodiment, the second metal digestion composition can be used to separate gold ions from the first extraction solid. As illustrated inFIGS. 2 and 3 , the second extraction liquid can comprise gold ions, while the second extraction solid can comprise residual plastics. It should be appreciated by the skilled artisan that the residual plastics may be disposed of or alternatively, recycled or reclaimed for reuse. Following the extraction of the metal ions into the second extraction liquid, the metal can be obtained by reducing the metal ions, as will be discussed at length hereinbelow. - Following separation of the first extraction solid from the first extraction liquid, an additive can be added to further separate metals that are present in the first extraction liquid. The additive can be a pH adjusting agent or an organic phase such that upon addition of the additive to the first extraction liquid, a second metal ion is separated from a third metal ion based using precipitation or separation. Alternatively, or in addition to the addition of the pH adjusting agent or organic additive, the temperature of the contacting conditions can be varied.
- It is known in the art that some metal ions readily form hydroxide solids as the pH of a solution is raised. Accordingly, in one embodiment, the additive is a pH adjusting agent wherein the pH of the first extraction liquid is raised to a pH in a range from about 6 to about 12, preferably about 9 to about 11, to separate a second metal ion from the first extraction liquid. pH adjusting agents contemplated herein preferably include hydroxide ions such as alkali and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, or barium hydroxide. Alternatively, the pH adjusting agents can include quaternary ammonium bases having the formula [NR1R2R3R4]+OH−, wherein R1, R2, R3 and R4 can be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained or branched C1-C6 alkyls (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), C6-C10 aryls (e.g., benzyl), and combinations thereof. The addition of the pH adjusting agent to the first extraction liquid preferably substantially separates a second metal ion from the first extraction liquid into a fraction that can be further processed to reclaim said metal. For example, as illustrated in
FIG. 2 , following the pH ramp to a range of about 6 to about 12, preferably about 9 to about 11, a precipitate (the “pH ramp solid”) comprising metal hydroxides will form, said precipitate being readily separable from the remaining liquid comprising the second metal ion (the “pH ramp liquid”). The pH ramp solid can be separated from the pH ramp liquid using methods well known in the art (e.g., filtration means, centrifugation and decanting, etc.). For example, the second metal ions in the pH ramp liquid can comprise silver ions, which are substantially separable from other metals in the first extraction liquid which readily formed hydroxide solids in the presence of a pH adjusting agent. The pH ramp liquid comprising silver ions can be reduced to silver metal in a subsequent step to be discussed below. - The pH ramp solid remaining subsequent to separation from the pH ramp liquid can comprise several metals, most notably copper, in the form of metal hydroxide salts. The copper ions can subsequently be extracted from the pH ramp solid into an aqueous phase, followed by reduction to copper metal. For example, the copper ions can be extracted from the solid using a dilute sulfuric acid solution.
- Accordingly, another embodiment relates to a method of removing more than one metal from e-waste as illustrated in
FIG. 2 , said method comprising: - (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions; and
(e) contacting the first extraction liquid with a pH adjusting agent to separate second metal ions from third metal ions. - Still another embodiment relates to a method of removing more than one metal from e-waste as illustrated in
FIG. 2 , said method comprising: - (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions;
(e) contacting the first extraction liquid with a pH adjusting agent to separate second metal ions from third metal ions; and
(f) reducing the first metal ions to a first metal, the second metal ions to a second metal, and the third metal ions to a third metal. - In another embodiment, the additive is an organic component which is added to the first extraction liquid to separate a metal ion (e.g., the second metal ions) from another metal ion (e.g., the third metal ions). Specifically, the organic component is added to the first extraction liquid and two phases will form (the organic component is substantially immiscible with the first extraction liquid, which is aqueous), one phase comprising the second metal ions and the other phase comprising the third metal ions. Organic components contemplated herein include hydroxyoximes such as ACORGA® M5774 metal extraction reagent (Cytec Industries, Inc.) or the equivalent thereof. The addition of the organic component to the first extraction liquid preferably substantially separates a second metal ion from the first extraction liquid into a fraction that can be further processed to reclaim said metal. For example, referring to
FIG. 3 , the aqueous phase can comprise the silver ions and the organic phase can comprise copper ions. The pH of the aqueous phase comprising the silver ions can be ramped to a range from about 6 to about 12, preferably about 9 to about 11, as described hereinabove, wherein the silver ions are substantially separable from other metals in the aqueous phase which readily formed hydroxide solids in the presence of a pH adjusting agent. Following separation of the pH ramp solid from the pH ramp liquid, the silver ions in the pH ramp liquid can be reduced to obtain silver metal. The third metal ions can be extracted out of the organic phase into an aqueous phase and the aqueous phase comprising the third metal ions can be reduced to obtain the copper metal. The extraction of the copper ions from the organic phase can be effectuated using dilute sulfuric acid. - Reduction of the metal ions to solid, high purity metals is well known to the skilled artisan. Preferably, the reducing agent is a so-called environmentally friendly chemical. Moreover, preferably the reduction occurs rapidly with minimal heating requirements. For example, preferred reducing agents include, but are not limited to, ascorbic acid, diethyl malonate, sodium metabisulfite,
polyphenon 60, glucose and sodium citrate. - Accordingly, another embodiment relates to a method of removing more than one metal from e-waste as illustrated in
FIG. 3 , said method comprising: - (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions; and
(e) contacting the first extraction liquid with an organic component that is immiscible with the first extraction liquid to separate second metal ions from third metal ions. - Yet another embodiment relates to a method of removing more than one metal from e-waste as illustrated in
FIG. 3 , said method comprising: - (a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions;
(e) contacting the first extraction liquid with an organic component that is immiscible with the first extraction liquid to separate second metal ions from third metal ions; and
(f) reducing the first metal ions to a first metal, the second metal ions to a second metal, and the third metal ions to a third metal. - The compositions described herein are easily formulated by simple addition of the respective ingredients and mixing to homogeneous condition. Furthermore, the compositions may be readily formulated as single-package formulations or multi-part formulations that are mixed at or before the point of use, e.g., the individual parts of the multi-part formulation may be mixed at the tool or in a storage tank upstream of the tool. The concentrations of the respective ingredients may be widely varied in specific multiples of the composition, i.e., more dilute or more concentrated, and it will be appreciated that the compositions described herein can variously and alternatively comprise, consist or consist essentially of any combination of ingredients consistent with the disclosure herein.
- Using the methods described herein, greater than 90 wt % of the metals in the e-waste can be reclaimed.
- In another aspect, the methods described herein can be used in the mining industry to separate metals from ores. For example, instead of starting with e-waste, the original material to be extracted using the first metal digestion composition is an ore or some other product of the mining industry.
- In another aspect, a method of removing a metal from e-waste is described, said method comprising contacting the e-waste with a composition under conditions to extract a metal ion from said e-waste into an extraction composition, wherein said composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. Suitable oxidizing agent(s), complexing agent(s) and catalyst(s) have been described herein. In one embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether. In another embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether. In a preferred embodiment, the method further comprises separating the extraction composition comprising the metal ion from the solid e-waste. Solid metal can be obtained by reducing the metal ion in the extraction composition (e.g., with a reducing agent suitable for such purpose). In an embodiment, the e-waste treated with the extraction compositions described herein may contain two or more different metals.
- In still another aspect, a method of removing a metal from e-waste is described, said method comprising: (a) contacting the e-waste with a composition under conditions to extract a metal ion from said e-waste into an extraction composition; (b) separating the extraction composition comprising the metal ion from the solid e-waste; and (c) obtaining solid metal from the extraction composition comprising the metal ion, wherein said composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. Suitable oxidizing agent(s), complexing agent(s) and catalyst(s) have been described herein. In one embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether. In another embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether. Solid metal can be obtained by reducing the metal ion in the extraction composition (e.g., with a reducing agent suitable for such purpose). In an embodiment, the e-waste treated with the extraction compositions described herein may contain two or more different metals.
- In another aspect, a method of separating a first metal from at least a second metal, said method comprising contacting a material comprising the first and second metal with a composition under conditions to extract a first metal ion from said material into an extraction composition, wherein said composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. Suitable oxidizing agent(s), complexing agent(s) and catalyst(s) have been described herein. In one embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether. In another embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether. In another aspect, the method further comprises separating the extraction composition comprising the first metal ion from the material. Solid first metal can be obtained by reducing the first metal ion in the extraction composition (e.g., with a reducing agent suitable for such purpose).
- In another aspect, a method of separating a first metal from at least a second metal, said method comprising: (a) contacting a material comprising the first and second metal with a composition under conditions to extract a first metal ion from said material into an extraction composition; (b) separating the extraction composition comprising the first metal ion from the material; and (c) obtaining a solid first metal from the first metal ion, wherein said composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one complexing agent, and at least one catalyst. Suitable oxidizing agent(s), complexing agent(s) and catalyst(s) have been described herein. In one embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and a glycol or glycol ether. In another embodiment, the composition comprises, consists of, or consists essentially of hydrochloric acid, hydrogen peroxide, and diethylene glycol monobutyl ether. Solid first metal can be obtained by reducing the first metal ion in the extraction composition (e.g., with a reducing agent suitable for such purpose).
- The features and advantages of the invention are more fully shown by the illustrative examples discussed below.
- The first extraction of e-waste using variations of the first metal digestion composition described herein was performed. The e-waste was ground into a course powder. Single and multiple digestions of the powder were performed in duplicate and the first extraction compositions and the first extraction solids were analyzed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). All digestions were performed using 500 mg-10 g powder in 10 mL-200 mL of first metal digestion composition. Agitation occurred throughout the digestions. Digestion times ranged from about 30 minutes to about 135 minutes at temperatures in a range from about room temperature to about 50° C.
- The first metal digestion compositions tested were as follows:
- Formulation A: Aqua regia (Control, 3:1 HCl:HNO3)
- Formulation B: 37% HCl:30% H2O2 (90%: 10% by vol.)
- Formulation C: 37% HCl:30% H2O2 (90%:10% by vol.) with NH4Cl or NH4SCN
- Formulation D: 37% HCl:30% H2O2 (90%:10% by vol.+0.75 vol. % DEGBE)
- Formulation E: 37% HCl:30% H2O2 (90%:10% by vol.+0.75 vol. % propylene glycol)
- Formulation F: 37% HCl:30% H2O2 (90%:10% by vol.+0.75 vol. % DPGBE)
- Formulation G: Etidronic acid+DEGBE (99%:1% by vol.)
- Formulation H: 1:1:6 H2SO4:H2O2:H2O
- Formulation I: 37% HCl:30% H2O2 (90%: 10% by vol.+0.5 vol. % DEGBE)
- Formulation J: 37% HCl:30% H2O2 (90%:10% by vol.+1 vol. % DEGBE)
- Formulation K: 95% H2SO4:30% H2O2 (90%:10% by vol.)
- Formulation L: 95% H2SO4:30% H2O2 (90%:10% by vol.+0.75 vol. % DEGBE
- Formulation M: 37% HCl:30% H2O2 (90%:10% by vol.+25 vol. % DEGBE)
- Formulation N: 75 vol. % Etidronic acid+25 vol. % DEGBE
- Formulation O: Etidronic acid+DEGBE+NH4Cl (94%:1%:5% by vol.)
- Experimental results for the extraction of gold, silver and copper from e-waste using the methods described herein and the formulations are shown in Table 1 below. The aqua regia (formulation A) result was normalized to allow for easy comparison to other digests.
-
TABLE 1 Metal extraction efficiencies relative to aqua regia (formulation A). Formu- Au/ Ag/ Cu/ lation Conditions ppm ppm ppm A 100° C., 60 min 100% 100% 100% B room temperature (RT), 30 min, 101% 36% 32% small scale* B 50° C., 30 min, small scale 54% 54% 66% I RT, 30 min, small scale 126% 71% 44% I 50° C., 30 min, small scale 42% 40% 57% J RT, 30 min, small scale 132% 90% 72% J 50° C., 30 min, small scale 0% 79% 95% H 50° C., 30 min, small scale 0% 8% 58% K 50° C., 30 min, small scale 0% 2% 1% D RT, 30 min, small scale 55% 40% 33% D 50° C., 30 min, small scale 14-16% 81-83% 46-100% D RT, 135 min, small scale, 198% 111% 50% serial extraction (total) D 50° C., 135 min, large scale,† 24-42% 57-83% 63-77% serial extraction (total) E RT, 30 min, small scale 164% 101% 71% E 50° C., 30 min, small scale 38% 26% 24% F RT, 30 min, small scale 106% 31% 23% F 50° C., 30 min, small scale 0% 62% 71% *small scale is 500 mg e-waste + 10 mL digestion formulation †large scale is 10 g e-waste + 200 mL digestion formulation - It can be seen that a variety of digestion methods yielded greater than 90% extraction efficiency of one or more metals relative to aqua regia (formulation A). Values greater than 100% indicated an extraction efficiency greater than aqua regia for that metal. Multiple extractions can result in 100% recovery of Au, Ag and Cu relative to aqua regia.
- It can be seen that formulations and reaction conditions can be selected to ensure the selective extraction of silver and copper ions relative to gold. For example, the first extraction can be carried out using formulation J as the first metal digestion composition at 50° C. for 30 minutes and silver ions and copper ions are extracted with 79% and 95% efficiency, respectively (relative to aqua regia), while no gold is extracted. Clean formulation J can then be used as the second metal digestion composition at room temperature for 30 minutes and gold ions can be readily extracted from the e-waste. In another alternative, the first metal digestion composition can be formulation F at 50° C. for 30 minutes while the second metal digestion composition can be clean formulation F at room temperature for 30 minutes. It should be appreciated that these are just examples to demonstrate that it is possible to formulate a digestion composition and select the appropriate temperature and time to selectively extract metal ions relative to gold for the first extraction step described herein.
- An alternative way to determine the efficiency of metal extraction is to determine the total mass of a single metal extracted into the liquid relative to the total mass of that metal in the e-waste powder. In this method, the e-waste powder is digested and then the liquid is separated from the solid, the liquid and solid are both analyzed to determine their metal contact, and the percent metal in the liquid relative to the total amount of metal in the e-waste calculated. If the extraction is highly efficient, the metals of interest should be found in the liquid, having been extracted from the solid. Results are shown in Table 2.
-
TABLE 1 Metal extraction efficiencies relative to the total mass of the metal extracted. Formu- Au/ Ag/ Cu/ lation Conditions ppm ppm ppm M 50° C., 30 min, small scale* 47% 47% 9% I room temperature (RT), 30 min, 61% 74% 87% small scale I 50° C., 30 min, small scale 23% 84% 99% J RT, 30 min, small scale 66% 98% 100% J 50° C., 30 min, small scale 0% 99% 100% E RT, 30 min, small scale 86% 99% 100% E 50° C., 30 min, small scale 23% 81% 60% F RT, 30 min, small scale 76% 63% 47% D 50° C., 30 min, large scale, † 0% 69-88% 98% serial, 1st extraction D 50° C., 105 min, large scale, 72-100% 100% 100% serial, total H 50° C., 30 min, small scale 0% 1% 48% L 50° C., 30 min, small scale 6% 71% 100% L 50° C., 30 min, small scale 26% 99% 29% G 50° C., 30 min, small scale 28% 2% 87% N 50° C., 30 min, small scale 28% 26% 96% N 50° C., 30 min, small scale 19% 6% 62% O 50° C., 30 min, small scale 0% 88% 91% *small scale is 500 mg e-waste + 10 mL digestion formulation † large scale is 10 g e-waste + 200 mL digestion formulation - It can be seen that the most efficient extraction was the formulation D serial extraction, wherein the e-waste was digested in formulation D at 50° C. for 30 minutes, the digestion solution was removed, the remaining e-waste was digested in clean formulation D for another 75 min at 50° C., and the digestion solution removed.
- Small scale serial extractions were performed using formulation D by extracting the e-waste at 50° C. for 30 minutes, followed by two additional extractions with clean formulation D for 30 min and 75 min. The results are shown in
FIG. 4 , wherein at 50° C. all metals except Au were strongly extracted in the first 30 minute extraction and 93% of the total mass of Au was extracted in the second 30 minute and third 75 minute extraction. - Large scale serial extractions (scaled 20 times relative to the small scale serial extraction) were performed using formulation D by extracting the e-waste at 50° C. for 30 minutes, followed by an additional extraction with clean formulation D for 105 min. The results are shown in
FIG. 5 , wherein better separation of the Ag and Cu from the Au was achieved at the larger scale. - Accordingly, serial extractions could be used to separated Ag and Cu from Au.
- Then, starting with an aliquot of the small scale first extraction liquid of this example (formulation D, 50° C., 30 minutes), which is substantially devoid of Au, NaOH was added dropwise (see, e.g.,
FIG. 2 , pH ramp). A precipitate formed at aboutpH 6. Both the precipitate (pH ramp solid at pH 6) and remaining liquid (pH ramp liquid at pH 10) were analyzed for metal ion content using ICP-MS. The results are shown in Table 3: -
TABLE 3 Parts per million of metal ions in pH ramp solid relative to pH ramp liquid for small scale extraction. Au Ag Cu Al Fe Mn Ni Pb Sb Sn Zn pH ramp liquid 0 88 0 0 0 64 42 0 2 0 6 pH ramp solid 0 12 100 100 100 36 58 100 98 100 93 - It can be seen that with the small scale extraction pH ramp that the pH ramp liquid contained mostly Ag (82%) while the precipitate contained 100% of the copper and most of the remaining metals.
- Then, starting with an aliquot of the large scale first extraction liquid of this example (formulation D, 50° C., 30 minutes), which is substantially devoid of Au, NaOH was added dropwise. A precipitate formed at about
pH 6. Both the precipitate (pH ramp solid at pH 6) and remaining liquid (pH ramp liquid at pH 12) were analyzed for metal ion content using ICP-MS. The results are shown in Table 4: -
TABLE 3 Parts per million of metal ions in pH ramp solid relative to pH ramp liquid for large scale extraction. Au Ag Cu Al Fe Mn Ni Pb Sb Sn Zn pH ramp liquid 0 100 1 100 0 0 0 0 0 84 0 pH ramp solid 0 0 99 0 100 100 100 0 100 16 100 - It can be seen that with the large scale extraction pH ramp that the pH ramp liquid contained 100% Ag while the precipitate contained 99% of the copper and most of the remaining metals.
- Alternatively, an organic component can be combined with the first extraction liquid to enable selective precipitation of desired metal ions (see, e.g.,
FIG. 3 , add additive). An organic component of interest is M-5774, which is a proprietary mixture of oximes and aldoximes which is selective for Cu ions and phase separates from aqueous solutions. The organic layer extracts Cu ions from aqueous solutions comprising same. Following extraction into M-5774, copper ions can be recovered from the organic M-5774 layer using a dilute sulfuric acid wash. - Starting with an aliquot of the small scale first extraction liquid of this example (formulation D, 50° C., 30 minutes), which is substantially devoid of Au, M-5774 was added under different pH and temperature conditions for 30 minutes (see, e.g.,
FIG. 3 , add additive). Two layers were created, one aqueous and one organic. Following separation of the layers, the aqueous layer was analyzed for metal ion content using ICP-MS. The results are shown in Table 5: -
TABLE 5 Parts per million of metal ions in aqueous phase for small scale extraction. Au Ag Cu Al Fe Mn Ni Pb Sb Sn Zn pH < 1, 50° C. 24.19 94.10 100.57 143.02 9.11 122.72 125.97 131.84 87.90 93.08 150.27 pH 4, 50° C.0 112.18 14.95 184.25 93.80 94.82 97.00 24.85 92.50 86.32 49.13 pH < 1, RT 13.98 101.61 103.07 113.49 5.12 97.89 99.67 111.94 57.15 67.72 100.06 pH 4,RT 0 98.26 8.45 171.97 80.81 84.41 86.97 19.03 76.09 69.50 42.73 - It can be seen that with the small scale extraction, at
pH 4 and room temperature, Ag (98%) can be selectively extracted from Cu (8%). - Once separated, for example as described in the description herein, the metal ions are preferably reduced to metal solid. Preferably, the reducing agent is a so-called environmentally friendly chemical. Moreover, preferably the reduction occurs rapidly with minimal heating requirements.
- In order to gauge effectiveness of the reducing agents, the reduction of standard solutions of Au+3 (ICP gold standard in dilute HCl (approximately 0.05 M)), Ag+ (1 M AgNO3) and Cu+2 (1 M CuSO4) was performed. Environmentally friendly reducing agents were added to the standard solutions and time, temperature and pH were controlled. The pH was adjusted by adding HCl, NaHCO3 or NaOH before or after addition of the environmentally friendly reducing agent. The pH of the solutions influences the oxidation state of the metal ion and therefore the potential for reduction to the metal solid. The initial amount of metal ion in the solution and the final amount of solid collected following the reduction were compared to determine percent recovery.
- Six environmentally friendly chemical reducing agents were tested: ascorbic acid, diethyl malonate, sodium metabisulfite, polyphenon 60 (P60, green tea extract), D-glucose and sodium citrate, as will be discussed individually below.
- Ascorbic acid (AA) was added to each of the Au3+, Ag+ and Cu2+ solutions at the conditions disclosed in Table 6 and room temperature for less than 1 hour and the solids recovered were analyzed using ICP-MS to test for purity. The results are shown in Table 6.
-
TABLE 6 Ascorbic acid reduction results Elemental Metal Ion Conditions Recovered? Analysis Notes Au+3 Au3+ in soln at pH 1,Brown solid formed, 98% Au High purity AA soln at pH 1104% formation of Au(s) Au+3 Au3+ in soln at pH 1,Brown solid formed, 87% Au Au(s) formation, AA soln at pH 5.5 103% likely contains trace salts Au+3 Au3+ in soln at pH 7,Brown solid formed, 73% Au Likely contains AA soln at pH 5.5 + 107% oxide and chloride base (NaOH) salts Au+3 Au3+ in soln at pH 10,Brown solid formed, 39% Au Likely contains AA soln at pH 5.5 + 113% oxide and chloride base (NaOH) salts Ag+ Ag+ in soln at pH 7,Gray solid formed, 70% Ag Likely contains AA soln at pH 1103% oxide and chloride salts Ag+ Ag+ in soln at pH 7,Dark gray solid 56% Ag Likely contains AA soln at pH 5.5 formed, 111% oxide salts Cu2+ Cu2+ in soln at pH 1,Red-orange solid, 78% Cu Likely contains AA soln at pH 5.5 98% chloride salts Cu2+ Cu2+ in soln at pH 7,Copper colored 98% Cu High purity AA soln at pH 5.5 solid, 110% formation of Cu(s) - It can be seen that high purity Au and Cu was recovered using ascorbic acid in less than one hour.
- Diethyl malonate is not miscible with aqueous solutions and Au can be selectively extracted into the organic layer, forming the CH2(COOC2H5)Au(H2O)4Cl3 complex at low pH. Thereafter, the organic extract containing the Au can be washed by mixing with HNO3 to remove impurities and then FeSO4 at 80° C. can be used to reduce to Au metal.
- Diethyl malonate (DEM) was added to each of the Au3+, Ag+ and Cu2+ solutions at the conditions disclosed in Table 7 and room temperature for less than 1 hour and the solids recovered were analyzed using ICP-MS to test for purity. The results are shown in Table 7.
-
TABLE 7 Diethyl malonate reduction results Elemental Metal Ion Conditions Recovered? Analysis Notes Au+3 Au3+ in soln at pH 1No solid formed N/A Au move to DEM layer Au+3 Au3+ in soln at pH 7Brown solid formed 87% Au Au(s) formed, may contain oxide or chloride salts Au+3 Au3+ in soln at pH 10,Light yellow solid 93% Au Au(s) formed, may 50° C. for 20 min formed, 94% contain oxide or chloride salts Au+3 Au3+ in soln at pH 10,Yellow solid formed, 56% Au Likely contains 50° C. for 150 min 55% oxide or chloride salts Ag+ Ag+ in soln at pH 4No solid formed N/A Two clear layers Cu2+ Cu2+ in soln at pH 1No solid formed N/A Addition of DEM formed two layers Cu2+ Cu2+ in soln at pH 7No solid formed N/A Addition of DEM formed two layers Cu2+ Cu2+ in soln at pH 10No solid formed N/A Precipitate formed upon NaOH addition, Cu(OH)2 - It can be seen that diethyl malonate was more effective for Au reduction, relative to either Ag or Cu.
- Sodium metabisulfite (SMB) was added to each of the Au3+, Ag+ and Cu2+ solutions at the conditions disclosed in Table 8 and room temperature for less than 1 hour and the solids recovered were analyzed using ICP-MS to test for purity. The results are shown in Table 8.
-
TABLE 8 Sodium metabisulfite reduction results Elemental Metal Ion Conditions Recovered? Analysis Notes Au+3 Au3+ in soln at pH 1 Yellow solid formed 95% Au High purity formation of Au(s) Au+3 Au3+ in soln at pH 7 Au mirror observed 97% Au High purity at >3 hr, 142% formation of Au(s) Au+3 Au3+ in soln at pH 10 Au mirror formed 36% Au 36% Au(s) + 64% at >3 hr, 140% SMB contamination Ag+ Ag+ in soln at pH 1 White solid (AgCl) N/A AgCl forms when formed, 90% adjusted to pH 1 with HCl Ag+ Ag+ in soln at pH 4 White solid formed, 61% Ag 61% Ag(s) + 39% 92% SMB contamination Ag+ Ag+ in soln at pH 7 White solid formed, 48% Ag 48% Ag(s) + 52% 106% SMB contamination Ag+ Ag+ in soln at pH 10 Brown solid formed, 50% Ag 50% Ag(s) + 50% solid turned white SMB contamination with SMB addition, 106% Cu2+ Cu2+ in soln at pH 1 White solid formed, 33% Ag 33% Cu(s) + 67% 24% SMB contamination Cu2+ Cu2+ in soln at pH 7 White solid formed, 53% Ag Likely contains Cu 30% oxide salt Cu2+ Cu2+ in soln at pH 10 Blue solid formed, 28% Ag 28% Cu(s) + 72% solid turned brown SMB contamination with SMB addition, 70% - It can be seen that sodium metabisulfite was more effective for Au reduction, relative to either Ag or Cu.
- Polyphenon 60 (P60) was added to each of the Au3+, Ag+ and Cu2+ solutions at the conditions disclosed in Table 9 and room temperature and the solids recovered were analyzed using ICP-MS to test for purity. The results are shown in Table 9.
-
TABLE 9 P60 reduction results Elemental Metal Ion Conditions Recovered? Analysis Notes Au+3 Au3+ in soln at pH 1Red solid started to 32% form after 15 min Ag+ Ag+ in soln at pH 4Silver mirror formed 100% Ag(s) formed at after 15 min, 25% high purity. Ag at >4 hr continues to fall out of solution over time. Cu2+ Cu2+ in soln at pH 7No solid formed N/A - It can be seen that P60 was more effective for Ag reduction, relative to either Au or Cu.
- Glucose was added to each of the Au3+, Ag+ and Cu2+ solutions at the conditions disclosed in Table 10 and the solids recovered were analyzed using ICP-MS to test for purity. The results are shown in Table 10.
-
TABLE 10 Glucose reduction results Elemental Metal Ion Conditions Recovered? Analysis Notes Au+3 Au3+ in soln at pH 1No solid formed N/A (RT) Au+3 Au3+ in soln at pH 1No solid formed N/A (100° C.) Au+3 Au3+ in soln with Red-brown solid N/A Au continues to fall addition of NaOH formed immediately, out of soln over time (RT) Au flakes observed, 83% Ag+ Ag+ in soln at pH 4No solid formed N/A (RT) Ag+ Ag+ in soln at pH 4Ag mirror forms 23% 23% Ag(s) + 67% (100° C.) glucose Cu2+ Cu2+ in soln at pH 7No solid formed N/A (RT) Cu2+ Cu2+ in soln at pH 7No solid formed N/A (100° C.) - Ag and Au solids formed using glucose as a reducing agent, wherein Au required the presence of a base and Ag required high temperatures (100° C.).
- Although the invention has been variously disclosed herein with reference to illustrative embodiments and features, it will be appreciated that the embodiments and features described hereinabove are not intended to limit the invention, and that other variations, modifications and other embodiments will suggest themselves to those of ordinary skill in the art, based on the disclosure herein. The invention therefore is to be broadly construed, as encompassing all such variations, modifications and alternative embodiments within the spirit and scope of the claims hereafter set forth.
Claims (21)
1.-30. (canceled)
31. A method of removing more than one metal from e-waste, said method comprising:
(a) contacting the e-waste with a first metal digestion composition to form a first extraction liquid and a first extraction solid, wherein the first metal digestion composition comprises at least one oxidizing agent and at least one complexing agent;
(b) separating the first extraction solid from the first extraction liquid;
(c) contacting the first extraction solid with a second metal digestion composition to form a second extraction liquid and a second extraction solid, wherein the second metal digestion composition comprises at least one oxidizing agent and at least one complexing agent;
(d) separating the second extraction solid from the second extraction liquid, wherein the second extraction liquid comprises first metal ions; and
(e) contacting the first extraction liquid with an additive to separate second metal ions from third metal ions,
wherein the at least one oxidizing agent comprises methanesulfonic acid (MSA), ethanesulfonic acid, benzenesulfonic acid, 2-hydroxyethanesulfonic acid, cyclohexylaminosulfonic acid, n-propanesulfonic acid, n-butanesulfonic acid, or n-octanesulfonic acid, hydrogen peroxide (H2O2), FeCl3 (both hydrated and unhydrated), oxone (2KHSO5.KHSO4.K2SO4), ammonium peroxomonosulfate, ammonium chlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4ClO4), ammonium periodate (NH4IO3), ammonium persulfate ((NH4)2S2O8), ammonium hypochlorite (NH4ClO), sodium persulfate (Na2S2O8), sodium hypochlorite (NaClO), potassium iodate (KIO3), potassium permanganate (KMnO4), potassium persulfate, nitric acid (HNO3), potassium persulfate (K2S2O8), potassium hypochlorite (KClO), tetramethylammonium chlorite ((N(CH3)4)ClO2), tetramethylammonium chlorate ((N(CH3)4)ClO3), tetramethylammonium iodate ((N(CH3)4)IO3), tetramethylammonium perborate ((N(CH3)4)BO3), tetramethylammonium perchlorate ((N(CH3)4)ClO4), tetramethylammonium periodate ((N(CH3)4)IO4), tetramethylammonium persulfate ((N(CH3)4)S2O8), tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate (Fe(NO3)3), urea hydrogen peroxide ((CO(NH2)2)H2O2), peracetic acid (CH3(CO)OOH), sodium nitrate, potassium nitrate, ammonium nitrate, 4-methoxybenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, 4-nitrobenzenesulfonic acid, toluenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, 3-nitrobenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-nitronaphthalenesulfonic acid, 3-nitronaphthalenesulfonic acid, 2,3-dinitrobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 2,5-dinitrobenzenesulfonic acid, 2,6-dinitrobenzenesulfonic acid, 3,5-dinitrobenzenesulfonic acid, 2,4,6-trinitrobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 2-aminonaphthalenesulfonic acid, 3-aminonaphthalenesulfonic acid, 2,3-diaminobenzenesulfonic acid, 2,4-diaminobenzenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 2,6-diaminobenzenesulfonic acid, 3,5-diaminobenzenesulfonic acid, 2,4,6-triaminobenzenesulfonic acid, 3-hydroxybenzenesulfonic acid, 2-hydroxybenzenesulfonic acid, 2-hydroxynaphthalenesulfonic acid, 3-hydroxynaphthalenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,4-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 2,6-dihydroxybenzenesulfonic acid, 3,5-dihydroxybenzenesulfonic acid, 2,3,4-trihydroxybenzenesulfonic acid, 2,3,5-trihydroxybenzenesulfonic acid, 2,3,6-trihydroxybenzenesulfonic acid, 2,4,5-trihydroxybenzenesulfonic acid, 2,4,6-trihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid, 2,3,4,5-tetrahydroxybenzenesulfonic acid, 2,3,4,6-tetrahydroxybenzenesulfonic acid, 2,3,5,6-tetrahydroxybenzenesulfonic acid, 2,4,5,6-tetrahydroxybenzenesulfonic acid, 3-methoxybenzenesulfonic acid, 2-methoxybenzenesulfonic acid, 2,3-dimethoxybenzenesulfonic acid, 2,4-dimethoxybenzenesulfonic acid, 2,5-dimethoxybenzenesulfonic acid, 2,6-dimethoxybenzenesulfonic acid, 3,5-dimethoxybenzenesulfonic acid, 2,4,6-trimethoxybenzenesulfonic acid, and combinations thereof.
32. The method of claim 31 , wherein the e-waste has been pulverized to powder, shredded, crushed to expose the metals, or a combination thereof.
33. The method of claim 31 , wherein the method is carried out at temperature in a range from 20° C. to 70° C.
34. The method of claim 31 , wherein (i) the first metal digestion composition is the same as the second metal digestion composition, or (ii) the first metal digestion composition is different than the second metal digestion composition.
35. The method of claim 31 , wherein the first metal digestion composition further comprises at least one catalyst, wherein the at least one catalyst comprises a glycol or a glycol ether selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (DEGBE), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof. Most preferably, the catalyst comprises diethylene glycol monobutyl ether, propylene glycol, dipropylene glycol n-butyl ether, and combinations thereof.
36. The method of claim 31 , wherein the second metal digestion composition further comprises at least one catalyst, wherein the at least one catalyst comprises a glycol or a glycol ether selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (DEGBE), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof. Most preferably, the catalyst comprises diethylene glycol monobutyl ether, propylene glycol, dipropylene glycol n-butyl ether, and combinations thereof.
37. The method of claim 31 , wherein the at least one complexing agent comprises a species selected from the group consisting of acetylacetonate, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, formates, acetates, bis(trimethylsilylamide) tetramer, glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine, citric acid, acetic acid, maleic acid, oxalic acid, malonic acid, succinic acid, phosphonic acid, hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1,1-diphosphonic acid, nitrilo-tris(methylenephosphonic acid), nitrilotriacetic acid, iminodiacetic acid, etidronic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), and (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyme, pentamethyldiethylenetriamine (PMDETA), 1,3,5-triazine-2,4,6-thithiol trisodium salt solution, 1,3,5-triazine-2,4,6-thithiol triammonium salt solution, sodium diethyldithiocarbamate, disubstituted dithiocarbamates (R1(CH2CH2O)2NR2CS2Na) with one alkyl group (R2=hexyl, octyl, deceyl or dodecyl) and one oligoether (R1(CH2CH2O)2, where R1=ethyl or butyl), ammonium sulfate, monoethanolamine (MEA), Dequest 2000, Dequest 2010, Dequest 2060s, diethylenetriamine pentaacetic acid, propylenediamine tetraacetic acid, 2-hydroxypyridine 1-oxide, ethylendiamine disuccinic acid (EDDS), N-(2-hydroxyethyl)iminodiacetic acid (HEIDA), sodium triphosphate penta basic, ammonium chloride, ammonium sulfate, hydrochloric acid, sulfuric acid, and combinations thereof.
38. The method of claim 31 , wherein the at least one chelating agent comprises hydrochloric acid or sulfuric acid.
39. The method of claim 31 , wherein the at least one oxidizing agent comprises nitric acid.
40. The method of claim 31 , wherein the first and second metal digestion compositions are devoid of cyanide-containing compounds.
41. The method of claim 31 , wherein the additive comprises a pH adjusting agent.
42. The method of claim 41 , wherein the pH adjusting agent comprises hydroxide ions.
43. The method of claim 31 , wherein the pH of the first metal digestion composition is adjusted to pH in a range from about 6 to about 12.
44. The method of claim 41 , wherein the second metal ions are contained in a liquid fraction and the third metal ions are contained in a solid fraction.
45. The method of claim 31 , further comprising reducing the first metal ions to a first solid metal.
46. The method of claim 31 , further comprising reducing the second metal ions to a second solid metal.
47. The method of claim 31 , further comprising reducing the third metal ions to a third solid metal.
48. The method of claim 31 , wherein the first metal is gold.
49. The method of claim 31 , wherein the second metal is silver.
50. The method of claim 31 , wherein the third metal is copper.
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Also Published As
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CN105274338A (en) | 2016-01-27 |
TW201716588A (en) | 2017-05-16 |
TWI558818B (en) | 2016-11-21 |
US9238850B2 (en) | 2016-01-19 |
WO2012024603A2 (en) | 2012-02-23 |
CL2013000500A1 (en) | 2013-09-23 |
CN103249849A (en) | 2013-08-14 |
KR20130099948A (en) | 2013-09-06 |
WO2012024603A3 (en) | 2012-05-18 |
JP6068341B2 (en) | 2017-01-25 |
TW201229242A (en) | 2012-07-16 |
US20130336857A1 (en) | 2013-12-19 |
EP2606158A4 (en) | 2017-04-26 |
CN103249849B (en) | 2015-11-25 |
BR112013003854A2 (en) | 2016-06-07 |
JP2013540572A (en) | 2013-11-07 |
EP2606158A2 (en) | 2013-06-26 |
JP2017110301A (en) | 2017-06-22 |
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