GB2402388A - Composition for extraction of metals comprising a sulphonic acid and a 2-aryl-4-[alpha branched]alkanoyl-5-(aryl/alkyl)-(3H)-pyrazol-3-one derivative - Google Patents
Composition for extraction of metals comprising a sulphonic acid and a 2-aryl-4-[alpha branched]alkanoyl-5-(aryl/alkyl)-(3H)-pyrazol-3-one derivative Download PDFInfo
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- GB2402388A GB2402388A GB0313031A GB0313031A GB2402388A GB 2402388 A GB2402388 A GB 2402388A GB 0313031 A GB0313031 A GB 0313031A GB 0313031 A GB0313031 A GB 0313031A GB 2402388 A GB2402388 A GB 2402388A
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- United Kingdom
- Prior art keywords
- optionally substituted
- metal
- solvent
- alkyl group
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 75
- 239000002184 metal Substances 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000605 extraction Methods 0.000 title claims abstract description 17
- 150000002739 metals Chemical class 0.000 title claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 71
- 239000002904 solvent Substances 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 32
- 125000003118 aryl group Chemical group 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 238000000638 solvent extraction Methods 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 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 claims abstract description 4
- 235000010269 sulphur dioxide Nutrition 0.000 claims abstract description 4
- 239000004291 sulphur dioxide Substances 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims abstract description 3
- 125000001475 halogen functional group Chemical group 0.000 claims abstract 12
- 239000000243 solution Substances 0.000 claims description 57
- -1 naphthyl sulphonic acid Chemical class 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003929 acidic solution Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910006069 SO3H Inorganic materials 0.000 claims description 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 102220029346 rs34541442 Human genes 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 37
- 150000007513 acids Chemical class 0.000 description 22
- 125000005843 halogen group Chemical group 0.000 description 20
- 239000003446 ligand Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 125000002252 acyl group Chemical group 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 235000011149 sulphuric acid Nutrition 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 7
- 239000001117 sulphuric acid Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OUQNIRJSHYHXDV-UHFFFAOYSA-N 4-(2-butyloctanoyl)-5-methyl-2-phenyl-1h-pyrazol-3-one Chemical compound O=C1C(C(=O)C(CCCC)CCCCCC)=C(C)NN1C1=CC=CC=C1 OUQNIRJSHYHXDV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KZQYIMCESJLPQH-UHFFFAOYSA-N Demethylated antipyrine Chemical compound N1C(C)=CC(=O)N1C1=CC=CC=C1 KZQYIMCESJLPQH-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CTTJWXVQRJUJQW-UHFFFAOYSA-N 2,2-dioctyl-3-sulfobutanedioic acid Chemical compound CCCCCCCCC(C(O)=O)(C(C(O)=O)S(O)(=O)=O)CCCCCCCC CTTJWXVQRJUJQW-UHFFFAOYSA-N 0.000 description 1
- YZYZMGGVCYIIIU-UHFFFAOYSA-N 3-sulfo-2,2-di(tridecyl)butanedioic acid Chemical compound CCCCCCCCCCCCCC(C(O)=O)(C(C(O)=O)S(O)(=O)=O)CCCCCCCCCCCCC YZYZMGGVCYIIIU-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 125000005199 aryl carbonyloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 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
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 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 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229940093635 tributyl phosphate Drugs 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002351 wastewater Substances 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
-
- 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
- C22B3/40—Mixtures
- C22B3/406—Mixtures at least one compound thereof being a heterocyclic compound
-
- 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
- C22B15/0084—Treating 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
- 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
- C22B3/36—Heterocyclic compounds
- C22B3/362—Heterocyclic compounds of a single type
-
- 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)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A solvent extraction composition comprises a sulphonic acid and a solvent extractant of formula (1): <EMI ID=1.1 HE=34 WI=25 LX=867 LY=833 TI=CF> <PC>wherein ```R<1> is an aryl group optionally substituted with one or more groups selected from ```C1-12 alkyl or halo; ```R<2> is C1-12 alkyl group or a phenyl optionally substituted with one or more groups ```selected from C1-12 alkyl or halo; ```R<3> is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts or complexes thereof. It may also comprise a water immiscible organic solvent (the "preferred composition"). Such compositions may be used to in the solvent extraction of metals, such as cobalt, nickel, manganese, zinc and especially copper. The rate of metal transfer in the extraction stage is increased by the presence of the sulphonic acid. Extraction of a metal dissolved in an acidic (eg aqueous) solution is achieved by contacting the latter with the "preferred composition", whereby at least a fraction of the metal is extracted into the organic solution. The metal, optionally in the presence of one or more other metals, can be stripped from such an organic solution by contacting the latter with a medium capable of changing the oxidation state of the metal, eg a reducing medium, eg sulphur dioxide, hydrogen sulphide, zinc, aluminium, cadmium, manganese, magnesium, a zinc/acid mixture or a copper/acid mixture.
Description
- SMC 60597 2402388
PROCESS
The present invention concerns processes using 4-acyl-(3H)-pyrazol-3-ones for the solvent extraction of metals, particularly copper, from aqueous solutions, especially acidic solutions obtained by leaching ores.
Recently, in GB the use of 4-(alpha branched)acyl-(3H)-pyrazol-3-ones, and compositions thereof, in processes for the solvent extraction of metal, particularly copper, is described.
In certain applications, it can be desirable to alter the kinetics of the metal extraction process, particularly to increase the rate of metal transfer in the extraction stages of the process. Surprisingly, it has been found that compositions comprising lo sulphonic acid kinetics boosters and 4-(alpha branched)acyl-(3H)-pyrazol-3-ones show advantage in metal extraction processes.
According to a first aspect of the present invention, there is provided a solvent extraction composition comprising a sulphonic acid and a solvent extractant of formula (1) Rev Nit-OH R' Formula (1) wherein R' is an aryl group optionally substituted with one or more groups selected from C.-.2 alkyl or halo; R2 iS C, ,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or 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 4-(alpha branched) acyl-(3H)-pyrazol-3-ones and metals, particularly copper. An example of one tautomeric form of the compound of formula (1) is the tautomeric compound of formula (2): Rod
NAN O R'
Formula (2) À SMC 60597 : . - . wherein R', R2 and R3 are as defined above for the compound of Formula (1).
Aryl groups which may be represented by R' may contain 1 ring or 2 or more fused rings. Aryl groups include aromatic and heteroaromatic groups. When the aryl group comprises fused rings, the fused rings may include cycloalkyl, aryl or heterocyclic rings. Examples of aryl groups include optionally substituted phenyl, naphthyl, thienyl and pyridyl groups.
Preferably, R' is a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo.
Phenyl groups optionally substituted with one or more groups selected from C, ,2 To alkyl or halo which may be represented by R' or R2 include those of formula: R41_R8
R FIR R6
wherein R4 to RB each independently represent H. halo, or a C, ,2 alkyl group.
When any of R4 to R8 are halo, preferably the halo is Cl or F. When any of R4 to Re are a C, ,2 alkyl group, the C, ,2 alkyl group can be linear or branched, and preferably is methyl, ethyl or isopropyl.
Preferably only Re represents a halo group or a C,,2 alkyl group, with R4, R5, R7 and R8 representing H. When any of R' or R2 is an optionally substituted phenyl group, it is most preferred zo that R4 to RB are all hydrogen.
A preferred 4-(alpha branched)acyl-(3H)-pyrazol-3-one is one in which R' is a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo, preferably R' is an unsubstituted phenyl group; R2 is C,-,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo, preferably R2 is a methyl group; and R3 is an alpha branched alkyl group containing at least eight carbon atoms, preferably a tertiary alpha branched alkyl with at least eight carbon atoms, most preferably a secondary alpha branched alkyl with at least eleven carbon atoms.
Highly preferred 4-(alpha branched)acyl-(3H)-pyrazol-3-ones where R3 is a secondary alpha branched alkyl are 2-Phenyl-5-methyl-4-(2-hexyidecan-1oyl)-3 pyrazolone and 2-Phenyl-5-methyl-4-(2-butyloctan-1-oyl)-3pyrazolone.
Highly preferred are 4-(alpha branched)acyl-(3H)-pyrazol-3-ones wherein R3 is an isomeric mixture of tertiary alpha branched alkyl groups. The isomeric mixture of tertiary alpha branched alkyl groups is preferably derived from a Versatic acid. Versatic acids are isomeric mixtures of acids with a fixed number of carbons. Preferred Versatic acids are C10 and C13 Versatic acids which result in 4-(alpha branched)acyl-(3H)pyrazol-3-ones where R3 is a C9 or C12 alkyl group. Preferred 4-(alpha branched)acyl-(3H)-pyrazol-3 c: ad; À. '' I: - SMC 60597.. .: . : ', : : I. :. c. 'a' . . . ones are those where R3 is an isomeric mixture of tertiary alpha branched alky groups comprising 9 or more carbon atoms of formula: CH3 R3 = R9 R' where R9 and R' are independently linear or branched alkyl groups. The isomeric variation results from variations in the number of carbons atoms in the Ra and R' groups.
Sulphonic acids which are suitable for use in compositions of the present invention typically are soluble in the solvents used in metal extraction and show reduced solubility in aqueous acid solution.
Sulphonic acids which are suitable for use in compositions of the present o invention, generally are organic sulphonic acids, typically optionally substituted hydrocarbyl sulphonic acids.
Preferred are optionally substituted hydrocarbyl sulphonic acids of Formula (3): R"SO3H (3) wherein: R" is an optionally substituted hydrocarbyl group.
Optionally substituted hydrocarbyl groups which may be represented by R" preferably comprise optionally substituted alkyl and aryl groups including combinations of o these, such as optionally substituted aralkyl and alkaryl groups.
Optionally substituted alkyl groups which may be represented by R" include groups which contain a total number of alkyl carbons of from 7 to 50, especially from 8 to carbon atoms. A preferred optionally substituted alkyl sulphonic acid is one in which R" is alkyl, preferably containing more than 8, and especially more than 10, and more preferably more than 15 saturated aliphatic carbon atoms.
Optionally substituted aryl groups which may be represented by R" include optionally substituted phenyl groups and naphthyl groups. When R" is an aryl group, it is preferably a substituted naphthyl group.
When the optionally substituted hydrocarbyl sulphonic acid is an optionally so substituted naphthyl sulphonic acid, the optionally substituted naphthyl sulphonic acid is preferably a compound of formula (4): SO3H R12=R13 (4) wherein: 3 5 R'2 and R'3 are each independently an optionally substituted alkyl group.
8; 8 8 e t t - SMC60597: C't tl88 ''t '8 r 8 t 8 À t C 8 8t 8 8 8 8 It should be understood that as drawn, each ring of compound of formula (4) may independently be substituted with one or more groups represented by R'2 and R'3 respectively.
Optionally substituted alkyl groups which may be represented by R'2 and R'3 include groups which contain a total number of alkyl carbons of from 5 to 30, especially from 7 to 20 carbon atoms.
R'2 and R'3 may be the same or different. Preferably R'2 and R'3 are the same.
Preferably, R'2 and R'3 are unsubstituted alkyl groups. Most preferably C9 unsubstituted alkyl groups.
o Examples of optionally substituted naphthyl sulphonic acids include dinonyinaphthalenesulphonic acids.
Optional substituents, which may substitute the hydrocarbyl group of R", include halogen, nitro, cyano, hydrocarbyl, such as C, 20-alkyl, especially C, ,0-alkyl; hydrocarbyloxy, such as C,20-alkoxy, especially C, ,0-alkoxy; hydrocarbyloxycarbonyl, :5 such as C, 20-alkoxycarbonyl, especially C, ,0-alkoxycarbonyl; acyl, such as C,20-alkylcarbonyl and arylcarbonyl, especially C, ,0- alkylcarbonyl and phenylcarbonyl; and acyloxy, such as C, 20- alkylcarbonyloxy and arylcarbonyloxy, especially C, ,0-alkylcarbonyloxy and phenylcarbonyloxy. There may be more than one substituent in which case the substituents may be the same or different.
o The compositions of the present invention comprising optionally substituted hydrocarbyl sulphonic acids are advantageous in that they show increased extraction kinetics. However, with certain highly preferred compositions the increase in kinetics can also be achieved while ameliorating iron transfer.
According to a second aspect of the present invention there is provided a solvent extraction composition comprising a sulphonic acid of formula (5) : Rt3oJ5O3H 14 (CR15R15
R o (5)
wherein: R'3 and R'4 each independently is an optionally substituted alkyl group; so R'5 and R'e each independently is hydrogen or an optionally substituted alkyl group; and X is an integer, and a solvent extractant of formula (1): SMC 60597, , I', , R3 Rj__)Co 1IROH Formula (1) wherein R' is an aryl group optionally substituted with one or more groups selected from C, ,2 alkyl or halo; R2 is C, ,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
lo Preferences for the solvent extractant of formula (1) are described as herein before in connection with the first aspect the present invention.
R'3 and R'4 may be the same or different. Preferably, R'3 and R'4 are the same.
Optionally substituted alkyl groups which may be represented by R'3 and R'4 include groups which contain a total number of alkyl carbons of from 5 to 40, especially :5 from 7 to 30 carbon atoms. Examples of optionally substituted alkyl groups which may be represented by R'3 and R'4 include amyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl and nonadecyl.
Preferably, R'3 and R'4 are selected to be optionally substituted alkyl groups each containing eight or more alkyl carbons, for example octyl, nonyl, decyl, dodecyl, tridecyl o and nonadecyl groups. More preferably, R'3 and R'4 are selected to be tridecyl groups.
Optionally substituted alkyl groups which may be represented by R'5 and R'6 include groups which contain a total number of alkyl carbons of from 1 to 20.
R'5 and R'6 may be the same or different. Preferably, R'5 and R'e are the same.
More preferably R'5 and R'6 are both hydrogen.
z X is preferably 1, 2 or 3. Most preferably, X is 1.
The compositions of the present invention have been found to be most suited to use in solvent extraction systems where the solvent used has a low aromatic hydrocarbon content.
According to a third aspect of the present invention there is provided a solvent extraction composition comprising a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1) À Àe Àe À À.
SMC 60597. À . . , À . À . À À À À À À R;_)=0 NNoH R' Formula (1) wherein R' is an aryl group optionally substituted with one or more groups selected from C, ,2 alkyl or halo; R2 is C,-,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
Jo Preferences for the solvent extractant of formula (1) and the sulphonic acid are described as herein before in connection with the first and second aspects the present invention.
The composition may comprise one or more different 4-(alpha branched)acyl (3H)-pyrazol-3-ones, especially where the component 4-(alpha branched) acyl-(3H) :s pyrazol-3-ones are isomeric. Such isomeric mixtures may have better solubility in organic solvents than a single 4-acyl-(3H)-pyrazol-3-one and are preferred.
The 4-(alpha branched)acyl-(3H)-pyrazol-3-one 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 40 % w/w. Often, the 4-(alpha branched)acyl(3H)-pyrazol-3-one comprises at o least 1% by weight, commonly at least 2. 5% by weight and usually at least 5% by weight of composition, and preferably comprises from 7.5 to 20%, such as about 10%, by weight of the composition.
The composition may comprise one or more different sulphonic acids. The sulphonic acids are often present in an amount of up to 2% by weight based on the total z weight of 4-(alpha branched)acyl-(3H)-pyrazol-3-one present, commonly no more than 1.5%, and usually no more than 1% by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazol-3-one present. Often, the sulphonic acids comprise at least 0.01% by weight, commonly at least 0.05% by weight and usually at least 0. 1% by weight based on the total weight of 4-(alpha branched)acyl-(3H)- pyrazol-3-one present, and o preferably comprises from 0.05 to 1% such as about 0.2% by weight based on the total weight of 4-(alpha branched)acyl(3H)-pyrazol-3-one present Organic solvents which may be present in the composition 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. Preferably the organic solvent has a low aromatic hydrocarbon content.
SMC 60597 À . ... À À . À . . .. ....
À À À Preferred organic solvents are hydrocarbon solvents which include aliphatic, alicyclic and aromatic hydrocarbons and mixtures thereof as well as chlorinated hydrocarbons such as trichloroethylene, perchloroethylene, trichloroethane and chloroform.
Highly preferred organic solvents having a low aromatics content include solvents and solvent mixtures where the amount of aromatic hydrocarbons present in the organic solvent is less than 30%, usually around 23% or less, often less than 5%, and frequently less than 1 %.
Examples of suitable hydrocarbon solvents include ESCAID 110, ESCAID 115, lo ESCAID 120, ESCAID 200, and ESCAID 300 commercially available from Exxon (ESCAID is a trade mark), SHELLSOL D70 and D80 300 commercially available from Shell (SHELLSOL is a trade mark), and CONOCO 170 commercially available from Conoco (CONOCO is a trade mark). Suitable solvents are hydrocarbon solvents include high flash point solvents and solvents with a high aromatic content such as SOLVESSO s 150 commercially available from Exxon (SOLVESSO is a trade mark).
More preferred are solvents with a low aromatic content. Certain suitable solvents with a low aromatic content, have aromatic contents of <1 % w/w, for example, hydrocarbon solvents such as ESCAID 110 commercially available from Exxon (ESCAID is a trade mark), and ORFOM SX 10 and ORFOM SX11 commercially available from Phillips Petroleum (ORFOM 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 with a total aromatic content of 23% commercially available from Exxon (ESCAID is a trade mark), or ORFOM SX7, commercially available from Phillips Petroleum (ORFOM is a z trade mark).
In many embodiments, the composition comprises at least 30%, often at least 45% by weight, preferably from 50 to 95% w/w of water-immiscible hydrocarbon solvent.
Advantageously, it may be preferred to make and supply the composition in the form of a concentrate. The concentrate may then be diluted by the addition of organic so solvents as described herein above to produce compositions in the ranges as described herein above. Where the concentrate contains a solvent, it is preferred that the same solvent is used to dilute the concentrate to the tin use" concentration range. In many embodiments, the concentrate composition comprises up to 30%, often up to 20% by weight, preferably up to 10% w/w of water-immiscible hydrocarbon solvent. Often the concentrate composition comprises greater than 5% w/w of water-immiscible hydrocarbon solvent. The viscosity of the acylpyrazolones of the present invention means that concentrates do not display appreciably higher viscosity than extractant compositions at fin use" concentrations. In certain high strength concentrates it may be necessary to employ a higher than normal aromatic hydrocarbon content. In such cases where a high À eve Àe À ee.
SMC 60597. . . . À .. . À À À e e À À À À À À aromatic hydrocarbon containing solvent is used in the concentrate, solvent of very low aromatic hydrocarbon content may be used to dilute the concentrate to the "in use" concentration range.
If desired, compounds or mixtures of compounds selected from the group consisting of alcohols, esters, ethers, polyethers, carbonates, ketones, nitrites, amides, carbamates, sulphoxides, acids of sulphur and phosphorous compounds, for example sulphonic acids, and salts of amines and quaternary ammonium compounds may also be employed as additional modifiers or kinetics boosters in the composition of the invention.
Particularly preferred are mixtures comprising a first compound selected from the group To consisting of alcohols, esters, ethers, polyethers, carbonates, ketones, nitriles, amides, carbamates, sulphoxides, acids of sulphur and phosphorous compounds, for example sulphonic acids, 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 esters having from 7 to 30 carbon atoms, and tributylphosphate.
s According to a fourth aspect of the present invention, there is provided a process for the extraction of a metal from solution in which an acidic solution containing a dissolved metal is contacted with a solvent extraction composition comprising a water immiscible organic solvent and a solvent extractant, whereby at least a fraction of the metal is extracted into the organic solution, characterized in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1): Rat Nit-OH Formula (1) wherein R' is an aryl group optionally substituted with one or more groups selected from C.-.2 alkyl or halo; R2 is C,,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; o R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
Metals that may be extracted in the process according to the third aspect of the present invention include copper, cobalt, nickel, manganese and zinc, most preferably copper.
as The extractant of formula (1), the sulphonic acid and the water immiscible organic solvent are as herein described before.
À eve e. tee SAC 60597 a À À À À À . . Àe e The aqueous acidic solution from which metals are extracted by the process of the; third aspect of the present invention often has a pH in the range of from -1 to 7, preferably from O to 5, and most preferably from 0.25 to 3.5. Preferably, when the metal to be extracted is copper pH values of less than 3 chosen so that the copper is extracted essentially free of iron, cobalt or nickel. The solution can be derived from the leaching of 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 acidic solution will vary widely depending for example on the source of the solution. Where the solution is To derived from the leaching of ores, the metal concentration is often up to 75g/l and most often from 1 to 4Og/l. Where the solution is a waste stream, the metal concentrations can vary from 0.5 to 2g/l for a waste water stream, to somewhat higher for those from other waste streams, for example Printed Circuit Board waste streams, and can be up to 1 5Og/l, usually from 75 to 1 3Og/l.
:s Preferred solvent extraction compositions are those where the organic solvent solutions may contain the acyl pyrazolone in an amount approaching 100% ligand, but typically the acyl pyrazolone will be employed at about 10 to 40% by weight. Highly preferred solvent extraction compositions are those comprising an organic solvent with a total aromatic content of around 23% or less, one or more acyl pyrazolones selected from o 2-Phenyl-5-methyl-4-(2-hexyidecan-1 -oyl)-3- pyrazolone or 2-Phenyl-5-methyl-4-(2 butyloctan-1-oyl)-3-pyrazolone in a total amount of between 5 to 40% by weight and one or more sulphonic acids selected from dioctylsulphosuccinate or ditridecylsulphosuccinate in a total amount of between 0.01 to 2% by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazol-3-one present.
as The process of the fourth aspect of the present invention can be carried out by contacting the solvent extractant composition with the aqueous acidic solution containing a dissolved metal. Ambient or elevated temperatures, such as up to 75 C can be employed if desired. Often a temperature in the range of from 5 to 60 C, and preferably from 15 to 40 C, is employed. The aqueous solution and the solvent extractant are usually agitated together to maximise the interracial areas between the two solutions.
The volume ratio of solvent extractant to aqueous solution are commonly in the range of I 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 maintained by recycle of one of the streams.
as After contact with the aqueous acidic solution, the metal can be recovered from the solvent extractant by contact with an aqueous acidic strip solution.
The aqueous strip solution employed in the process according to the third aspect of the present invention is usually acidic, commonly having a pH of 2 or less, and I preferably a pH of 1 or less, for example, a pH in the range of from -1 to 0.5. The strip e eee as ee SMC 60597 À e À À e e À À e e À e e see e À 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 20Og/l and preferably from 150 to 1 8Og/l are employed.
When the extracted metal is copper, preferred strip solutions comprise stripped or spent electrolyte from a copper electro-winning cell, typically comprising up to 8Og/l copper, often greater than 2Og/l copper and preferably from 30 to 7Og/l copper, and up to 22Og/l sulphuric acid, often greater than 12Og/l sulphuric acid, and preferably from 150 to 18Og/l sulphuric acid.
The volume ratio of organic solution to aqueous strip solution in the process of the To fourth aspect of the present invention is commonly selected to be such so as to achieve transfer, per litre of strip solution, of up to 5Og/l of metal, especially copper into the strip solution from the organic solution. In many industrial copper electrowinning processes transfer is often from 1Og/l to 35g/1, and preferably from 15 to 2Og/l of copper per litre of strip solution is transferred from the organic solution. Volume ratios of organic solution to :s aqueous solution of from 1:2 to 15:1 and preferably from 1:1 to 10:1, especially less than 6:1 are commonly employed.
Both the separation and stripping process can be carried out by a conventional batch extraction technique or column contactors or by a continuous mixer settler technique. The latter technique is generally preferred as it recycles the stripped organic go phase in a continuous manner, thus allowing the one volume of organic reagent to be repeatedly used for metal recovery.
A preferred embodiment of the fourth aspect of the present invention comprises a process for the extraction of a metal from aqueous acidic solution in which: in step 1, the solvent extraction composition comprising an extractant of formula (1) is first contacted with the aqueous acidic solution containing metal, in step 2, separating the solvent extraction composition containing metal- solvent extractant complex from the aqueous acidic solution; in step 3, contacting the solvent extraction composition containing metal-solvent extractant complex with an aqueous acidic strip solution to effect the stripping of the metal 3 o from the water immiscible phase; in step 4, separating the metaldepleted solvent extraction composition from the loaded aqueous strip solution.
Where certain metals are present and are solvent extracted, it may be desirable that said metals are stripped by first changing the oxidation state of the metal in the metal solvent extractant complex.
According to a fifth aspect of the present invention, there is provided a process for the stripping of a metal from an organic solution in which a solvent extractant composition containing a complexed metal is contacted with a medium capable of changing the oxidation state of the metal, whereby at least a fraction of the metal is released from the À ace.. see SMC 60597 À 'e e À À e e ee e À À. ee e e organic solution, characterized in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1): R3 R:co Nt3-oH R' Formula (1) wherein R' is an aryl group optionally substituted with one or more groups selected from C,-,2 alkyl or halo; To R2 is C, ,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
In a further aspect of the present invention, there is provided a process for the stripping of a metal in the presence of one or more other metals from an organic solution in which a solvent extractant composition containing a complexed first metal and a complexed second metal is contacted with a medium capable of changing the oxidation state of the second metal, whereby at least a fraction of the second metal is released from the organic solution, characterized in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1): R3 jOH Formula (1) 2 5 wherein R' is an aryl group optionally substituted with one or more groups selected from C.-,2 alkyl or halo; R2 is C, ,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; o R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
The medium capable of changing the oxidation state of the metal may be an oxidising or a reducing medium. Preferably, the medium is a reducing medium.
À . . À . . . . SMC 60597 À. . . '. À.
. . . ..
À À À The reducing medium is typically selected according to the reduction potential which is matched to the complexed metal.
When the medium is a reducing medium, the complexed metal is preferably iron in oxidation state lilt Reducing mediums include metals and alloys of metals which are capable of reducing cations of the metal to a lower oxidation state, sulphur dioxide, hydrogen sulphide.
When metals or alloys of metals are employed as a reducing medium, preferably these metals or alloys of metals are used in the presence of an acid.
Preferred reducing mediums include zinc, aluminium, cadmium, manganese, magnesium, a zinc/acid mixture and a copper/acid mixture.
The invention is further illustrated, but not limited, by the following examples.
Examples
Preparation of 2-phenyl 4-(2-hexyidecan-1-oyl)-5-methyl -(3H)-pyrazol-3one A mixture of 2-phenyl-5-methyl-(3H)-pyrazol-3-one (1649, 1 M) and dioxane (700ml) were heated to 60 C until complete solution obtained. Calcium hydroxide (1489, 2M) was added and mixture stirred for 30 minutes, 2-hexyidecanoyl chloride (274.59, 1 M) added drop wise over 30 minutes. The temperature is raised to 95-100 C and held at this temperature, with stirring, overnight. Cooled to RT and reaction mixture drowned out into 2N hydrochloric acid solution (31itres). The brown oil was extracted into hexane and washed with methanol/water, the organic phase was separated offand dried over magnesium sulphate and solvent removed under reduced pressure. Yield 85% (strength 91.4%, calculated by copper uptake). The product can be further purified by high vacuum distillation.
Mass Spec:Molwt 412, found 411 (M-H)-, 413(M-H)+.
H'NMR (CDCI3, 300Hz) 60.85 (triplet, 2xCH3), 61.25 (multiplet, alkyl 20H), 81.50 (multiplet, CH2), 61.80 (multiplet, CH2), 82.50 (singlet, CH3), 62.95 (multiplet, CH), 87.30 (triplet, aryl H), 67.50 (triplet, aryl 2H), 57.90 (doublet, aryl 2H).
Preparation of 2-phenyl 4-(2-butyloctan-1-oyl)-5-methyl 3H)-pyrazol-3-one A mixture of 2-phenyl-5-methyl-(3H)-pyrazol-3-one (829, 0.5M) and dioxane as (400ml) were heated to 60 C until complete solution obtained. Calcium hydroxide (749, 1M) was added and mixture stirred for 30 minutes, 2-buyloctanoyl chloride (1099, 0.5M) added drop wise over 30 minutes. The temperature is raised to 95-100 C and held at this temperature, with stirring, ovemight. Cooled to RT and reaction mixture drowned out into 2N hydrochloric acid solution (1.51itres). The brown oil was extracted into hexane and À e. c À. À c SMC 60597 À À e c C À C À C À C À C C washed with water, the organic phase was separated off and dried over magnesium sulphate and solvent removed under reduced pressure. Product high vacuum distilled to yield a straw coloured oil. Wt 1169, Strength 96.4% (by copper uptake), Yield 56%.
Mass Spec: Mol wt 356, found 355 (M-H)-, 357 (M-H)H H'NMR (CDCI3, 300Hz) 80.80 (triplet, 2xCH3), 61.30 (multiplet, alkyl 11 H), 81.50 (multiplet, CH2), 61.80 (multiplet, CH2), 62.45 (singlet, CH3), 62.90 (multiplet, CH), 87.30 - 7.9(multiplets,aryl 5H), 612 -14 (broad singlet, OH).
To An extraction kinetics test was carried out to measure the time taken to achieve equilibrium distribution of copper under standard stirring conditions.
Reagents: Organic extractant solution (A): Acyl pyrazolone (0.2M) in Orfom SX7 (+ booster) Aqueous feedstock (B): Mixed metal solution containing 3 go copper and 3qL iron(l11) at pH2.0 Method: Transfer 400 ml of the sample solution (A) to the vessel and allow to equilibrate to the 2 o water bath temperature (25 i 1 C).
Separately equilibrate 400 ml of aqueous feedstock (B) to the water bath temperature.
When both solutions are at 25 C start the stirrer, pre-set to give 1270 rpm when stirring an aqueous/organic mixture, and add the aqueous feedstock solution to the vessel rapidly via a wide neck funnel, starting a stop clock halfway through the 2 5 addition.
After 29 seconds, transfer about 20 ml of the mixture into a separating funnel. This should take about 2 seconds and gives a sample representative of the condition after seconds of stirring. As the sample disengages in the separating funnel, run the aqueous layer off to prevent further copper transfer. Identify the remaining organic 3 o phase sample Org.0.5.
Similarly, draw another sample off after 1 min and identify this as Org.1.
Continue stirring for a total of 15 minutes taking samples at regular intervals (2,3,4,5,10,15 mine).
Separate the phases and analyse copper extracted into the organic phase Calculate the % copper extracted at the various time intervals using the following formula: % Cu extracted. (0.5 min) = Cu in Org. at t=0.5 X 100 Cu in Org. at equilibrium À: ee: .eÀe À: SMC 60597 À . . . .À.
. ......DTD: Àe À À À Comparitive Examples - Test to show the effects of additives without sulphonic acid groups on the extraction characteristics of acyl pyrazolones.
Contact Metal Extracted Time Acyl Acyl Pyrazolone Acyl Pyrazolone Acyl Pyrazolone (mine) Pyrazolone (0.2M) (0.2M) (0.2M) (0.2M) + + + 2-Hexyidecanoic 5-nonyl-2- 7-alkyl-8 acid (1g/l) hydroxyacetophenone hydroxyquinolene (19/1) (0.5g/l) Cu Cu Cu Cu Cu Cu Cu Cu (9/l) %ATE (9/l) %ATE (g/l) %ATE (gA) %ATE
O O O O O O O O O
0.25 0.1 3.6 0.1 3.6 0.1 3.6 0.2 7.1 0.5 0.2 7.1 0.2 7.1 0.2 7.1 0.3 10.7 1.0 0.3 10.7 0.3 10.7 0.4 14.3 0.5 17.9 2.0 0.6 21.4 0.6 21.4 0.7 25.0 0.8 28.6 3.0 0.8 28.6 0.8 28.6 0.9 32.1 1.0 35.7 5.0 1.2 42.9 1.2 1.2 1.3 46.4 1.4 50.0 15.0 2.1 75.0 2.1 75 2.2 78.6 30.0 2.6 92.9 2.5 89.3 2.7 96.4 2.7 96.4 60.0 2.8 100 2.8 100 2.8 100 2.8 100 * %ATE = Percent approach to equilibrium Example 1 - Test to show the effects sulphonic acids of formula (4) on extraction characteristics of acyl pyrazolones Contact Metal Extracted Time Acyl Pyrazolone (0.2M) Acyl Pyrazolone (0.2M) Acyl Pyrazolone (0.2M) (mine) + + DNNSA (0.25g/l) DNNSA (0.1g/l) Cu Cu Fe Cu Cu Fe Cu Cu Fe (9/l) %ATE ppm (9) %ATE ppm (9/l) %ATEppm
O O O O O O O O OO
0.25 0.1 3.6 1.8 66.7 1.5 51.7 0.5 0.2 7.1 2.3 85.2 2.1 72.4 1.0 0.3 10.7 2.6 96.3 2.7 93.1 ace À. ace SMC 60597 À . .. . À . c c À. À À À 2.0 0.6 21.4 1 - 1 2.7 100 1 - 1 2.8 96.6 3.0 0.8 28.6 3 2.7 100 70 2.9 100 47 5.0 1.2 42.9 2.7 100 2.9 100 15.0 2.1 75.0 2.7 100 2.9 100 30.0 2.6 92.9 2.7 100 2.9 100 60.0 2.8 100 2.7 100 2.9 100 Example 2 - Test to show the effects sulphonic acids of formula (5) on extraction characteristics of acyl pyrazolones.
Contact Metal Extracted Time Acyl Pyrazolone Acyl Pyrazolone (0.2M) Acyl Pyrazolone (0.2M) (mine) (0.2M) + + Dioctylsulphosuccinate Di(tridecyl)sulphosuccinate (0.2gA) (0.19/1) Cu Cu Cu Cu Cu Fe Cu Cu Fe (go) %ATE (9/l) (9/l) %ATE Ppm (9/l) %ATE ppm
O O O O O O O O O O
0.25 0.1 3.6 2.6 89.7 0.5 0.2 7.1 2.5 89.3 2.8 96.6 1.0 0.3 10.7 2.8 100 2.9 100 2.0 0.6 21.4 2.8 100 2.9 100 3.0 0.8 28.6 3 2.8 100 10 2.9 100 9 5.0 1.2 42.9 2.8 100 2.9 100 15.0 2.1 75.0 2.8 100 2.9 100 30.0 2.6 92.9 2.8 100 2.9 100 2.8 100 2.8 100 2.9 100
Conclusion
When conventional kinetics boosters are employed, there is little or no improvement in the time taken to achieve the 100% Cu ATE level. By comparison, when a sulphonic acid is employed, the time taken to achieve the 100% Cu ATE level is significantly reduced. Further, when the sulphonic acid is a compound of formula (5) kinetics are improved and also less iron transfer is achieved.
À .e Àse.
SMC 60597 ': ' : ::e e see e ee Reductive Strip Iron extracted by acyl pyrazolone extractants may be difficult to remove from the organic phase under normal strip conditions (ie contacting organic phase with strongly acidic aqueous solution).
The following examples show comparison test of various potential reductive strip mediums when applied to Fe(111) loaded acyl pyrazolones.
Example 3
Acyl pyrazolone (0.2M) in Orfom SX7 stirred with an aqueous solution containing Cu2+ (3g/l) and Fe3+ (3g/l) overnight. Iron extracted into organic phase analysed at 1278ppm. Portions of the iron loaded organic solution (10ml) were stirred for 1 hour with: (a) Copper powder (109) (b) Hydrochloric acid solution (1 Oml at 8M) s (c) Copper powder (109) and Hydrochloric acid solution (10ml at 8M) The organic phase was then analysed for Fe3+ content Ligand Ligand Ligand Ligand Ligand Ligand solution solution solution solution solution solution before after before after before after contact contact contact contact contact contact Fe ppm Fe ppm Fe ppm Fe ppm Fe ppm Fe ppm 1278 1227 1278 579 1278 1 Conclusion, Copper/Acid mixture is highly effective as a reductive medium for the stripping of iron.
Example 4
Acyl pyrazolone (0.2M) in Orfom SX7 stirred with an aqueous solution containing Cu2+ (3g/l) and Fe3+ (3g/l) for 1 hour. Iron extracted into organic phase analysed at 417ppm. Portions of the iron loaded organic solution (1 Oml) were stirred with: z (d) Sulphuric acid (10ml at 4M) ovemight (e) Activated zinc granules (109) and sulphuric acid (10 ml at 1 M) for 1 hour (n Water (1 Oml) and a stream of sulphur dioxide / hydrochloric acid gases for 5 minutes The organic phase was then analysed for Fe3+ content he.e. A. SMC 60597 À À : : : : : . : Stripping Conditions / Ret lacing Agent | (d) H29 O4 (40Og/l) (e) Zn / H2SO4 so2 ' HCI Ligand Ligand Ligand Ligand Ligand Ligand solution solution solution solution solution solution before after before after before after contact contact contact contact contact contact Fe ppm Fe ppm Fe ppm Fe ppm Fe ppm Fe ppm 417 410 417 2 417 3 Conclusion, the reductive mediums of Zn/H2SO4 and SO2/HCI are more effective in removing iron than the standard acid stripping conditions not employing reductive mediums.
Claims (11)
1. A solvent extraction composition comprising a sulphonic acid and a solvent extractant of formula (1): Rat Formula (1) wherein R' is an aryl group optionally substituted with one or more groups selected from C, ,2 alkyl or halo; ; R2 is C,,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
2. A solvent extraction composition comprising a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1): R;=0 1/ROH Formula (1) wherein R' is an aryl group optionally substituted with one or more groups selected from C.-.2 alkyl or halo; R2 is C, ,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
3. A solvent extraction composition according to Claim 1 or Claim 2 wherein the sulphonic acid is an optionally substituted naphthyl sulphonic acid of formula (4): c '.e ee À acc À SMC 60597 c. c a, e.
A C C C
CC C C C
19 1 SO3H R12= 13; (4) wherein R'2 and R'3 are each independently an optionally substituted alkyl group.
4. A solvent extraction composition according to Claim 1 or Claim 2 wherein the sulphonic acid is a compound of formula (5): R13oJ'SO3H 14 (CR R)X
O I
(5) ; wherein: To R'3 and R'4 each independently is an optionally substituted alkyl group; R'5 and R'6 each independently is hydrogen or an optionally substituted alkyl group, preferably with both R'5 and R'e being hydrogen; and X is an integer, preferably with X equals 1.
5. A process for the extraction of a metal from solution in which an acidic solution containing a dissolved metal is contacted with a solvent extraction composition comprising a water immiscible organic solvent and a solvent extractant, whereby at least a fraction of the metal is extracted into the organic solution, characterized in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1): R; SO Ni23-OH Formula (1) wherein R' is an aryl group optionally substituted with one or more groups selected from C'-2 alkyl or halo; R2 is C' '2 alkyl group or a phenyl optionally substituted with one or more groups selected from C' '2 alkyl or halo; o R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
e sea t. eca SMC 60597 c. e a a a a e c e era e a
6. A process for the stripping of a metal from an organic solution in which a solvent extractant composition containing a complexed metal is contacted with a medium capable of changing the oxidation state of the metal, whereby at least a fraction of the metal is released from the organic solution, characterized in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1): Rim \ R' Formula (1) 0 wherein R' is an aryl group optionally substituted with one or more groups selected from C.-2 alkyl or halo; R2 is C, ,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; :5 R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
7. A process for the stripping of a metal in the presence of one or more other metals from an organic solution in which a solvent extractant composition containing a complexed first metal and a complexed second metal is contacted with a medium capable of changing the oxidation state of the second metal, whereby at least a fraction of the second metal is released from the organic solution, characterized in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1): R3
R TO
N<3-oH R' Formula (1) wherein So R' is an aryl group optionally substituted with one or more groups selected from C.-.2 alkyl or halo; R2 is C,,2 alkyl group or a phenyl optionally substituted with one or more groups selected from C, ,2 alkyl or halo; À cee 's 81.
SMC 60597 e 8 C e R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
8. A process according to Claim 6 or 7 wherein the medium capable of changing the: oxidation state of the metal is a reducing medium.
9. A process according to Claim 8 wherein the reducing medium is sulphur dioxide, zinc, manganese, magnesium, a zinc/acid mixture and a copper/acid mixture.
To
10. A process according to any one of Claims 5 to 9 wherein the sulphonic acid is an optionally substituted naphthyl sulphonic acid of formula (4): SO3H R1213 (4) wherein R'2 and R'3 are each independently an optionally substituted alkyl group.
11. A process according to any one of Claims 5 to 9 wherein the sulphonic acid is a compound of formula (5): a R13 J:'SO3H R'4,0(CR R)X
O (5)
2 o wherein: R'3 and R'4 each independently is an optionally substituted alkyl group; R'5 and R'6 each independently is hydrogen or an optionally substituted alkyl group, preferably with both R'5 and R'5 being hydrogen; and X is an integer, preferably with X equals 1.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0313031A GB2402388A (en) | 2003-06-06 | 2003-06-06 | Composition for extraction of metals comprising a sulphonic acid and a 2-aryl-4-[alpha branched]alkanoyl-5-(aryl/alkyl)-(3H)-pyrazol-3-one derivative |
| PCT/GB2004/001855 WO2004108973A1 (en) | 2003-06-06 | 2004-04-29 | Solvent extraction composition comprising sulphonic acid with a 4-(alpha branched) acyl-(3h)-pyrazol-3-ones and processes of metal extraction |
| TW093114263A TW200508204A (en) | 2003-06-06 | 2004-05-20 | Process |
| PE2004000530A PE20050457A1 (en) | 2003-06-06 | 2004-05-25 | COMPOSITION OF EXTRACTION BY SOLVENT AND PROCESS TO EXTRACT WITH SUCH COMPOSITION A METAL FROM AN AQUEOUS ACID SOLUTION |
| ARP040101948A AR050475A1 (en) | 2003-06-06 | 2004-06-04 | SOLVENT EXTRACTION COMPOSITION, PROCESS FOR THE EXTRACTION OF A METAL AND PROCESS FOR THE DEPURATION OF THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0313031A GB2402388A (en) | 2003-06-06 | 2003-06-06 | Composition for extraction of metals comprising a sulphonic acid and a 2-aryl-4-[alpha branched]alkanoyl-5-(aryl/alkyl)-(3H)-pyrazol-3-one derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0313031D0 GB0313031D0 (en) | 2003-07-09 |
| GB2402388A true GB2402388A (en) | 2004-12-08 |
Family
ID=9959450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0313031A Withdrawn GB2402388A (en) | 2003-06-06 | 2003-06-06 | Composition for extraction of metals comprising a sulphonic acid and a 2-aryl-4-[alpha branched]alkanoyl-5-(aryl/alkyl)-(3H)-pyrazol-3-one derivative |
Country Status (5)
| Country | Link |
|---|---|
| AR (1) | AR050475A1 (en) |
| GB (1) | GB2402388A (en) |
| PE (1) | PE20050457A1 (en) |
| TW (1) | TW200508204A (en) |
| WO (1) | WO2004108973A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AP2382A (en) | 2005-09-14 | 2012-03-15 | Cytec Tech Corp | Phenoxypyrazole composition and process for the solvent extraction of metals. |
| CN105861827B (en) * | 2016-04-08 | 2017-09-12 | 中南大学 | A kind of soda acid coupling extraction system separated for many metal solution extractions and its application |
| CN106893874B (en) * | 2017-02-21 | 2018-01-05 | 中南大学 | A kind of method that nickel is reclaimed in the nickel-containing waste water from ammonia |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003054237A1 (en) * | 2001-12-20 | 2003-07-03 | Cytec Technology Corp. | 4-(alpha branched)acyl- (3h)-pyrazol-3-ones for use in the extraction of metals, especially copper, from solution |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166837A (en) * | 1978-03-31 | 1979-09-04 | King Industries, Inc. | Solvent-extraction process for recovery and separation of metal values |
| FR2544745B1 (en) * | 1983-04-19 | 1989-02-10 | Poudres & Explosifs Ste Nale | PROCESS FOR SELECTIVE EXTRACTION OF COPPER USING 4-ACYL (3H) PYRAZOL-3-ONES |
-
2003
- 2003-06-06 GB GB0313031A patent/GB2402388A/en not_active Withdrawn
-
2004
- 2004-04-29 WO PCT/GB2004/001855 patent/WO2004108973A1/en active Application Filing
- 2004-05-20 TW TW093114263A patent/TW200508204A/en unknown
- 2004-05-25 PE PE2004000530A patent/PE20050457A1/en not_active Application Discontinuation
- 2004-06-04 AR ARP040101948A patent/AR050475A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003054237A1 (en) * | 2001-12-20 | 2003-07-03 | Cytec Technology Corp. | 4-(alpha branched)acyl- (3h)-pyrazol-3-ones for use in the extraction of metals, especially copper, from solution |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200508204A (en) | 2005-03-01 |
| PE20050457A1 (en) | 2005-06-23 |
| WO2004108973A1 (en) | 2004-12-16 |
| GB0313031D0 (en) | 2003-07-09 |
| AR050475A1 (en) | 2006-11-01 |
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