CA2302353A1 - Process for the extraction of metals from ammoniacal solution - Google Patents
Process for the extraction of metals from ammoniacal solution Download PDFInfo
- Publication number
- CA2302353A1 CA2302353A1 CA002302353A CA2302353A CA2302353A1 CA 2302353 A1 CA2302353 A1 CA 2302353A1 CA 002302353 A CA002302353 A CA 002302353A CA 2302353 A CA2302353 A CA 2302353A CA 2302353 A1 CA2302353 A1 CA 2302353A1
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- copper
- alkyl
- solvent
- water
- 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
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000000605 extraction Methods 0.000 title claims abstract description 16
- 150000002739 metals Chemical class 0.000 title abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000003607 modifier Substances 0.000 claims abstract description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- -1 copper Chemical class 0.000 claims abstract description 21
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- 238000000638 solvent extraction Methods 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 150000001298 alcohols Chemical class 0.000 claims abstract description 16
- 150000001408 amides Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 9
- 150000002576 ketones Chemical class 0.000 claims abstract description 8
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims abstract description 7
- 150000002170 ethers Chemical class 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract 2
- 150000002825 nitriles Chemical class 0.000 claims abstract 2
- 239000002904 solvent Substances 0.000 claims description 32
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- UNJGEWYTCXNJEE-UHFFFAOYSA-N 3-butyl-1-hydroxyimino-1-phenylheptan-2-ol Chemical compound CCCCC(CCCC)C(O)C(=NO)C1=CC=CC=C1 UNJGEWYTCXNJEE-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 150000002826 nitrites Chemical class 0.000 claims description 6
- 229940093635 tributyl phosphate Drugs 0.000 claims description 6
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 56
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000001117 sulphuric acid Substances 0.000 description 8
- 235000011149 sulphuric acid Nutrition 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 150000002923 oximes Chemical class 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000003929 acidic solution Substances 0.000 description 4
- 238000005363 electrowinning Methods 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- OMVSWZDEEGIJJI-UHFFFAOYSA-N 2,2,4-Trimethyl-1,3-pentadienol diisobutyrate Chemical compound CC(C)C(=O)OC(C(C)C)C(C)(C)COC(=O)C(C)C OMVSWZDEEGIJJI-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N 3-Pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZZILRVYYTFVLGI-UHFFFAOYSA-N Pentanol-2-caprylat Natural products CCCCCCCC(=O)OC(C)CCC ZZILRVYYTFVLGI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- NCDCLPBOMHPFCV-UHFFFAOYSA-N hexyl hexanoate Chemical compound CCCCCCOC(=O)CCCCC NCDCLPBOMHPFCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical class OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- VARQGBHBYZTYLJ-UHFFFAOYSA-N tricosan-12-one Chemical compound CCCCCCCCCCCC(=O)CCCCCCCCCCC VARQGBHBYZTYLJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- HNSJWDQXCSDHFY-UHFFFAOYSA-N 1,3-diethyl-1-hexylurea Chemical compound CCCCCCN(CC)C(=O)NCC HNSJWDQXCSDHFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- DXXURQRPWATHQW-UHFFFAOYSA-N 11-methyldodecyl hydrogen carbonate Chemical compound CC(C)CCCCCCCCCCOC(O)=O DXXURQRPWATHQW-UHFFFAOYSA-N 0.000 description 1
- AEOLPHGBVSKUIW-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethoxymethylbenzene Chemical compound CCCCOCCOCCOCC1=CC=CC=C1 AEOLPHGBVSKUIW-UHFFFAOYSA-N 0.000 description 1
- XVTOMLAMPUXGPS-UHFFFAOYSA-N 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctan-1-ol Chemical compound CC(C)(C)CC(C)CCC(CO)C(C)CC(C)(C)C XVTOMLAMPUXGPS-UHFFFAOYSA-N 0.000 description 1
- CROPCLKVTSNPEY-UHFFFAOYSA-N 2-(N-hydroxy-C-phenylcarbonimidoyl)-4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C(C(=NO)C=2C=CC=CC=2)=C1 CROPCLKVTSNPEY-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- YEBIIRHMHYYWAR-UHFFFAOYSA-N 2-butoxyethoxymethylbenzene Chemical compound CCCCOCCOCC1=CC=CC=C1 YEBIIRHMHYYWAR-UHFFFAOYSA-N 0.000 description 1
- HJBUWTLHZIRBIM-UHFFFAOYSA-N 2-chloro-4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C(Cl)=C1 HJBUWTLHZIRBIM-UHFFFAOYSA-N 0.000 description 1
- SWZMVPJGNFUOLG-UHFFFAOYSA-N 2-ethyl-n-hexylhexanamide Chemical compound CCCCCCNC(=O)C(CC)CCCC SWZMVPJGNFUOLG-UHFFFAOYSA-N 0.000 description 1
- GMORVOQOIHISPT-UHFFFAOYSA-N 2-ethylhexanamide Chemical compound CCCCC(CC)C(N)=O GMORVOQOIHISPT-UHFFFAOYSA-N 0.000 description 1
- IEBAJFDSHJYDCK-UHFFFAOYSA-N 2-methylundecan-4-one Chemical compound CCCCCCCC(=O)CC(C)C IEBAJFDSHJYDCK-UHFFFAOYSA-N 0.000 description 1
- WTSHXGXZNWHRQM-UHFFFAOYSA-N 3-methyl-4-pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1C WTSHXGXZNWHRQM-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- CILYKUDMVIRMGY-UHFFFAOYSA-N 4-dodecyl-2-(N-hydroxy-C-phenylcarbonimidoyl)phenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C(C(=NO)C=2C=CC=CC=2)=C1 CILYKUDMVIRMGY-UHFFFAOYSA-N 0.000 description 1
- QHBWOETXANVQER-UHFFFAOYSA-N 4-hexanoyloxybutyl hexanoate Chemical compound CCCCCC(=O)OCCCCOC(=O)CCCCC QHBWOETXANVQER-UHFFFAOYSA-N 0.000 description 1
- KNDDEFBFJLKPFE-UHFFFAOYSA-N 4-n-Heptylphenol Chemical compound CCCCCCCC1=CC=C(O)C=C1 KNDDEFBFJLKPFE-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- YRRCBRRCKPKZCF-UHFFFAOYSA-N 5,8-diethyldodecane-6,7-dione Chemical compound CCCCC(CC)C(=O)C(=O)C(CC)CCCC YRRCBRRCKPKZCF-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- CRKWWBFTYGZTBS-UHFFFAOYSA-N 8-methylnonyl acetate Chemical compound CC(C)CCCCCCCOC(C)=O CRKWWBFTYGZTBS-UHFFFAOYSA-N 0.000 description 1
- KVFJBGFUUKVTCS-UHFFFAOYSA-N C1(=C(C=CC=C1)NC(OCCCCCCCCCCC(C)C)=O)C Chemical compound C1(=C(C=CC=C1)NC(OCCCCCCCCCCC(C)C)=O)C KVFJBGFUUKVTCS-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UMVMVEZHMZTUHD-UHFFFAOYSA-N DL-Propylene glycol dibenzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)COC(=O)C1=CC=CC=C1 UMVMVEZHMZTUHD-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- 239000005640 Methyl decanoate Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 101710199392 TATA-box-binding protein 1 Proteins 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- XVKPYHKSXUGUIY-UHFFFAOYSA-N benzoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound OC(=O)C1=CC=CC=C1.CC(C)C(O)C(C)(C)CO XVKPYHKSXUGUIY-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- CFSSWEQYBLCBLH-UHFFFAOYSA-N iso-hexadecyl alcohol Natural products CC(C)CCCCCCCCCCCCCO CFSSWEQYBLCBLH-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- UIAMCVSNZQYIQS-KTKRTIGZSA-N oleonitrile Chemical compound CCCCCCCC\C=C/CCCCCCCC#N UIAMCVSNZQYIQS-KTKRTIGZSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
- SZKKNEOUHLFYNA-UHFFFAOYSA-N undecanenitrile Chemical compound CCCCCCCCCCC#N SZKKNEOUHLFYNA-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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
- 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
- C22B15/00—Obtaining copper
-
- 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
- C22B3/30—Oximes
-
- 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
- C22B3/306—Ketones or aldehydes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
A process for the solvent extraction of metals, particularly copper, from aqueous ammoniacal solutions is provided. The extractant is an orthohydroxyarylketoxime of Formula (1), wherein R1 is a hydrocarbyl group, and R2 is an ortho-hydroxyaryl group and the extraction process is carried out in the presence of a kinetic modifier. Suitable thermodynamic modifiers which can be employed include alkylphenols, alcohols, esters, ethers and polyethers, carbonates, ketones, nitriles, amides, carbamates, sulphoxides, and salts of amines and quaternary ammonium compounds. Preferred orthohydroxyarylketoximes are 5-(C9 to C14 alkyl)-2-hydroxyacetophenone oximes. Preferred modifiers are highly-branched alkyl esters comprising from 10 to 30 carbon atoms, or highly-branched alkanols comprising from 14 to 30 carbon atoms, or trialkyl phosphates wherein the alkyl groups comprise from 4 to 14 carbon atoms.
Extractant compositions comprising a ketoxime and modifier are also provided.
Extractant compositions comprising a ketoxime and modifier are also provided.
Description
PROCESS FOR THE EXTRACTION OF METALS FROM AMMONIACAL SOLUTION
The present invention concerns a solvent extraction process and especially a process for the extraction of metals, particularly copper, from aqueous ammoniacal solutions, especially solutions obtained by leaching ores with ammonia.
It is known to extract metals, especially copper, from aqueous solutions containing the metal in the form of, for example, a salt, by contacting the aqueous solution with a solution of a solvent extractant in a water immiscible organic solvent and then separating the solvent phase loaded with metal, i.e. containing at least a part of the metal in the form of a complex. The metal can then be recovered by stripping with solution of lower pH followed for example, by electrowinning. Most commonly, the 1 o aqueous metal-containing solutions for extraction are the result of the acid leaching of ores. However it is known that copper can be preferentially leached from certain ores with ammoniacal solutions. This has the advantage that solutions containing especially high concentrations of copper are derived and that there is little contamination of the solution with iron.
Solvent extractants which have found favour in recent years particularly for the recovery of copper from aqueous acidic solutions include oxime reagents, especially o-hydroxyaryloximes. Whilst such reagents have been found to work extremely well in the recovery of copper from acidic solutions, problems have been encountered in the application of such reagents to extraction from ammoniacal solutions. One of these 2o problems results from the high copper concentrations encountered in the ammoniacal solution. This can cause a very high copper loading in the organic solutions, which results in the viscosity of the organic solution increasing to a point where the solution can be difficult to process on an industrial scale. EP-A-0 036 401 solves this problem by the use of an extractant composition comprising two extractants, one being a strong copper extractant, such as an oxime, the other being a weak extractant, a beta-diketone. The use of beta-diketones is also taught by WO 93104208, where they are the preferred extractant, and the only type to be exemplified.
It has now been found that beta-diketones can suffer from poor chemical stability in the presence of the aqueous ammoniacal leach solution, and therefore rapidly lose their effectiveness and form undesirable impurities. Alternative extractants contemplated by WO 93104208, orthohydroxyaryl aldoximes, which have proved to be the most effective extractants for copper from acidic solutions, also suffer problems with stability under ammoniacal leach conditions. Furthermore, most extractants are designed for use in acid leach systems, and operate at relatively low pH. WO 93104208 teaches that employing extractants designed for use with acidic solutions in an ammoniacal system leads to carry over of ammonia into the stripping solution and results in an unacceptable loss of ammonia from the system. The carry over of ammonia is taught to necessitate the further treatment of the organic phase to remove the loaded ammonia.
Amongst the non-beta-diketone reagents contemplated by WO 93/04208 are three ketoximes, 5-nonyl-2-hydroxyacetophenone oxime, 5-nonyl-2 hydroxybenzophenone oxime and 5-dodecyl-2-hydroxybenzophenone oxime. These reagents are disclosed as being equivalent to aldoximes as less preferred alternatives to the beta-diketones.
The beta-diketone and oxime extractants contemplated by WO 93104208 are taught to be soluble to the necessary extent in the water-immiscible solvents commonly employed in solvent extraction. WO 93/04208 discloses that for extractants other than beta-diketones and oximes, a solubility modifier such as an alcohol or ester can be employed where the solubility of the extractant needs to be increased.
During the course of the studies leading to the present invention, it was found that one or more of the problems of poor chemical stability, solution viscosity and ammonia transfer could be ameliorated by the use of a solvent extractant comprising an orthohydroxyarylketoxime and a thermodynamic modifier.
According to a first aspect of the present invention, there is provided a process for the extraction of a metal from ammoniacal solution in which an aqueous ammoniacal solution containing a dissolved metal is contacted with a solvent extraction composition 2 o comprising a water immiscible organic solvent and a water-immiscible solvent extractant, whereby at least a fraction of the metal is extracted into the organic solution, characterised in that the solvent extraction composition comprises an orthohydroxyarylketoxime and a thermodynamic modifier.
Metals that may be extracted in the process according to the present invention include copper, cobalt, nickel and zinc, most preferably copper.
The orthohydroxyarylketoxime compounds employed in the present invention are substantially water insoluble and have the formula:
NOH
2/ ' 1 R R
3o Formula (1) wherein R' is an optionally substituted hydrocarbyl group R2 is an optionally substituted ortho-hydroxyaryl group, and salts thereof.
Whilst the invention is described herein with reference to a compound of Formula (1), it is understood that it relates to said compound in any possible tautomeric forms, and also the complexes formed between orthohydroxyarylketoximes and metals, particularly copper.
Optionally substituted hydrocarbyl groups which may be represented by R' preferably comprise optionally substituted alkyl and aryl groups including combinations of these, such as optionally substituted aralkyl and alkaryl groups.
Examples of optionally substituted alkyl groups which may be represented by R' include groups in which the alkyl moieties can contain from 1 to 20, especially from 1 to 4, carbon atoms. A preferred orthohydroxyarylketoxime is one in which R' is alkyl, preferably containing up to 20, and especially up to 10, and more preferably up to 3 1 o saturated aliphatic carbon atoms. Most preferably R' is a methyl group.
Examples of optionally substituted aryl groups include optionally substituted phenyl groups. When R' is an aryl group, it is preferably an unsubstituted phenyl group.
Optionally substituted ortho-hydroxyaryl groups which may be represented by R2 include optionally substituted phenols. Examples of optionally substituted phenols which may be represented by RZ include those of formula:
OH
Ra ~ Rs wherein R3 to Rs each independently represent H or a C, to C22, preferably a C~ to C,5, linear or branched alkyl group. Particularly preferably only RS
represents a C,_ZZ alkyl 2 o group, most preferably a C, to C,5 alkyl group, with R3; R° and Rfi representing H.
When R' or Rz is substituted, the substituent{s) should be such as not to affect adversely the ability of the orthohydroxyarylketoxime to complex with metals, especially copper. Suitable substituents include halogen, nitro, cyano, hydrocarbyl, such as C,_~-alkyl, especially C,_,o-alkyl; hydrocarbyloxy, such as C,_~-alkoxy, especially 2 5 C,_,o-alkoxy; hydrocarbyloxycarbonyl, such as C,_ZO-alkoxycarbonyl, especially C,_,o-alkoxycarbonyl; aryl, such as C,_ZO-alkylcarbonyl and arylcarbonyl, especially C,_,o-alkylcarbonyl and phenylcarbonyl; and acyloxy, such as C,_ZO-alkylcarbonyloxy and ~rylcarbonyloxy, especially C,_,o-alkylcarbonyloxy and phenylcarbonyloxy.
There may be more than one substituent in which case the substituents may be the same or different.
3o In many preferred embodiments, the orthohydroxyarylketoxime employed is a 5-(C8 to C,4 alkyl)-2-hydroxyacetophenone oxime, particularly 5-nonyl-2-hydroxyacetophenone oxime.
The composition may comprise one or more different orthohydroxyarylketoximes in which the nature of the substituent groups represented by R' and R2 differ between 35 component orthohyd~oxyarylketoximes, especially where the component orthohydroxyarylketoximes are isomeric. Such isomeric mixtures may have better solubility in organic solvents than a single orthohydroxyarylketoxime.
The orthohydroxyarylketoximes are often present in an amount of up to 60% by weight of the composition, commonly no more than 50%, and usually no more than wlw. Often, the orthohydroxyarylketoxime comprises at least 5% by weight, commonly at least 10% by weight and usually at least 20% by weight of composition, and preferably comprises from 25 to 35%, such as about 30%, by weight of the composition.
Thermodynamic modifiers employed in the present invention are substantially water insoluble. Suitable thermodynamic modifiers can be alkyiphenols, alcohols, esters, to ethers and polyethers, carbonates, ketones, nitrites, amides, carbamates, sulphoxides, and salts of amines and quaternary ammonium compounds.
Alkylphenols which may be used as modifiers in conjunction with the extractant include alkylphenols containing from 3 to 15 alkyl carbon atoms, for example 4-tert-butylphenol, 4-heptylphenol, 5-methyl-4-pentylphenol, 2-chloro-4-nonylphenol, 2-cyano-1 s 4-nonylphenol, 4-dodecylphenol, 3-pentadecylphenol and 4-nonylphenol and mixtures thereof. The preferred phenols contain alkyl groups having from 4 to 12 carbon atoms, especially the mixed 4-nonylphenols obtained by condensation of phenol and propylene trimer.
Alcohols which may be used as modifiers in conjunction with the extractant 2 o include saturated and unsaturated hydrocarbon alcohols and polyols containing 14 to 30, preferably 15 to 25 carbon atoms. The alcohols are preferably highly branched with the hydroxyl group located approximately midway along the hydrocarbon backbone.
Especially preferred are the branched chain alcohols that may be made by condensation of short chain alcohols by the Guerbet process, such alcohols sometimes being referred 25 to as Guerbet alcohols. Optionally, the alcohols may contain an aromatic group or other functional group, particularly an ester group.
Especially useful alcohols may be synthesised from highly branched precursors leading to very highly branched Guerbet alcohols containing a large number of terminal methyl groups. Examples of particularly efficient alcohol modifiers include highly 3o branched isohexadecyl alcohol and iso-octadecyl alcohol, the latter being 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctan-1-ol.
Esters which may be used as modifiers in conjunction with the extractant include saturated and unsaturated aliphatic and aromatic-aliphatic esters containing from 10 to 30 carbon atoms. The esters may be mono-esters or polyesters, especially di-esters.
35 The esters are preferably highly branched. Optionally, the esters may contain other functional groups, particularly a hydroxyl group or ether group. Where the ester is a product of the reaction of an alcohol and a mono-carboxylic acid, it is preferred that the alcohol is an alkyl alcohol and comprises from 1 to 6 carbon atoms, and the mono-carboxylic acid comprise from 2 to 16 carbon atoms. Where the ester is a product of the reaction of an alcohol and a di-carboxylic acid, it is preferred that the alcohol is an alkyl alcohol and comprises from 1 to 6 carbon atoms, and the di-carboxylic acid comprises from 4 to 12 carbon atoms. Where the ester is a product of the reaction of a diol and a mono-carboxylic acid, it is preferred that the diol is an alkyl diol and comprises from up to 5 6 carbon atoms, and the mono-carboxylic acid comprises from 6 to 16 carbon atoms.
Where the ester is a tri-alkyl phosphate, the alkyl groups each commonly comprise from 4 to 14 carbon atoms. Examples of useful esters include isodecyl acetate, methyl decanoate, 2-pentyl octanoate, n-hexyl hexanoate, methly isooctanoate, 1,4-butanediol dihexanoate, butyl adipate, isobutyl adipate, bis-2-ethoxyethyl adipate, dipropylene glycol 1 o dibenzoate, propylene glycol dibenzoate, tributyl phospate, trioctylphosphate and triethylhexylphosphate, and particularly 2,2,4-trimethyl-1,3-pentanediol isobutyrate and 2,2,4-trimethyl-1,3-pentanediol benzoate.
Ethers which may be used as modifiers in conjunction with the extractant include hydrocarbon ethers and polyethers containing 12 to 30, preferably 15 to 25 carbon atoms. Examples of useful ethers and pofyethers include benzyl 2-(2-butoxyethoxy)ethyl ether and benzyl 2-butoxyethyl ether.
Carbonates which may be used as modifiers in conjunction with the extractant include carbonates containing from 4 to 16 carbon atoms. Commonly, the carbonates are alkyl carbonates. Examples of useful carbonates include isobutylcarbonate, isotridecylcarbonate and a carbonate mixture comprising a mixture of Ce and C,o alkyl groups.
Ketones which may be used as modifiers in conjunction with the extractant include alkyl ketones in which the alkyl group contains from 1 to 20 carbon atoms.
Examples of useful ketones include isobutyl heptylketone, diundecyl ketone and 5,8 diethyldodecane-6,7-dione.
Nitrites which may be used as modifiers in conjunction with the extractant include aliphatic and arafiphatic hydrocarbonitriles which comprise from 10 to 36 carbon atoms.
Examples of useful nitrites include undecylnitrile and oleonitrile.
Amides which may be used as modifiers in conjunction with the extractant include 3o amides containing from 8 to 20 carbon atoms. Amides comprise products which may be derived from the reaction of a primary or secondary amine with a mono- or di carboxylate acid or equivalent, in particular phosgene or equivalents. Examples of useful amides include N,N'-bis-2-ethylhexyl urea, N,N'-bis-2-ethylhexyl 2-ethylhexanamide, N-hexyl 2-ethylhexanamide, N,N'-dibutyl benzamide, N,N'-dibutyl octanamide, N,N'-dimethyl octanamide and N,N'-bis-2-ethylhexyl versatamide.
Carbamates which may be used as modifiers in conjunction with the extractant include alkyl and aryl carbamates. Examples of useful carbamates include N-octyl isotridecylcarbamate and isotridecyl N-tolylcarbamate.
Sulphoxides which may be used as modifiers in conjunction with the extractant include alkyl sulphoxides. An example of a useful sulpoxide is di-2-ethylhexyl sulphoxide.
Salts of amines and quaternary ammonium compounds which may be used as modifiers in conjunction with the extractant include tertiary amines and quaternary ammonium compounds containing alkyl groups having from 8 to 18 carbon atoms and sulphonic acid salts thereof. Examples of sulphonic acids include dinonylnapthalene sulphonic acid and toluene sulphonic acid.
In the context of the present invention, 'highly branched' as applied to the alcohols and esters means that the ratio of the number of methyl carbon atoms to non-methyl 1 o carbon atoms is higher than 1:5 and preferably higher than 1:3.
If desired, mixtures of compounds selected from the group consisting of alkylphenols, alcohols, esters, ethers, polyethers, carbonates, ketones, nitrites, amides, carbamates, sulphoxides, and salts of amines and quaternary ammonium compounds may be employed as modifiers. Particularly preferred are mixtures comprising a first compound selected from the group consisting of alkylphenols, alcohols, esters, ethers, polyethers, carbonates, ketones, nitrites, amides, carbamates, sulphoxides, and salts of amines and quaternary ammonium compounds and a second compound selected from the group consisting of alkanols having from 6 to 18 carbon atoms, an alkyl phenol in which the alkyl group contains from 7 to 12 carbon atoms, and tributylphosphate.
2o The modifiers often comprise up to 20% w!w of the composition, preferably from 5 to 15 % w/w, and most preferably from 8 to 12% wlw. The weight ratio of modifier to ketoxime is often in the range of from 10:1 to 1:10, commonly from 5:1 to 1:5, and preferably from 1:1 to 1:4.
The aforementioned modifiers may be used in the preparation of extractant compositions containing one or more extractants and one or more modifiers.
Organic solvents which may be used for the extraction include any mobile organic solvent, or mixture of solvents, which is immiscible with water and is inert under the extraction conditions to the other materials present. Examples of suitable solvents include aliphatic, alicyclic and aromatic hydrocarbons and mixtures of any of these as well as chlorinated hydrocarbons such as trichforoethylene, perchioroethylene, trichloroethane and chloroform. Examples of suitable hydrocarbon solvents include low aromatic (<1% wlw) content hydrocarbon solvents such as ESCAID 110 commercially available from Exxon (ESCAID is a trade mark), and ORFOM SX11 commercially available from Phillips Petroleum (ORFOM is a trade mark). Preferred solvents are hydrocarbon solvents including high flash point solvents with a high aromatic content such as SOLVESSO 150 commercially available from Exxon (SOLVESSO is a trade mark) and includes solvents which consist essentially of a mixture of trimethylbenzenes such as AROMASOL H, commercially available from Imperial Chemical Industries PLC
(AROMASOL is a trade mark). Especially preferred, however, on grounds of low toxicity and wide availability are hydrocarbon solvents of relatively low aromatic content such as kerosene, for example ESCAID 100 which is a petroleum distillate comprising 20°~
aromatics, 56.6% paraf~ns and 23.4% naphthenes commercially available from Exxon (ESCAID is a trade mark), or ORFOM SX7, commercially available from Phillips Petroleum (ORFOM is a trade mark).
In many embodiments, the composition comprises at least 35%, often at least 45% by weight, preferably from 50 to 70% w!w of water-immiscible hydrocarbon solvent.
The composition will comprise at least ane orthohydroxyarylketoxime which may be present in an amount up to 54% w/w, and preferably from 25 to 35% .w/w. A
modifier, 1 o particularly an alkylphenol, alcohol or ester modifier may also be present in an amount up to 20%, preferably from 5 to 15%, w/w. Compositions comprising an orthohyrdoxyarylketoxime which is present in an amount from 25 to 35% w/w and an alkylphenol, alcohol or ester mod~er which is present in an amount of from 5 to 15% wlw are particularly preferred.
Particularly preferred solvent extraction compositions are those comprising from to 35% wlw of 5-(C8 to C,4 alkyl)-2-hydroxyacetophenone oxime, 5 to 15% wlw of tridecanol, tributyphosphate, or 2,2,4-trimethyl-1,3-pentanediol isobutyrate or the benzoic acid ester thereof, and from 50 to 70% of water-immiscible hydrocarbon solvent.
The aqueous ammoniacal solution from which metals are extracted by the 2 o process of the present invention often has a pH in the range of from 7 to 12, preferably from 8 to 11, and most preferably from 9 to 10. The solution can be derived from the leaching of ores, particularly chalcocite ores, or may be obtained from other sources, for example metal containing waste streams such as from copper etching baths.
The concentration of metal, particularly copper, in the aqueous ammoniacal 2 5 solution will vary widely depending for example on the source of the solution. Where the solution is derived from the leaching of ores, the metal concentration is often up to 758/1 and most often from 10 to 408/1. Where the solution is a waste stream, the metal concentrations are often somewhat higher than those from the leaching of ores, for example up to 150811, usually from 75 to 130811.
3 o The process of the present invention can be carried out by contacting the solvent extractant composition with the aqueous ammoniacal solution. Ambient or elevated temperatures, such as up to 75°C can be employed if desired. Often a temperature in the range of from 15 to 60°C, and preferably from 30 to 50°C, is employed. The aqueous solution and the solvent extractant are usually agitated together to maximise the interfacial areas between the two solutions. The volume ratio of solvent extractant to aqueous solution are commonly in the range of from 20:1 to 1:20, and preferably in the range of from 5:1 to 1:5. In many embodiments, to reduce plant size and to maximise the use of solvent extractant, organic to aqueous volume ratios close to 1:1 are employed, such as 1.5:1 or less, and preferably 1.3:1 or less.
WO 99/10546 PC1'IUS98/17712 The mole ratio of orthohydroxyarylketoxime to copper transferred is often selected to be in the range of from 2.7:1 to 2:1. Preferably, to achieve improved hydrometallurgical properties, such as reduced viscosity and improved phase disengagement, the mole ratio of oxime to copper transferred is from 2.3:1 to 2.0:1.
After contact with the aqueous ammoniacal solution, the metal can be recovered from the solvent extractant by contact with an aqueous strip solution having a pH lower than that from which the metal was extracted.
The aqueous lower pH strip solution employed in the process according to the present invention is usually acidic, commonly having a pH of 2 or less, and preferably a pH of 1 or less, for example, a pH in the range of from -1 to 0.5. The strip solution commonly comprises a mineral acid, particularly sulphuric acid, nitric acid or hydrochloric acid. In many embodiments, acid concentrations, particularly for sulphuric acid, in the range of from 130 to 200g/l and preferably from 150 to 180g/l are employed. A
low acid concentration but at least 4M chloride containing strip solution as described in European Patent application no. 93301095.1 (publication no. 0 562 709 A2) or fntemational application publication No. W095104835 (both of which are incorporated herein by reference) can be employed. When the extracted metal is copper or zinc, preferred strip solutions respectively comprise stripped or spent electrolyte from a copper or zinc electro-winning cell, typically comprising up to 80g/l copper or zinc, often greater than 2 0 40g11 copper or zinc and preferably from 50 to 70g/l copper or zinc, and up to 200g/l sulphuric acid, often greater than 130g/l sulphuric acid, and preferably from 150 to 180811 sulphuric acid.
The volume ratio of organic solution to aqueous strip solution in the process of the present invention is commonly selected to be such so as to achieve transfer, per litre of strip solution, of up to 50811 of metal, especially copper into the strip solution from the organic solution. In many industrial copper electrowinning processes often at least 108/1, preferably from 25 to 358/1 and especially about 30811 of copper per litre of strip solution is transferred from the organic solution. Volume ratios of organic solution to aqueous solution of from 1:2 to 15:1 and preferably from 1:1 to 10:1, especially less than 3:1 are 3o commonly employed.
A preferred embodiment of the present invention comprises a process for the extraction of a metal from aqueous ammoniacal solution in which:
in step 1, a water-imrniscible solvent extraction composition comprising a orthohydroxyarylketoxime and a thermodynamic modifier is first contacted with the aqueous ammoniacal solution containing metal, in step 2, separating the solvent extraction composition containing metal-solvent extractant complex from the aqueous ammoniacal solution;
WO 99/10546 PCT/US98/1??12 9.
in step 3, contacting the solvent extraction composition containing metal-solvent extractant complex with an aqueous strip solution of lower pH than the ammoniacal solution to effect the stripping of the copper from the water immiscible phase;
in step 4, separating the metal-depleted solvent extraction composition from the lower pH aqueous solution.
The metal can be recovered from the aqueous strip solution by conventional methods, for example by electrowinning.
The invention is further illustrated, but not limited, by the following examples.
1 o Examples 1 and 2 and Comparison A
A mini-rig trial was carried out to investigate the performance of different solvent extraction compositions in the extraction of copper from a typical ammoniacal copper solution. The process comprised two extraction stages, one wash stage and one strip stage. 500 ml counter-current mixer-settlers stirred at 1000 rpm were employed in each stage. The extraction stages were operated at an organic:aqueous (O:A) ratio of 1.2:1, and the wash and strip stages were operated at an organic:aqueous (O:A) ratio of 1:1.
Residence times in each stage were about 3 minutes. The ammoniacal copper solution comprised 30g/l copper, 45g1f ammonia and 75g/l sulphate. The wash solution was a dilute sulphuric acid solution having a pH of 2. The strip solution was an aqueous copper 2o sulphate solution comprising 30g/l copper and 180g11 sulphuric acid. Three different solvent extraction compositions were employed. In Example 1, the extractant comprised 282g/1 of 5-nonyl-2-hydroxyacetophenone oxime and 11 % w/w 2,2,4-trimethyl-1,3-pentanediol isobutyrate in the hydrocarbon solvent ORFOMT"" SX7. In Example 2, the extractant comprised 247g/l of 5-nonyl-2-hydroxyacetophenone oxime and 9.7%
wlw 2,2,4-trimethyl-1,3-pentanediol isobutyrate in the hydrocarbon solvent ORFOMT"" SX7. In Comparison A, the extractant comprised 282g/l of 5-nonyl-2-hydroxyacetophenone oxime in the hydrocarbon solvent ORFOMT"" SX7. During each of the trials, the copper content of the advance electrolyte produced from the strip solution was determined at periodic intervals and used to calculate the percentage copper recovery based on the copper content of the aqueous ammoniacal solution. The percentage copper recoveries achieved were as follows:
Trial % copper recovery Example 1 100 (average of 7 determinations) Example 2 100 (average of 4 determinations) Comparison A 90.3 (average of 3 determinations) The results of Examples 1 and 2 clearly demonstrate the improved performance of the process according to the present invention, compared with the results for Comparison A (not according to the present invention) in which a process omitting the thermodynamic mod~er was employed.
Examples 3, 4, 5, 6, 7 and 8, and Comparisons B and C
5 In a separate test, extraction and stripping isotherms were determined for the solvent extraction compositions. In each case, the extractant comprised 118811 (0.56M) of 5-nonyl-2-hydroxyacetophenone oxime, the Comparison compositions (B and C) had no modifier and the Examples compositions contained 85811 of modifier chosen from tridecanol (Examples 3 and 6), 2,2,4-trimethyl-1,3-pentanediol isobutyrate (Examples 4 to and 7) or tributylphosphate (Examples 5 and 8), in the hydrocarbon solvent ORFORMT""
SX7.
The loading isotherm was generated using a feed composition comprising 30811 copper and 45811 ammonia (2-3811 free ammonia) at 40°C. This was carried out by contacting the formulated reagent at different organic:aqueous (O:A) ratios, allowing the phases to reach equilibrium and then separating the phases and analysing each phase for metal values. The stripping isotherm was generated by contacting an organic phase loaded with copper with a stripping acid composition comprising 35811 copper and 150811 sulphuric acid at 40°C. This was carried out at different organic:aqueous (O:A) ratios, allowing the phases to reach equilibrium and then separating the phases and analysing 2 o each phase for metal values. For Examples 3 and 6, the stripping isotherm was measured at O:A ratios of 2:1, 1.5:1, 1:1, 1:2, 1:6, 1:10 and the extract isotherm was measured at O:A ratios of 1:2, 1:3, 1:5, 1:10. For Examples 4 and 7, the stripping isotherm was measured at O:A ratios of 3:1, 2:1, 1.5:1, 1:1, 1:2, 1:4, 1:10 and the extract isotherm was measured at O:A ratios of 1:2, 1:3, 1:10. For Examples 5 and 8, the stripping isotherm was measured at O:A ratios of 2:1, 1.5:1, 1:1, 1:2, 1:5 and the extract isotherm was measured at O:A ratios of 1.5:1, 1:1, 1:1.5, 1:3. For Comparisons B and C, the stripping isotherm was measured at O:A ratios of 3:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:5 and the extract isotherm was measured at O:A ratios of 1.5:1, 1:1, 1:2, 1:3.
The expected recoveries were then predicted by iterative means using a McCabe-Thiele construction, utilising the isotherm data generated from the experimental data.
The expected recoveries for a 2 extract, 1 strip process at the quoted O:A
ratios for extract and strip stages were:
i ' Modifier OlA Ratio h Ext Strip Recovery Comparison B -- 1:1 1:1 51.45 Example 3 TDA 1:1 1:1 55.75 Example 4 TXIB 1:1 1:1 55.73 Example 5 TBP 1:1 1:1 56.42 Comparison C - 2.02:1 1:1 96.68 Example 6 TDA 2.17:1 1:1 99.68 Example 7 TXIB 1.97:1 1:1 99.91 Example 8 TBP 2.14:1 1:1 98.33 TDA = Tridecanol TXIB = 2,2,4-Trimethyl-1,3-pentanediol isobutyrate TBP = Tributylphosphate The results clearly demonstrate that improved pertormance of the process can be achieved according to the present invention, for a range of modifiers, compared with the results for Comparisons B and C (not according to the present invention) in which a process omitting the thermodynamic modifier was employed.
The present invention concerns a solvent extraction process and especially a process for the extraction of metals, particularly copper, from aqueous ammoniacal solutions, especially solutions obtained by leaching ores with ammonia.
It is known to extract metals, especially copper, from aqueous solutions containing the metal in the form of, for example, a salt, by contacting the aqueous solution with a solution of a solvent extractant in a water immiscible organic solvent and then separating the solvent phase loaded with metal, i.e. containing at least a part of the metal in the form of a complex. The metal can then be recovered by stripping with solution of lower pH followed for example, by electrowinning. Most commonly, the 1 o aqueous metal-containing solutions for extraction are the result of the acid leaching of ores. However it is known that copper can be preferentially leached from certain ores with ammoniacal solutions. This has the advantage that solutions containing especially high concentrations of copper are derived and that there is little contamination of the solution with iron.
Solvent extractants which have found favour in recent years particularly for the recovery of copper from aqueous acidic solutions include oxime reagents, especially o-hydroxyaryloximes. Whilst such reagents have been found to work extremely well in the recovery of copper from acidic solutions, problems have been encountered in the application of such reagents to extraction from ammoniacal solutions. One of these 2o problems results from the high copper concentrations encountered in the ammoniacal solution. This can cause a very high copper loading in the organic solutions, which results in the viscosity of the organic solution increasing to a point where the solution can be difficult to process on an industrial scale. EP-A-0 036 401 solves this problem by the use of an extractant composition comprising two extractants, one being a strong copper extractant, such as an oxime, the other being a weak extractant, a beta-diketone. The use of beta-diketones is also taught by WO 93104208, where they are the preferred extractant, and the only type to be exemplified.
It has now been found that beta-diketones can suffer from poor chemical stability in the presence of the aqueous ammoniacal leach solution, and therefore rapidly lose their effectiveness and form undesirable impurities. Alternative extractants contemplated by WO 93104208, orthohydroxyaryl aldoximes, which have proved to be the most effective extractants for copper from acidic solutions, also suffer problems with stability under ammoniacal leach conditions. Furthermore, most extractants are designed for use in acid leach systems, and operate at relatively low pH. WO 93104208 teaches that employing extractants designed for use with acidic solutions in an ammoniacal system leads to carry over of ammonia into the stripping solution and results in an unacceptable loss of ammonia from the system. The carry over of ammonia is taught to necessitate the further treatment of the organic phase to remove the loaded ammonia.
Amongst the non-beta-diketone reagents contemplated by WO 93/04208 are three ketoximes, 5-nonyl-2-hydroxyacetophenone oxime, 5-nonyl-2 hydroxybenzophenone oxime and 5-dodecyl-2-hydroxybenzophenone oxime. These reagents are disclosed as being equivalent to aldoximes as less preferred alternatives to the beta-diketones.
The beta-diketone and oxime extractants contemplated by WO 93104208 are taught to be soluble to the necessary extent in the water-immiscible solvents commonly employed in solvent extraction. WO 93/04208 discloses that for extractants other than beta-diketones and oximes, a solubility modifier such as an alcohol or ester can be employed where the solubility of the extractant needs to be increased.
During the course of the studies leading to the present invention, it was found that one or more of the problems of poor chemical stability, solution viscosity and ammonia transfer could be ameliorated by the use of a solvent extractant comprising an orthohydroxyarylketoxime and a thermodynamic modifier.
According to a first aspect of the present invention, there is provided a process for the extraction of a metal from ammoniacal solution in which an aqueous ammoniacal solution containing a dissolved metal is contacted with a solvent extraction composition 2 o comprising a water immiscible organic solvent and a water-immiscible solvent extractant, whereby at least a fraction of the metal is extracted into the organic solution, characterised in that the solvent extraction composition comprises an orthohydroxyarylketoxime and a thermodynamic modifier.
Metals that may be extracted in the process according to the present invention include copper, cobalt, nickel and zinc, most preferably copper.
The orthohydroxyarylketoxime compounds employed in the present invention are substantially water insoluble and have the formula:
NOH
2/ ' 1 R R
3o Formula (1) wherein R' is an optionally substituted hydrocarbyl group R2 is an optionally substituted ortho-hydroxyaryl group, and salts thereof.
Whilst the invention is described herein with reference to a compound of Formula (1), it is understood that it relates to said compound in any possible tautomeric forms, and also the complexes formed between orthohydroxyarylketoximes and metals, particularly copper.
Optionally substituted hydrocarbyl groups which may be represented by R' preferably comprise optionally substituted alkyl and aryl groups including combinations of these, such as optionally substituted aralkyl and alkaryl groups.
Examples of optionally substituted alkyl groups which may be represented by R' include groups in which the alkyl moieties can contain from 1 to 20, especially from 1 to 4, carbon atoms. A preferred orthohydroxyarylketoxime is one in which R' is alkyl, preferably containing up to 20, and especially up to 10, and more preferably up to 3 1 o saturated aliphatic carbon atoms. Most preferably R' is a methyl group.
Examples of optionally substituted aryl groups include optionally substituted phenyl groups. When R' is an aryl group, it is preferably an unsubstituted phenyl group.
Optionally substituted ortho-hydroxyaryl groups which may be represented by R2 include optionally substituted phenols. Examples of optionally substituted phenols which may be represented by RZ include those of formula:
OH
Ra ~ Rs wherein R3 to Rs each independently represent H or a C, to C22, preferably a C~ to C,5, linear or branched alkyl group. Particularly preferably only RS
represents a C,_ZZ alkyl 2 o group, most preferably a C, to C,5 alkyl group, with R3; R° and Rfi representing H.
When R' or Rz is substituted, the substituent{s) should be such as not to affect adversely the ability of the orthohydroxyarylketoxime to complex with metals, especially copper. Suitable substituents include halogen, nitro, cyano, hydrocarbyl, such as C,_~-alkyl, especially C,_,o-alkyl; hydrocarbyloxy, such as C,_~-alkoxy, especially 2 5 C,_,o-alkoxy; hydrocarbyloxycarbonyl, such as C,_ZO-alkoxycarbonyl, especially C,_,o-alkoxycarbonyl; aryl, such as C,_ZO-alkylcarbonyl and arylcarbonyl, especially C,_,o-alkylcarbonyl and phenylcarbonyl; and acyloxy, such as C,_ZO-alkylcarbonyloxy and ~rylcarbonyloxy, especially C,_,o-alkylcarbonyloxy and phenylcarbonyloxy.
There may be more than one substituent in which case the substituents may be the same or different.
3o In many preferred embodiments, the orthohydroxyarylketoxime employed is a 5-(C8 to C,4 alkyl)-2-hydroxyacetophenone oxime, particularly 5-nonyl-2-hydroxyacetophenone oxime.
The composition may comprise one or more different orthohydroxyarylketoximes in which the nature of the substituent groups represented by R' and R2 differ between 35 component orthohyd~oxyarylketoximes, especially where the component orthohydroxyarylketoximes are isomeric. Such isomeric mixtures may have better solubility in organic solvents than a single orthohydroxyarylketoxime.
The orthohydroxyarylketoximes are often present in an amount of up to 60% by weight of the composition, commonly no more than 50%, and usually no more than wlw. Often, the orthohydroxyarylketoxime comprises at least 5% by weight, commonly at least 10% by weight and usually at least 20% by weight of composition, and preferably comprises from 25 to 35%, such as about 30%, by weight of the composition.
Thermodynamic modifiers employed in the present invention are substantially water insoluble. Suitable thermodynamic modifiers can be alkyiphenols, alcohols, esters, to ethers and polyethers, carbonates, ketones, nitrites, amides, carbamates, sulphoxides, and salts of amines and quaternary ammonium compounds.
Alkylphenols which may be used as modifiers in conjunction with the extractant include alkylphenols containing from 3 to 15 alkyl carbon atoms, for example 4-tert-butylphenol, 4-heptylphenol, 5-methyl-4-pentylphenol, 2-chloro-4-nonylphenol, 2-cyano-1 s 4-nonylphenol, 4-dodecylphenol, 3-pentadecylphenol and 4-nonylphenol and mixtures thereof. The preferred phenols contain alkyl groups having from 4 to 12 carbon atoms, especially the mixed 4-nonylphenols obtained by condensation of phenol and propylene trimer.
Alcohols which may be used as modifiers in conjunction with the extractant 2 o include saturated and unsaturated hydrocarbon alcohols and polyols containing 14 to 30, preferably 15 to 25 carbon atoms. The alcohols are preferably highly branched with the hydroxyl group located approximately midway along the hydrocarbon backbone.
Especially preferred are the branched chain alcohols that may be made by condensation of short chain alcohols by the Guerbet process, such alcohols sometimes being referred 25 to as Guerbet alcohols. Optionally, the alcohols may contain an aromatic group or other functional group, particularly an ester group.
Especially useful alcohols may be synthesised from highly branched precursors leading to very highly branched Guerbet alcohols containing a large number of terminal methyl groups. Examples of particularly efficient alcohol modifiers include highly 3o branched isohexadecyl alcohol and iso-octadecyl alcohol, the latter being 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctan-1-ol.
Esters which may be used as modifiers in conjunction with the extractant include saturated and unsaturated aliphatic and aromatic-aliphatic esters containing from 10 to 30 carbon atoms. The esters may be mono-esters or polyesters, especially di-esters.
35 The esters are preferably highly branched. Optionally, the esters may contain other functional groups, particularly a hydroxyl group or ether group. Where the ester is a product of the reaction of an alcohol and a mono-carboxylic acid, it is preferred that the alcohol is an alkyl alcohol and comprises from 1 to 6 carbon atoms, and the mono-carboxylic acid comprise from 2 to 16 carbon atoms. Where the ester is a product of the reaction of an alcohol and a di-carboxylic acid, it is preferred that the alcohol is an alkyl alcohol and comprises from 1 to 6 carbon atoms, and the di-carboxylic acid comprises from 4 to 12 carbon atoms. Where the ester is a product of the reaction of a diol and a mono-carboxylic acid, it is preferred that the diol is an alkyl diol and comprises from up to 5 6 carbon atoms, and the mono-carboxylic acid comprises from 6 to 16 carbon atoms.
Where the ester is a tri-alkyl phosphate, the alkyl groups each commonly comprise from 4 to 14 carbon atoms. Examples of useful esters include isodecyl acetate, methyl decanoate, 2-pentyl octanoate, n-hexyl hexanoate, methly isooctanoate, 1,4-butanediol dihexanoate, butyl adipate, isobutyl adipate, bis-2-ethoxyethyl adipate, dipropylene glycol 1 o dibenzoate, propylene glycol dibenzoate, tributyl phospate, trioctylphosphate and triethylhexylphosphate, and particularly 2,2,4-trimethyl-1,3-pentanediol isobutyrate and 2,2,4-trimethyl-1,3-pentanediol benzoate.
Ethers which may be used as modifiers in conjunction with the extractant include hydrocarbon ethers and polyethers containing 12 to 30, preferably 15 to 25 carbon atoms. Examples of useful ethers and pofyethers include benzyl 2-(2-butoxyethoxy)ethyl ether and benzyl 2-butoxyethyl ether.
Carbonates which may be used as modifiers in conjunction with the extractant include carbonates containing from 4 to 16 carbon atoms. Commonly, the carbonates are alkyl carbonates. Examples of useful carbonates include isobutylcarbonate, isotridecylcarbonate and a carbonate mixture comprising a mixture of Ce and C,o alkyl groups.
Ketones which may be used as modifiers in conjunction with the extractant include alkyl ketones in which the alkyl group contains from 1 to 20 carbon atoms.
Examples of useful ketones include isobutyl heptylketone, diundecyl ketone and 5,8 diethyldodecane-6,7-dione.
Nitrites which may be used as modifiers in conjunction with the extractant include aliphatic and arafiphatic hydrocarbonitriles which comprise from 10 to 36 carbon atoms.
Examples of useful nitrites include undecylnitrile and oleonitrile.
Amides which may be used as modifiers in conjunction with the extractant include 3o amides containing from 8 to 20 carbon atoms. Amides comprise products which may be derived from the reaction of a primary or secondary amine with a mono- or di carboxylate acid or equivalent, in particular phosgene or equivalents. Examples of useful amides include N,N'-bis-2-ethylhexyl urea, N,N'-bis-2-ethylhexyl 2-ethylhexanamide, N-hexyl 2-ethylhexanamide, N,N'-dibutyl benzamide, N,N'-dibutyl octanamide, N,N'-dimethyl octanamide and N,N'-bis-2-ethylhexyl versatamide.
Carbamates which may be used as modifiers in conjunction with the extractant include alkyl and aryl carbamates. Examples of useful carbamates include N-octyl isotridecylcarbamate and isotridecyl N-tolylcarbamate.
Sulphoxides which may be used as modifiers in conjunction with the extractant include alkyl sulphoxides. An example of a useful sulpoxide is di-2-ethylhexyl sulphoxide.
Salts of amines and quaternary ammonium compounds which may be used as modifiers in conjunction with the extractant include tertiary amines and quaternary ammonium compounds containing alkyl groups having from 8 to 18 carbon atoms and sulphonic acid salts thereof. Examples of sulphonic acids include dinonylnapthalene sulphonic acid and toluene sulphonic acid.
In the context of the present invention, 'highly branched' as applied to the alcohols and esters means that the ratio of the number of methyl carbon atoms to non-methyl 1 o carbon atoms is higher than 1:5 and preferably higher than 1:3.
If desired, mixtures of compounds selected from the group consisting of alkylphenols, alcohols, esters, ethers, polyethers, carbonates, ketones, nitrites, amides, carbamates, sulphoxides, and salts of amines and quaternary ammonium compounds may be employed as modifiers. Particularly preferred are mixtures comprising a first compound selected from the group consisting of alkylphenols, alcohols, esters, ethers, polyethers, carbonates, ketones, nitrites, amides, carbamates, sulphoxides, and salts of amines and quaternary ammonium compounds and a second compound selected from the group consisting of alkanols having from 6 to 18 carbon atoms, an alkyl phenol in which the alkyl group contains from 7 to 12 carbon atoms, and tributylphosphate.
2o The modifiers often comprise up to 20% w!w of the composition, preferably from 5 to 15 % w/w, and most preferably from 8 to 12% wlw. The weight ratio of modifier to ketoxime is often in the range of from 10:1 to 1:10, commonly from 5:1 to 1:5, and preferably from 1:1 to 1:4.
The aforementioned modifiers may be used in the preparation of extractant compositions containing one or more extractants and one or more modifiers.
Organic solvents which may be used for the extraction include any mobile organic solvent, or mixture of solvents, which is immiscible with water and is inert under the extraction conditions to the other materials present. Examples of suitable solvents include aliphatic, alicyclic and aromatic hydrocarbons and mixtures of any of these as well as chlorinated hydrocarbons such as trichforoethylene, perchioroethylene, trichloroethane and chloroform. Examples of suitable hydrocarbon solvents include low aromatic (<1% wlw) content hydrocarbon solvents such as ESCAID 110 commercially available from Exxon (ESCAID is a trade mark), and ORFOM SX11 commercially available from Phillips Petroleum (ORFOM is a trade mark). Preferred solvents are hydrocarbon solvents including high flash point solvents with a high aromatic content such as SOLVESSO 150 commercially available from Exxon (SOLVESSO is a trade mark) and includes solvents which consist essentially of a mixture of trimethylbenzenes such as AROMASOL H, commercially available from Imperial Chemical Industries PLC
(AROMASOL is a trade mark). Especially preferred, however, on grounds of low toxicity and wide availability are hydrocarbon solvents of relatively low aromatic content such as kerosene, for example ESCAID 100 which is a petroleum distillate comprising 20°~
aromatics, 56.6% paraf~ns and 23.4% naphthenes commercially available from Exxon (ESCAID is a trade mark), or ORFOM SX7, commercially available from Phillips Petroleum (ORFOM is a trade mark).
In many embodiments, the composition comprises at least 35%, often at least 45% by weight, preferably from 50 to 70% w!w of water-immiscible hydrocarbon solvent.
The composition will comprise at least ane orthohydroxyarylketoxime which may be present in an amount up to 54% w/w, and preferably from 25 to 35% .w/w. A
modifier, 1 o particularly an alkylphenol, alcohol or ester modifier may also be present in an amount up to 20%, preferably from 5 to 15%, w/w. Compositions comprising an orthohyrdoxyarylketoxime which is present in an amount from 25 to 35% w/w and an alkylphenol, alcohol or ester mod~er which is present in an amount of from 5 to 15% wlw are particularly preferred.
Particularly preferred solvent extraction compositions are those comprising from to 35% wlw of 5-(C8 to C,4 alkyl)-2-hydroxyacetophenone oxime, 5 to 15% wlw of tridecanol, tributyphosphate, or 2,2,4-trimethyl-1,3-pentanediol isobutyrate or the benzoic acid ester thereof, and from 50 to 70% of water-immiscible hydrocarbon solvent.
The aqueous ammoniacal solution from which metals are extracted by the 2 o process of the present invention often has a pH in the range of from 7 to 12, preferably from 8 to 11, and most preferably from 9 to 10. The solution can be derived from the leaching of ores, particularly chalcocite ores, or may be obtained from other sources, for example metal containing waste streams such as from copper etching baths.
The concentration of metal, particularly copper, in the aqueous ammoniacal 2 5 solution will vary widely depending for example on the source of the solution. Where the solution is derived from the leaching of ores, the metal concentration is often up to 758/1 and most often from 10 to 408/1. Where the solution is a waste stream, the metal concentrations are often somewhat higher than those from the leaching of ores, for example up to 150811, usually from 75 to 130811.
3 o The process of the present invention can be carried out by contacting the solvent extractant composition with the aqueous ammoniacal solution. Ambient or elevated temperatures, such as up to 75°C can be employed if desired. Often a temperature in the range of from 15 to 60°C, and preferably from 30 to 50°C, is employed. The aqueous solution and the solvent extractant are usually agitated together to maximise the interfacial areas between the two solutions. The volume ratio of solvent extractant to aqueous solution are commonly in the range of from 20:1 to 1:20, and preferably in the range of from 5:1 to 1:5. In many embodiments, to reduce plant size and to maximise the use of solvent extractant, organic to aqueous volume ratios close to 1:1 are employed, such as 1.5:1 or less, and preferably 1.3:1 or less.
WO 99/10546 PC1'IUS98/17712 The mole ratio of orthohydroxyarylketoxime to copper transferred is often selected to be in the range of from 2.7:1 to 2:1. Preferably, to achieve improved hydrometallurgical properties, such as reduced viscosity and improved phase disengagement, the mole ratio of oxime to copper transferred is from 2.3:1 to 2.0:1.
After contact with the aqueous ammoniacal solution, the metal can be recovered from the solvent extractant by contact with an aqueous strip solution having a pH lower than that from which the metal was extracted.
The aqueous lower pH strip solution employed in the process according to the present invention is usually acidic, commonly having a pH of 2 or less, and preferably a pH of 1 or less, for example, a pH in the range of from -1 to 0.5. The strip solution commonly comprises a mineral acid, particularly sulphuric acid, nitric acid or hydrochloric acid. In many embodiments, acid concentrations, particularly for sulphuric acid, in the range of from 130 to 200g/l and preferably from 150 to 180g/l are employed. A
low acid concentration but at least 4M chloride containing strip solution as described in European Patent application no. 93301095.1 (publication no. 0 562 709 A2) or fntemational application publication No. W095104835 (both of which are incorporated herein by reference) can be employed. When the extracted metal is copper or zinc, preferred strip solutions respectively comprise stripped or spent electrolyte from a copper or zinc electro-winning cell, typically comprising up to 80g/l copper or zinc, often greater than 2 0 40g11 copper or zinc and preferably from 50 to 70g/l copper or zinc, and up to 200g/l sulphuric acid, often greater than 130g/l sulphuric acid, and preferably from 150 to 180811 sulphuric acid.
The volume ratio of organic solution to aqueous strip solution in the process of the present invention is commonly selected to be such so as to achieve transfer, per litre of strip solution, of up to 50811 of metal, especially copper into the strip solution from the organic solution. In many industrial copper electrowinning processes often at least 108/1, preferably from 25 to 358/1 and especially about 30811 of copper per litre of strip solution is transferred from the organic solution. Volume ratios of organic solution to aqueous solution of from 1:2 to 15:1 and preferably from 1:1 to 10:1, especially less than 3:1 are 3o commonly employed.
A preferred embodiment of the present invention comprises a process for the extraction of a metal from aqueous ammoniacal solution in which:
in step 1, a water-imrniscible solvent extraction composition comprising a orthohydroxyarylketoxime and a thermodynamic modifier is first contacted with the aqueous ammoniacal solution containing metal, in step 2, separating the solvent extraction composition containing metal-solvent extractant complex from the aqueous ammoniacal solution;
WO 99/10546 PCT/US98/1??12 9.
in step 3, contacting the solvent extraction composition containing metal-solvent extractant complex with an aqueous strip solution of lower pH than the ammoniacal solution to effect the stripping of the copper from the water immiscible phase;
in step 4, separating the metal-depleted solvent extraction composition from the lower pH aqueous solution.
The metal can be recovered from the aqueous strip solution by conventional methods, for example by electrowinning.
The invention is further illustrated, but not limited, by the following examples.
1 o Examples 1 and 2 and Comparison A
A mini-rig trial was carried out to investigate the performance of different solvent extraction compositions in the extraction of copper from a typical ammoniacal copper solution. The process comprised two extraction stages, one wash stage and one strip stage. 500 ml counter-current mixer-settlers stirred at 1000 rpm were employed in each stage. The extraction stages were operated at an organic:aqueous (O:A) ratio of 1.2:1, and the wash and strip stages were operated at an organic:aqueous (O:A) ratio of 1:1.
Residence times in each stage were about 3 minutes. The ammoniacal copper solution comprised 30g/l copper, 45g1f ammonia and 75g/l sulphate. The wash solution was a dilute sulphuric acid solution having a pH of 2. The strip solution was an aqueous copper 2o sulphate solution comprising 30g/l copper and 180g11 sulphuric acid. Three different solvent extraction compositions were employed. In Example 1, the extractant comprised 282g/1 of 5-nonyl-2-hydroxyacetophenone oxime and 11 % w/w 2,2,4-trimethyl-1,3-pentanediol isobutyrate in the hydrocarbon solvent ORFOMT"" SX7. In Example 2, the extractant comprised 247g/l of 5-nonyl-2-hydroxyacetophenone oxime and 9.7%
wlw 2,2,4-trimethyl-1,3-pentanediol isobutyrate in the hydrocarbon solvent ORFOMT"" SX7. In Comparison A, the extractant comprised 282g/l of 5-nonyl-2-hydroxyacetophenone oxime in the hydrocarbon solvent ORFOMT"" SX7. During each of the trials, the copper content of the advance electrolyte produced from the strip solution was determined at periodic intervals and used to calculate the percentage copper recovery based on the copper content of the aqueous ammoniacal solution. The percentage copper recoveries achieved were as follows:
Trial % copper recovery Example 1 100 (average of 7 determinations) Example 2 100 (average of 4 determinations) Comparison A 90.3 (average of 3 determinations) The results of Examples 1 and 2 clearly demonstrate the improved performance of the process according to the present invention, compared with the results for Comparison A (not according to the present invention) in which a process omitting the thermodynamic mod~er was employed.
Examples 3, 4, 5, 6, 7 and 8, and Comparisons B and C
5 In a separate test, extraction and stripping isotherms were determined for the solvent extraction compositions. In each case, the extractant comprised 118811 (0.56M) of 5-nonyl-2-hydroxyacetophenone oxime, the Comparison compositions (B and C) had no modifier and the Examples compositions contained 85811 of modifier chosen from tridecanol (Examples 3 and 6), 2,2,4-trimethyl-1,3-pentanediol isobutyrate (Examples 4 to and 7) or tributylphosphate (Examples 5 and 8), in the hydrocarbon solvent ORFORMT""
SX7.
The loading isotherm was generated using a feed composition comprising 30811 copper and 45811 ammonia (2-3811 free ammonia) at 40°C. This was carried out by contacting the formulated reagent at different organic:aqueous (O:A) ratios, allowing the phases to reach equilibrium and then separating the phases and analysing each phase for metal values. The stripping isotherm was generated by contacting an organic phase loaded with copper with a stripping acid composition comprising 35811 copper and 150811 sulphuric acid at 40°C. This was carried out at different organic:aqueous (O:A) ratios, allowing the phases to reach equilibrium and then separating the phases and analysing 2 o each phase for metal values. For Examples 3 and 6, the stripping isotherm was measured at O:A ratios of 2:1, 1.5:1, 1:1, 1:2, 1:6, 1:10 and the extract isotherm was measured at O:A ratios of 1:2, 1:3, 1:5, 1:10. For Examples 4 and 7, the stripping isotherm was measured at O:A ratios of 3:1, 2:1, 1.5:1, 1:1, 1:2, 1:4, 1:10 and the extract isotherm was measured at O:A ratios of 1:2, 1:3, 1:10. For Examples 5 and 8, the stripping isotherm was measured at O:A ratios of 2:1, 1.5:1, 1:1, 1:2, 1:5 and the extract isotherm was measured at O:A ratios of 1.5:1, 1:1, 1:1.5, 1:3. For Comparisons B and C, the stripping isotherm was measured at O:A ratios of 3:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:5 and the extract isotherm was measured at O:A ratios of 1.5:1, 1:1, 1:2, 1:3.
The expected recoveries were then predicted by iterative means using a McCabe-Thiele construction, utilising the isotherm data generated from the experimental data.
The expected recoveries for a 2 extract, 1 strip process at the quoted O:A
ratios for extract and strip stages were:
i ' Modifier OlA Ratio h Ext Strip Recovery Comparison B -- 1:1 1:1 51.45 Example 3 TDA 1:1 1:1 55.75 Example 4 TXIB 1:1 1:1 55.73 Example 5 TBP 1:1 1:1 56.42 Comparison C - 2.02:1 1:1 96.68 Example 6 TDA 2.17:1 1:1 99.68 Example 7 TXIB 1.97:1 1:1 99.91 Example 8 TBP 2.14:1 1:1 98.33 TDA = Tridecanol TXIB = 2,2,4-Trimethyl-1,3-pentanediol isobutyrate TBP = Tributylphosphate The results clearly demonstrate that improved pertormance of the process can be achieved according to the present invention, for a range of modifiers, compared with the results for Comparisons B and C (not according to the present invention) in which a process omitting the thermodynamic modifier was employed.
Claims (11)
1. A process for the extraction of a metal from ammoniacal solution in which an aqueous ammoniacal solution containing a dissolved metal is contacted with a solvent extraction composition comprising a water immiscible organic solvent and a water-immiscible solvent extractant, whereby at least a fraction of the metal is extracted into the organic solution, characterised in that the solvent extraction composition comprises an orthohydroxyarylketoxime and a thermodynamic modifier.
2. A process according to claim 1, wherein the metal is copper, zinc, cobalt or nickel, and is preferably copper.
3. A process according to claim 1 or 2, wherein the orthohydroxyarylketoxime is selected from the class of compounds represented by the Formula (1), wherein R1 is an optionally substituted hydrocarbyl group, and R2 is an optionally substituted ortho-hydroxyaryl group;
and salts thereof.
and salts thereof.
4. A process according to claim 3, wherein the orthohydroxyarylketoxime has the general chemical formula:
wherein R3 to R6 each independently represent H or a C1 to C22, preferably a C7 to C15, linear or branched alkyl group.
wherein R3 to R6 each independently represent H or a C1 to C22, preferably a C7 to C15, linear or branched alkyl group.
5. A process according to claim 4, wherein the orthohydroxyarylketoxime is a 5-(C9 to C14 alkyl)-2-hydroxyacetophenone oxime, preferably 5-nonyl-2-hydroxy-acetophenone oxime.
6. A process according to any preceding claim, wherein the thermodynamic modifier is an alkylphenol, alcohol, ester, ether, polyether, carbonate, ketone, nitrile, amide, carbamate, sulphoxide, or a salt of an amine or quaternary ammonium compound.
7. A process according to any of claims 1-5, wherein the thermodynamic modifier is a mixture comprising a first compound selected from the group consisting of alkylphenols, alcohols, esters, ethers, polyethers, carbonates, ketones, nitrites, amides, carbamates, sulphoxides, and salts of amines and quaternary ammonium compounds and a second compound selected from the group consisting of alkanols having from 6 to 18 carbon atoms, an alkyl phenol in which the alkyl group contains from 7 to 12 carbon atoms, and tributylphosphate
8. A process according to claim 6 or claim 7, wherein the modifier comprises a highly-branched alkyl ester comprising from 10 to 30 carbon atoms, or a highly-branched alkanol comprising from 14 to 30 carbon atoms, or a trialkyl phosphate wherein the alkyl groups comprise from 4 to 14 carbon atoms.
9. A process for the extraction of copper from ammoniacal solution in which an aqueous ammoniacal solution containing dissolved copper is contacted with a solvent extraction composition comprising a water immiscible organic solvent and a water-immiscible solvent extractant, whereby at least a fraction of the copper is extracted into the organic solution, characterised in that the solvent extraction composition comprises from 25 to 35% wlw of 5-(C8 to C14 alkyl)-2-hydroxyacetophenone oxime, 5 to 15% w/w of tridecanol, tributylphosphate, or 2,2,4-trimethyl-1,3-pentanediol isobutyrate or the benzoic acid ester thereof, and a water-immiscible hydrocarbon solvent.
10. A solvent extraction composition comprising a water immiscible organic solvent, a water insoluble orthohydroxyarylketoxime and a water insoluble thermodynamic modifier.
11. A composition according to Claim 10 wherein the solvent extraction composition comprises from 25 to 35% wlw of 5-(C8 to C14 alkyl)-2-hydroxyacetophenone oxime, 5 to 15% wlw of tridecanol, tributylphosphate, or 2,2,4-trimethyl-1,3-pentanediol isobutyrate or the benzoic acid ester thereof, and a water-immiscible hydrocarbon solvent.
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PCT/US1998/017712 WO1999010546A1 (en) | 1997-08-28 | 1998-08-27 | Process for the extraction of metals from ammoniacal solution |
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US6231784B1 (en) | 1995-02-16 | 2001-05-15 | Henkel Corporation | Water insoluble composition of an aldoxime extractant and an equilibrium modifier |
GB9827288D0 (en) | 1998-12-12 | 1999-02-03 | Zeneca Ltd | Composition and process for the extraction of metals |
GB9914669D0 (en) * | 1999-06-24 | 1999-08-25 | Zeneca Ltd | Composition and process |
WO2001012589A1 (en) | 1999-08-12 | 2001-02-22 | Cognis Corporation | Method for separating copper from iron |
US7993613B2 (en) | 2006-12-21 | 2011-08-09 | Cognis Ip Management Gmbh | More efficient ether modifiers for copper extractant formulations |
RU2623552C1 (en) * | 2009-07-07 | 2017-06-27 | Сайтек Текнолоджи Корп. | Methods of extracting metals from water solutions |
US8529850B2 (en) * | 2011-02-25 | 2013-09-10 | Cognis Ip Management Gmbh | Compositions and methods of using a ketoxime in a metal solvent |
US20140271415A1 (en) * | 2013-03-15 | 2014-09-18 | Cory Pecinovsky | Modified oxime extractant formulation |
JP6248861B2 (en) * | 2014-08-19 | 2017-12-20 | 信越化学工業株式会社 | Chemically amplified resist material and pattern forming method |
CN108277344B (en) * | 2018-02-11 | 2022-03-11 | 福建紫金选矿药剂有限公司 | Efficient copper extraction agent in cobalt wet process |
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US3981969A (en) * | 1975-10-15 | 1976-09-21 | Uop Inc. | Pressurized column solvent extraction of nickel from ammoniacal solutions |
SE420737B (en) * | 1980-03-18 | 1981-10-26 | Mx Processer Reinhardt | PROCEDURE FOR EXTRACTION OF COPPER FROM AN AMMONIACAL COPPER SOLUTION AND MEANS FOR EXECUTING THE PROCEDURE |
CA1338345C (en) * | 1988-06-14 | 1996-05-28 | Gary A. Kordosky | Nickel extraction with oxime extractants |
-
1997
- 1997-08-28 GB GBGB9718123.4A patent/GB9718123D0/en active Pending
-
1998
- 1998-08-18 ZA ZA987435A patent/ZA987435B/en unknown
- 1998-08-19 PE PE1998000747A patent/PE96499A1/en not_active Application Discontinuation
- 1998-08-27 BR BR9811404-2A patent/BR9811404A/en unknown
- 1998-08-27 EP EP98943409A patent/EP1025269A1/en not_active Withdrawn
- 1998-08-27 JP JP2000507851A patent/JP2001514324A/en active Pending
- 1998-08-27 KR KR1020007002022A patent/KR20010023382A/en not_active Application Discontinuation
- 1998-08-27 WO PCT/US1998/017712 patent/WO1999010546A1/en not_active Application Discontinuation
- 1998-08-27 CA CA002302353A patent/CA2302353A1/en not_active Abandoned
- 1998-08-27 AU AU91216/98A patent/AU9121698A/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
AU9121698A (en) | 1999-03-16 |
BR9811404A (en) | 2000-08-29 |
KR20010023382A (en) | 2001-03-26 |
EP1025269A1 (en) | 2000-08-09 |
ZA987435B (en) | 1999-03-01 |
GB9718123D0 (en) | 1997-10-29 |
JP2001514324A (en) | 2001-09-11 |
WO1999010546A1 (en) | 1999-03-04 |
PE96499A1 (en) | 1999-10-25 |
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FZDE | Discontinued |