WO1995015329A1 - Amides of acids of phosphorus for the extraction of metals - Google Patents
Amides of acids of phosphorus for the extraction of metals Download PDFInfo
- Publication number
- WO1995015329A1 WO1995015329A1 PCT/GB1994/002485 GB9402485W WO9515329A1 WO 1995015329 A1 WO1995015329 A1 WO 1995015329A1 GB 9402485 W GB9402485 W GB 9402485W WO 9515329 A1 WO9515329 A1 WO 9515329A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- optionally substituted
- group
- alkylphenoxy
- tert
- compound
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 76
- 239000002184 metal Substances 0.000 title claims abstract description 76
- 150000002739 metals Chemical class 0.000 title abstract description 18
- 238000000605 extraction Methods 0.000 title description 22
- 229910052698 phosphorus Inorganic materials 0.000 title description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title description 13
- 239000002253 acid Substances 0.000 title description 12
- 150000001408 amides Chemical class 0.000 title description 6
- 239000011574 phosphorus Substances 0.000 title description 5
- 150000007513 acids Chemical class 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 164
- -1 2,4-dimethylphenoxy Chemical group 0.000 claims abstract description 75
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 68
- 239000011701 zinc Substances 0.000 claims abstract description 68
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 125000005415 substituted alkoxy group Chemical group 0.000 claims abstract description 15
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 117
- 238000000034 method Methods 0.000 claims description 65
- 239000002904 solvent Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 22
- 239000012074 organic phase Substances 0.000 claims description 21
- 239000008346 aqueous phase Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 9
- 150000004696 coordination complex Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 96
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 54
- 238000006243 chemical reaction Methods 0.000 description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 29
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 27
- 238000012360 testing method Methods 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 21
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 19
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 19
- 239000012312 sodium hydride Substances 0.000 description 19
- 229910000104 sodium hydride Inorganic materials 0.000 description 19
- 229910001868 water Inorganic materials 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 125000001309 chloro group Chemical group Cl* 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 13
- 239000003607 modifier Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001298 alcohols Chemical class 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 12
- 125000004437 phosphorous atom Chemical group 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- 235000019341 magnesium sulphate Nutrition 0.000 description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 10
- 238000004448 titration Methods 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 9
- 239000012527 feed solution Substances 0.000 description 9
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 9
- 238000004679 31P NMR spectroscopy Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- JLYVRXJEQTZZBE-UHFFFAOYSA-N ctk1c6083 Chemical compound NP(N)(N)=S JLYVRXJEQTZZBE-UHFFFAOYSA-N 0.000 description 5
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LDXAOOOQBGRLFY-UHFFFAOYSA-N C1(=CC=CC=C1)N(P(O)=S)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)N(P(O)=S)C1=CC=CC=C1 LDXAOOOQBGRLFY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000005363 electrowinning Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-UHFFFAOYSA-N 0.000 description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- KYDJVKJYIMQCOP-UHFFFAOYSA-N chloro-di(pentan-2-yloxy)-sulfanylidene-$l^{5}-phosphane Chemical compound CCCC(C)OP(Cl)(=S)OC(C)CCC KYDJVKJYIMQCOP-UHFFFAOYSA-N 0.000 description 3
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 3
- SXIWNIQDOJKDGB-UHFFFAOYSA-N dichloro-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound ClP(Cl)(=S)C1=CC=CC=C1 SXIWNIQDOJKDGB-UHFFFAOYSA-N 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-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
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BATHVJUJMWQPMV-UHFFFAOYSA-M [Br-].CCCC(C)[Mg+] Chemical compound [Br-].CCCC(C)[Mg+] BATHVJUJMWQPMV-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical compound [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- CYXFIEPNEXBRTG-UHFFFAOYSA-N chloro-di(pentan-2-yl)phosphane Chemical compound CCCC(C)P(Cl)C(C)CCC CYXFIEPNEXBRTG-UHFFFAOYSA-N 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LGAJYTCRJPCZRJ-UHFFFAOYSA-N 2-bromopentane Chemical compound CCCC(C)Br LGAJYTCRJPCZRJ-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
- XLBCWXYKVPIVHH-UHFFFAOYSA-N 2-hydroxy-5-nonylbenzonitrile Chemical compound CCCCCCCCCC1=CC=C(O)C(C#N)=C1 XLBCWXYKVPIVHH-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- FIYXJPQDNPKZJJ-UHFFFAOYSA-N C1(=CC=CC=C1)[ClH]P(=S)[ClH]C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[ClH]P(=S)[ClH]C1=CC=CC=C1 FIYXJPQDNPKZJJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DTDWTFYDXWCOKB-UHFFFAOYSA-N [bis(2-tert-butylphenoxy)-lambda4-sulfanylidene]-chloro-dihydroxy-lambda5-phosphane Chemical compound CC(C)(C)C1=CC=CC=C1OS(=P(O)(O)Cl)OC2=CC=CC=C2C(C)(C)C DTDWTFYDXWCOKB-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000002252 acyl group Chemical group 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
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HPFKOFNYNQMWEF-UHFFFAOYSA-N chloro-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(Cl)=S HPFKOFNYNQMWEF-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000286 fullers earth Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- CFSSWEQYBLCBLH-UHFFFAOYSA-N iso-hexadecyl alcohol Natural products CC(C)CCCCCCCCCCCCCO CFSSWEQYBLCBLH-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 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
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 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
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
- C07F9/2495—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-P (X = O, S, Se; n = 0, 1)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/36—Amides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
- C07F9/4461—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4484—Compounds containing the structure C-P(=X)(N-acyl)-X, C-P(=X)(N-heteroatom)-X or C-P(=X)(N-CN)-X (X = O, S, Se)
-
- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/386—Polyphosphoric oxyacids, or derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- This invention relates to chemical compounds and more particularly to certain aryloxy-substituted amidobis (thiophosphoryl) compounds and to their use as extractants in a solvent extraction process for extracting metal values from aqueous solutions of metal salts.
- the metal which complexes with the metal and extracts it into the non-aqueous phase.
- the metal may then be recovered by a further extraction step in which the organic solution containing the metal complex is contacted with another aqueous phase containing an agent, usually a strong acid, capable of decomposing the complex so that the metal is extracted into the aqueous phase from which it can be recovered by suitable procedures such as electrowinning.
- an agent usually a strong acid
- Free hydrochloric acid is recovered by a further step in which the ferric chloride in hydrochloric acid is contacted with an organic solution containing tributyl phosphate from which the ferric chloride is stripped using water.
- the additional stages required to remove iron add to the complexity and cost of the procedure and hence are undesirable.
- amidobis(thiophosphoryl) group are excellent metal extractants, particularly for the separation of other metals from solutions containing iron.
- these amidobis(thiophosphoryl) compounds are highly effective in selectively extracting zinc from acidic aqueous solutions containing both zinc (II) and iron (III) ions.
- certain of the amido-bis (thiophosphoryl) compounds are strong extractants, that is that they extract zinc from aqueous solutions at pH values below 2 without requiring the addition of base to neutralise the protons liberated by the complexation reaction.
- the present invention provides a compound of the formula:
- R 1 is an optionally substituted 2-alkylphenoxy group
- each of R 2 , R 3 and R 4 is a group selected from optionally substituted 2-alkylphenoxy, optionally substituted phenyl, optionally substituted alkyl and optionally substituted alkoxy and at least one optionally substituted 2-alkylphenoxy group has a tertiary alkyl substituent except the compound wherein each of R 1 and R 2 is 2-isopropyl-4-tert-nonylphenoxy and each of R 3 and R 4 is phenyl and the compound wherein R 1 is 2-methyl-4-tert-nonylphenoxy, R 2 is 2,4-dimethylphenoxy and each of R 3 and R 4 is phenyl.
- R 1 -R 4 are as already defined. Whilst the invention is described herein with reference to compounds of Formula I, it is to be understood that it relates to said compounds in any of their possible tautomeric forms.
- 2-alkylphenoxy groups which may be present in the compounds of Formula I, there may be mentioned phenoxy groups wherein the alkyl substituent in the 2-position relative to the oxygen atom contains from 1 to 20, for example from 1 to 10, carbon atoms.
- Such alkyl groups may be primary alkyl groups having one or more carbon atoms, secondary alkyl groups having three or more carbon atoms or tertiary alkyl groups having four or more carbon atoms.
- the phenoxy residue may optionally carry one or more additional alkyl substituents, for example an alkyl substituent in the 4-position.
- the optionally substituted 2-alkylphenoxy group has a tertiary alkyl substituent
- the latter may be present in addition to the alkyl substituent in the 2-position and/or the alkyl substituent in the 2-position may itself be a tertiary alkyl group.
- optionally substituted 2-alkylphenoxy groups include 2-tert-butylphenoxy, 2-tert-butyl-4-methylphenoxy, 2-tert-butyl-5-methylphenoxy, 2,4-di-tert-butylphenoxy, 2, 4-di-tert-pentylphenoxy, 2-methyl-4-tert-nonylphenoxy, 2-tert-butyl-4-tert-nonylphenoxy, 4-octylphenoxy, 4-tert-dodecylphenoxy, 4-tert-dodecyl-2-methylphenoxy, 2-sec-butylphenoxy and the like.
- At least one 2-alkylphenoxy group is a 2-tert-alkylphenoxy group and preferably at least two 2-alkylphenoxy groups are 2-tert-alkylphenoxy groups.
- Preferred 2-tert-alkyl groups include 2-tert-butyl groups.
- Optionally substituted phenyl groups which may be represented by R 2 and/or R 3 and/or R 4 in the compounds of Formula I include alkyl substituted phenyl groups, for example o-tolyl, m-tolyl, p-tolyl and xylyl groups and mixtures of such groups.
- the preferred optionally substituted phenyl group is the unsubstituted phenyl group.
- alkyl and alkoxy groups which may be represented by R 2 and/or R 3 and/or R 4
- alkyl and alkoxy groups containing from 1 to 20, for example from 1 to 10, carbon atoms.
- the alkyl groups and the alkyl moieties of alkoxy groups may be primary alkyls having one or more carbon atoms, secondary alkyls containing three or more carbon atoms or tertiary alkyls containing four or more carbon atoms.
- substituents which may be present in
- R 1 is an optionally substituted 2-alkylphenoxy group
- R 2 , R 3 and R 4 is either an optionally substituted 2-alkylphenoxy group or an optionally
- substituted phenyl group and at least one optionally substituted 2-alkylphenoxy group has a tertiary alkyl substituent except the compound wherein each of R 1 and R 2 is 2-isopropyl-4-tert-nonylphenoxy and each of R 3 and R 4 is phenyl and the compound wherein R 1 is 2-methyl-4-tert-nonylphenoxy, R 2 is 2,4-dimethylphenoxy and each of R 3 and R 4 is phenyl.
- R 1 in this class of compounds is an optionally substituted 2-alkylphenoxy group, R 2 , R 3 and R 4 being phenyl groups, it is preferred that the phenoxy group is heavily substituted with aliphatic groups as in, for example, the 2-tert-butyl-4-tert-nonylphenoxy group to provide the extractant compound with good solubility in hydrocarbon solvents.
- At least one of R 2 , R 3 and R 4 is an optionally substituted 2-alkylphenoxy group so that the compound of Formula I contains at least two optionally substituted 2-alkylphenoxy groups and it is further preferred that at least two optionally substituted 2-alkylphenoxy groups have a tertiary alkyl substituent.
- substituted phenyl are strong metal extractants.
- each of R 1 and R 2 is 2-methyl-4-tert-nonylphenoxy and each of R 3 and R 4 is phenyl.
- R 1 and R 3 are optionally substituted 2-alkylphenoxy groups, R 2 and R 4 being optionally substituted 2-alkylphenoxy groups, R 2 and R 4 being optionally substituted 2-alkylphenoxy groups, R 2 and R 4 being optionally substituted 2-alkylphenoxy groups, R 2 and R 4 being optionally substituted 2-alkylphenoxy groups, R 2 and R 4 being optionally substituted 2-alkylphenoxy groups, R 2 and R 4 being optionally
- substituted phenyl include compounds in which the alkyl substituents in the 2-position are tertiary alkyl groups, for example the compound in which each of R 1 and R 3 is 2-tert-butyl-4-methvlphenoxy and each of R 2 and R 4 is phenyl.
- each of R 1 , R 2 and R 3 is an optionally substituted 2-alkylphenoxy group and R 4 is optionally substituted phenyl.
- at least one of the 2-alkylphenoxy groups is a 2-tert-alkylphenoxy group, the others preferably being 2-tert-alkyl and/or 2-sec-alkylphenoxy.
- preferred sec-alkyl groups having at least four carbon atoms. Examples of compounds containing one 2-tert-alkyl substituent and two 2-sec-alkyl substituents include the compound wherein each of R 1 and R 2 is 2-sec-butylphenoxy, R 3 is 2,4-di-tert-pentylphenoxy and R 4 is phenyl.
- Examples of compounds containing two 2-tert-alkyl substituents and one 2-sec-alkyl substituent include the compound wherein each of R 1 and R 3 is 2-tert-butylphenoxy, R 2 is 2-sec-butylphenoxy and R 4 is phenyl.
- each of R 1 , R 2 , R 3 and R 4 is an optionally substituted 2-alkylphenoxy group
- at least one is a 2-tert-alkylphenoxy group and more preferably two and especially three of the optionally substituted 2-alkylphenoxy groups are 2-tert-alkylphenoxy groups.
- Useful structures include those compounds in which R 1 and R 2 are 2-tert-alkylphenoxy groups especially when R 3 and R 4 are 2 -sec-alkylphenoxy groups.
- a second valuable class of compounds falling within the scope of Formula I comprises the compounds wherein R 1 is an optionally substituted 2-alkylphenoxy group, at least one of R 2 , R 3 and R 4 is an optionally substituted alkyl or optionally substituted alkoxy group, any remaining group or groups from R 2 , R 3 and R 4 being selected from optionally substituted 2-alkylphenoxy and optionally substituted phenyl and at least one optionally substituted 2-alkylphenoxy group has a tertiary alkyl substituent.
- R 1 is an optionally substituted 2-tert-alkylphenoxy group
- R 2 is an optionally substituted alkoxy group
- each of R 3 and R 4 independently, is an optionally substituted 2-alkylphenoxy group or an optionally substituted alkoxy group.
- At least one of R 3 and R 4 is a 2-tert-alkylphenoxy group.
- R 2 is an optionally substituted alkoxy group or an optionally substituted phenyl group and R 3 and R 4 are optionally substituted alkoxy groups which may be the same or different.
- R 2 is an optionally substituted 2-alkylphenoxy group or an optionally substituted phenyl group and R 3 and R 4 are optionally substituted alkyl groups which may be the same or different.
- a chloro compound of formula C or D may be reacted with an excess of ammonia to give a phosphoramide, E.
- the amide E may be reacted with a chloro compound C or D in the presence of a strong base.
- diarylchlorophosphine may be oxidised by reaction with thiophosphoryl chloride to give C.
- a Grignard reagent may be reacted with a dialkyl phosphite to give a dialkyl phosphine oxide which is converted into the acid chloride by reaction with phosphorus trichloride as described by Robert H Williams and Lyle A Hamilton, J.Am.Chem.Soc., 74, 5418, 1952.
- Useful available compounds of formula A or B include chlorodiphenylphosphine.
- R 1 -R 4 are aryloxy groups
- a wide range of dithiophosphoric acids for use in the reaction above may be prepared by reaction of the appropriate phenol either with phosphorus
- the present invention provides a process for extracting metal values from aqueous solutions of metal salts with an organic phase comprising a compound of the invention as hereinbefore defined.
- the organic phase employed in the extraction process typically contains a water-immiscible inert organic solvent, that is to say a water-immiscible organic liquid that is inert under the extraction conditions and is a good solvent for the extractant compound and the metal complex thereof.
- the extraction process may be incorporated into a wide variety of different procedures for the recovery of metals from their ores or from other metal-bearing sources. Details of these procedures will vary depending on the metal concerned and the nature and composition of the leach solution. An integrated process which is especially suitable for sulphate leach solutions can be carried out using operations well known to the skilled person.
- the extractive process comprises a sequence of stages in which the metal is extracted into an organic solution, stripped into an aqueous phase and recovered from the aqueous phase by any suitable means, for example by electrowinning.
- the extraction process may be applied to the extraction from aqueous solution of any metal capable of forming a stable complex with a compound of the invention in the organic phase.
- the process is especially suitable for the solvent extraction of zinc from aqueous solutions of zinc salts, especially solutions obtained by the acid leaching of zinc ores.
- examples, however, of other metals which can be extracted from acidic solutions having pH values of pH 2 and below are bismuth, cadmium, silver, mercury and copper but many other metals may also be extracted at higher pH values.
- the amount of extractant compound to be used will depend upon the concentration of metal salt in the aqueous solution and also on the plant design. It is preferred, however, to use from 5g to 400g of compound of the invention per dm 3 (litre) of organic solution. Higher concentrations may be used but tend to afford organic phases of too high viscosity for convenient handling. Lower concentrations can also be used but involve the use of unnecessarily large volumes of solvent.
- the extractant compound can be used together with an agent which modifies the behaviour thereof in the extraction process, for example an alkylphenol, alcohol or ester which may be used in an amount of from 10% to 200%, especially from 20% to 100% by weight of extractant compound.
- an agent which modifies the behaviour thereof in the extraction process for example an alkylphenol, alcohol or ester which may be used in an amount of from 10% to 200%, especially from 20% to 100% by weight of extractant compound.
- Such compounds weaken the extractant but facilitate the subsequent stripping of metal therefrom. In this way, a very strong extractant may be adjusted in strength to the requirements of different feed solutions and different stripping solutions.
- Alkylphenols which may be used as modifiers in conjunction with the extractant compounds of the invention 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-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 compounds of the invention 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.
- branched chain alcohols that may be made by condensation of short chain alcohols by the Guerbet process, such alcohols sometimes being referred to as
- 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.
- particularly efficient alcohol modifiers include highly branched isohexadecyl alcohol and iso-octadecyl alcohol, the latter being 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctanol.
- Esters which may be used as modifiers in conjunction with the extractant compounds of the invention 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.
- the esters are preferably highly branched.
- esters may contain other functional groups,
- esters include
- 'highly branched' as applied to the alcohols and esters means that the ratio of the number of methyl carbon atoms to non-methyl carbon atoms is higher than 1:5. Preferably, this ratio is higher than 1:3.
- mixtures of alkylphenols and/or alcohols and/or esters may be employed as modifiers.
- the aforementioned modifiers may be used in the preparation of extractant compositions containing one or more extractant compound of the invention and one or more modifier.
- extractants for zinc are soluble in the organic phase but with fast rates of extraction.
- Compounds found to be effective in this aspect are other known zinc extractants such as esters of phosphoric acid, (eg D2EHPA), and particularly surface active agents capable of transferring metal ions such as alkyl and aryl sulphonic acids having solubility in the organic phase.
- Stages (1) and (2) of the aforementioned process may conveniently be carried out using well known conventional solvent extraction techniques.
- the aqueous solution containing metal values is intimately contacted, in a single stage or in multiple stages but preferably continuously, with the organic phase (for example by agitating the two phases together in a suitable vessel) for a time sufficient to allow substantial extraction of the metal values from the aqueous solution, the two phases then being separated in any conventional manner.
- the extraction is usually carried out at ambient temperature although somewhat higher temperatures, for example up to 100°C but preferably not more than 50°C, may be used if operationally convenient.
- Organic solvents which may be used in 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.
- suitable solvents include aliphatic, alicyclic and aromatic hydrocarbons and mixtures of any of these as well as chlorinated hydrocarbons such as trichloroethylene, perchloroethylene, trichloroethane and chloroform.
- 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 AROMASOL H which consists essentially of a mixture of trimethylbenzenes and is commercially available from Imperial Chemical Industries PLC (AROMASOL is a trade mark) .
- hydrocarbon solvents of relatively low aromatic content such as kerosene, for example ESCAID 100 which is a petroleum distillate comprising 20% aromatics, 56.6% paraffins and 23.4% naphthenes commercially available from Exxon (ESCAID is a trade mark).
- the conditions under which the solvent extraction is performed are chosen to suit the metal or metals present in the aqueous solution. It is generally desirable that conditions are selected such that any other metals present do not form stable complex compounds with the extractant compound in order that substantially only the desired metal is extracted from the aqueous solution. Since formation of the complex may involve the liberation of acid, it may be necessary to add, for example, alkali during the process to maintain the pH within a desired range but it is generally preferred to avoid this, especially in a continuously-operated process. It is a particular advantage of the process of the invention that zinc can be extracted selectively even in the presence of iron.
- Stages (3) and (4) of the process may conveniently be carried out by intimately contacting the solution of metal complex in the organic solvent obtained in stage (2) with an aqueous solution of a mineral acid at a suitable temperature, the two phases then being separated in conventional manner.
- the operations are usually performed at ambient temperature although somewhat higher
- temperatures for example up to 100°C but preferably not more than 50°C, may be used if operationally convenient.
- the aqueous strip solution used in stage (3) preferably contains sulphuric acid, suitable strengths being from 100 to 250g of acid per dm 3 of solution.
- the recovered aqueous acid, containing residual metal salt may be re-used in stage (3) of the process.
- the extractant compound regenerated in stage (3) may be recycled for use in stage (1).
- Suitable relative volumes of organic to aqueous phases are those conventionally used in metal extraction processes and in the stripping stage will be typically not more than 10:1.
- the stripped organic layer, containing regenerated extractant compound and some residual metal, may be re-used in stage (1) of the process.
- the aqueous layer from stage (4), containing metal salt, may be treated in any conventional manner to obtain the metal.
- the extractant compounds of the invention are valuable in that, when subjected to Test 1, they are generally capable of providing an organic solution containing from 1500 to 4500 parts per million, often 3000 to 4500 parts per million and preferably 3600 to
- Examples 1-5 relating to compounds in which no 2-alkylphenoxy group contains a tertiary alkyl substituent, are included for the sake of comparison.
- Test 1 The General Method designated Test 1 of testing the product for its strength as an extractant for zinc, with the result which is ennumerated in Table 1, is also described.
- the chloro compound was isolated by diluting the mixture with diethyl ether (300cm 3 ); the ether solution was extracted with water (three 100 cm 3 portions) and the organic layer was separated, dried with magnesium sulphate, filtered and concentrated by evaporation of the ether under reduced pressure yielding O,O'-bis(2-isopropyl-5-methylphenyl) chlorothiophosphate which was an oil
- the oil was dissolved in hexane (100 cm 3 ) and the hexane solution was twice extracted with 100 cm 3 portions of a mixed solvent prepared by adding 5 parts by volume of water to 95 parts by volume of methanol. The hexane solution was then discarded. The methanolic solutions were combined and dilute sulphuric acid was added to reduce the pH to about 2.0. This solution was then extracted with hexane (two 100 cm 3 portions) and the hexane solutions were combined and dried (magnesium sulphate) and concentrated by
- a 0.20 molar solution of the compound to be tested in ESCAID 100 is shaken with an equal volume of a 0.1 molar aqueous solution of zinc sulphate containing sufficient sulphuric acid to give an initial pH value of 2.0.
- Samples of the dispersion are withdrawn periodically and the aqueous layer is separated and analysed for zinc by titration with EDTA according to the usual procedure, until successive samples give the same zinc value denoting that equilibrium has been reached.
- the amount of zinc which has passed into the organic solution expressed as a concentration in parts of zinc by weight per million parts of solution by volume (ppm) is calculated.
- the chloro compounds and amino compounds listed in Table 1 were prepared by the methods of Example 1, using as appropriate 2-sec-butylphenol, 2,4-dimethylphenol, 2-isopropyl-5-methylphenol or 2,6-dimethylphenol as starting materials. The chloro and amino compounds were then reacted together, also by the method of Example 1 to give the compounds of Formula 1 having the groups R 1 -R 4 listed. The strengths of these compounds as zinc extractants were examined by Test 1 with the results listed. The results show that the compounds of these Examples have strengths similar to the compound of Example 1.
- This Example demonstrates the preparation of a compound of Formula 1 in which differently substituted phenoxy groups are attached to the same phosphorus atom.
- phenylphosphonothioic dichloride Ph.PS.Cl 2 , obtainable from Jansen Chemical Company
- a solution of the sodium salt of 2-sec-butylphenol was then prepared from 90.0g of the phenol, sodium hydride (14.4g) and tetrahydrofuran (250 cm 3 ) and added to the reaction mixture, again maintaining the temperature at -40°C.
- the mixture was allowed to warm to room temperature.
- Hexane (250 cm 3 ) was added and the mixture was extracted with water (three 200cm 3 portions).
- the hexane solution was dried with magnesium sulphate and concentrated by evaporation of hexane under reduced pressure yielding an oil (231g) which is the chloro compound of Example 24.
- the product prepared in this way contained ⁇ 9% of the two isomers having identical phenoxy groups.
- the product was purified and isolated as follows: the reaction mixture was extracted twice with 300 cm 3 portions of a solution comprising methanol (540 cm 3 ) and water (60 cm 3 ). The methanolic solutions were combined, and extracted with hexane (200 cm 3 ), and the hexane extract was discarded. The methanol solution was acidified with concentrated hydrochloric acid (100cm 3 ) and water (100 cm 3 ) was added. The product was extracted into hexane (400 cm 3 ) and the hexane was washed with three 100 cm 3 portions of methanol/water made up as previously described.
- This Example describes the preparation of a compound of Formula 1 in which one phenyl group is attached to each phosphorus atom.
- the chloro compound listed in Table 1 was prepared by reacting 2-tert-butyl-4-methylphenol (1.0M, 164.3g) with sodium hydride (1.0 M, 24.0g) and then with phenylphosphonothioic dichloride (1.0.M, 211g) as described in Example 24. On this occasion, the reaction solution was not treated with ammonia but, instead, was concentrated by evaporation of the tetrahydrofuran under reduced pressure, and the concentrate was redissolved in ethyl acetate (400 cm 3 ) and the solution was extracted with water (three 100 cm 3
- this Example describes the preparation of diphenylphosphonothioic amide (Ph 2 PS.NH 2 ) and its use in preparation of a compound of Formula 1 in which two phenyl groups are attached to the same phosphorus atom.
- Propylene trimer (2.0M, 252g) and 2-methylphenol (2.0M, 216g) and an activated Fullers earth catalyst (FULLCAT 22B supplied by Laporte Industries, 5.4g) and phosphoric acid (4 drops) were stirred and heated at 80°C for 48 hours. The mixture was then allowed to cool, filtered and distilled, yielding 2-methyl-4-tert-nonylphenol (245g) as the fraction of b.p. 114-132°C under a pressure of 0.2-0.3mm of mercury.
- FULLCAT 22B activated Fullers earth catalyst
- Test 1 shows this compound to be a stronger extractant for zinc than the products of Example 25, teaching that stronger extractants are obtained when two phenyl groups are attached to the same phosphorus atom than when each phenyl group is attached to a different phosphorus atom.
- Example 26 The procedure of Example 26 was used to prepare 2-sec-butyl-4-tert-nonylphenol (b.p. 148-150°C at a pressure of 1.5mm of mercury) from 2-sec-butylphenol and propylene trimer. This compound was further reacted with phenylphosphonothoic dichloride using the procedure of Example 24 to give the chloro compound listed in Table 1 ( 31 P NMR in CDCl 3 , multiplet 82.6ppm downfield of phosphoric acid).
- An organic solution was prepared containing 0.5 moles per litre of the extractant of Example 24 in the hydrocarbon solvent Escaid 100.
- a simulated high concentration zinc feed solution was prepared that contained 20.1 g/l zinc, 12.5 g/l ferric iron, 0.47 g/l calcium, and 2.6 g/l magnesium in an aqueous sulphate medium at pH 1.8.
- the extractant In a solvent extraction process for the recovery of a metal, it is essential that the extractant is not only capable of extracting metal efficiently from the aqueous feed solution, but that the metal can be recovered subsequently from the metal loaded organic phase by a stripping operation.
- the stripping is carried out with an acidic aqueous solution such as a spent electrowinning electrolyte.
- an acidic aqueous solution such as a spent electrowinning electrolyte.
- Example 28 The phases were allowed to disengage, separated, the organic filtered and analysed for both zinc and iron.
- Example 28 A portion of the zinc loaded organic phase was then contacted with an aqueous strip solution as used in Example 28 in the ratio of 15 parts of organic to 7 parts of strip solution. Contacting was carried out by vigorous stirring for 2 hours at 50°C. After the phases had disengaged, the phases were separated, filtered, and analysed for zinc . The results for the compounds tested in this way are as follows:
- Solutions were prepared containing (A) 0.5 moles per litre of the extractant of Example 24 in the hydrocarbon solvent Escaid 100.
- one of the solutions (B) contained 50 g/litre (0.25 molar) of isotridecyl alcohol added as modifier.
- a third solution of the extractant (C) contained as modifier 72 g/l, being 0.25 moles per litre, of the ester 2,2,4-trimethyl-1,3-pentanediol diisobutyrate available commercially under the name KODAFLEX TXIB (Eastman Kodak).
- extractant (g/l) extractant (g/l) transferred (g/l)
- This Example demonstrates the preparation of a compound of Formula I in which two optionally substituted 2-tert-alkylphenoxy groups are attached to the same phosphorus atom and two optionally substituted alkyl groups are attached to the other phosphorus atom.
- the Example describes the preparation of bis-(2-pentyl)chlorothiophosphate, which is the chloro compound listed in Table 6, and the reaction of the chloro compound with O,O'-(bis-2-tert-butylphenoxy)thiophosphoramide, which is the amino compound listed in Table 6 :
- a solution of 2-pentylmagnesium bromide was prepared by adding 2-bromopentane (2554.74g, 16.93M) to magnesium turnings (422g, 17.6M) in diethyl ether over a period of 2M hours. The temperature of the reaction mixture was maintained at 38-40°C by external cooling. The diethyl ether solution of 2-pentylmagnesium bromide was then added to a solution of phosphorus trichloride (946g, 6.88M) in diethyl ether (946 cm 3 ) during 3 hours. Throughout the addition, the temperature of the reaction mixture was maintained at -20°C or lower by external cooling.
- reaction mixture was stirred at 0°C for 2 hours, over which time, a greyish solid resulted.
- Water (3000cm 3 ) was added to the reaction mixture over a period of 2 hours and the temperature was allowed to rise freely to 20°C.
- the diethyl ether solution was separated and washed with brine (1 ⁇ 2000cm 3 ) , then with brine/Na 2 Co 3 (15% wt Vol NaCl, 2% wt.vol. Na 2 CO 3 ; 5 ⁇ 3000cm 3 ) and again with brine (1 ⁇ 2000cm 3 ).
- the diethyl ether solution was then concentrated by evaporation under reduced pressure. Low boiling impurities were removed by heating the residue under reduced pressure (25 mmHg) at a temperature of 80°C for 30 minutes.
- the clear oil (541.2g) was taken as the product bis-(2-pentyl)chlorophosphine 31 P, n.m.r in CDCl 3 , singlet at 130.7 ppm.
- the amino compound, O,O'-bis(2-tert-butylphenoxy)thiophosphoramide was prepared from bis(2-tert-butylphenoxy)chlorothiophosphate by the method of Example 1, and O,O'-bis(2-tert-butylphenoxy)chlorothiophosphate was also prepare by the method of Example 1.
- the compound of Formula 1 was prepared by reacting bis(2-pentyl)chlorothiophosphate and O,O'-bis(2-tert-butylphenoxy)thiophosphoramide by the method of Example 1.
- the compound isolated was a brown oil (44.04g).
- the purity of the compound was estimated by titration as 89% of theoretical for M.W. of 580.6. 31 P n.m.r. in CDCl 3 , having two sets of multiplets centred at 41.80 ppm and 90.85 ppm.
- Example in Test 1 which is set out on Table 6, shows it to be a very strong extractant for zinc.
- This Example describes the preparation of compounds of Formula 1, wherein R 3 and R 4 are alkoxy groups and R 1 and R 2 are 2-alkylphenoxy groups.
- the Example describes the preparation of O,O'-(bis-2-ethylhexyl)chlorothiophosphate, its conversion to phosphoramide and the preparation of O,O'-(bis-2-tert-butylphenoxy)thiophosphoryl chloride.
- the oil residue was the product O,O'-(bis-2-tert-ethylhexyl)chlorothiophosphate (225.24g), 31 P n.m.r. in CDCl 3 singlet at 67.28 ppm.
- the chloro compound (lO0g) was dissolved in
- the amino compound (0.2M, 67.4g) was reacted with O,O'- (bis-2-tert-butylphenoxy)chlorothiophosphate, prepared as described in Example 10, (0.2M, 79.3g) and sodium hydride (0.46M, 11.06g) in tetrahydrofuran (500cm 3 ) and refluxed for 12 hrs. After purification and isolation as described in Example 1, the reaction product was obtained (90.3g), which was found by titration to be 89% pure. The purity of the sample was further improved to 93% by redissolving the product in hexane and washing the solution with a methanol/H 2 0 (90% Vol : 10% Vol) mixture 4-5 times.
- the compounds of Formula I, listed in Table 6, were prepared by the methods of Example 34 using, where appropriate, O,O'-(bis-1,3-dimethylbutoxy)phosphorodithioate, O,O'-(bis-ethoxy)phosphorodithioate, O,O'-(bis-n-propoxy)phosphorodithioate, O,O'-(bis-isopropoxy)phosphorodithioate and O,O'-(bis-2-tert-butylphenoxy)chlorothioate as the starting materials.
- the chloro and amino compounds were then reacted together, by the methods of Example 1 to give compounds of Formula 1.
- the compounds, together with their performance in Test 1 are set out in Table 6. The results show that the compounds of these Examples have strengths similar to the compound of Example 34.
- a suspension of sodium hydride (1.0M, 24g) in tetrahydrofuran (150cm 3 ) was added portionwise to a stirred solution of 2-tert-butylphenol (150g) in tetrahydrofuran (250cm 3 ) over a period of 2 hours, whilst the temperature was maintained below 30°C by external cooling.
- This solution was then added during 2 hours to a stirred solution of thiophosphoryl chloride (1.0M, 169.4g) in tetrahydrofuran (350cm 3 ) whilst the reaction temperature was
- reaction mixture was allowed to warm up to ambient temperature to complete the reaction, and after 30 minutes, was cooled to -30°C. To this solution was then added a solution of sodium isopropoxide prepared by adding a suspension of sodium hydride (1.0M, 24g) in tetrahydrofuran (150cm 3 ) to a solution of commercial isopropanol (60g) in tetrahydrofuran (250cm 3 ). The addition lasted 2 hours and the temperature was maintained below -30°C. The reaction mixture was allowed to warm to ambient temperature after which analysis by GC indicated that reaction was complete. The
- the amide (0.1M, 28.7g) was reacted with the chloro compound (0.1M, 30.65g) and sodium hydride (0.23M, 5.52g) in
- the chloro compound listed in Table 6 was prepared by the method of Example 39.
- the amino compound listed in Table 6 was prepared by the method of Example 34.
- the chloro and amino compounds were reacted together by the methods of Example 1 to give the compound of Formula I having the groups R 1 - R 4 listed.
- the purity of the compound was estimated by titration as 86% for MW of 557.
- This Example demonstrates the preparation of a compound of Formula I, wherein R 1 is a 2-alkylphenoxy group, R 2 is a phenyl group and R 3 and R 4 are alkoxy groups.
- the chloro compound listed in Table 6 was prepared by the methods of Example 24.
- the amino compound listed in Table 6 was prepared by the methods of Example 34.
- the chloro and amino compounds were reacted together by the methods of Example 1 to give the compound of Formula I listed in Table 6.
- the purity of the compound was estimated by titration as 91%.
- Example 43 Formula I by the methods described in Example 1.
- the chloro compound listed in Table 6 was prepared by the methods of Example 31.
- the amino compound was prepared by the methods of Example 24.
- the chloro and amino compounds were reacted together by the methods of Example 1.
- the purity of the compound having R 1 - R 4 listed in Table 6 was 84% for a compound of MW 509. The behaviour of this compound in Test 1, is enumerated in Table 6.
- the chloro compound listed in Table 6 was prepared by the methods of Example 39.
- the amino compound listed in Table 6 was prepared by the methods of
- Example 10 The chloro and amino compounds were reacted together by the methods of Example 1. The purity of the compound having R 1 - R 4 listed in Table 6 was 76% for a compound of MW 647. The behaviour of this compound in Test 1, is enumerated in Table 6.
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Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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AU81490/94A AU685192C (en) | 1993-12-02 | 1994-11-11 | Amides of acids of phosphorus for the extraction of metals |
EP95900829A EP0731805A1 (en) | 1993-12-02 | 1994-11-11 | Amides of acids of phosphorus for the extraction of metals |
CA002177064A CA2177064A1 (en) | 1993-12-02 | 1994-11-11 | Amides of acids of phosphorus for the extraction of metals |
JP7515460A JPH09506349A (en) | 1993-12-02 | 1994-11-11 | Chemical compound |
BR9408208A BR9408208A (en) | 1993-12-02 | 1994-11-11 | Compound to extract valuable metal contents from aqueous solutions of metal salts |
PL94314792A PL314792A1 (en) | 1993-12-02 | 1994-11-11 | Phosphoric acid amides used for extraction of metals |
FI962306A FI962306A (en) | 1993-12-02 | 1996-05-31 | Amides of phosphoric acids for the extraction of metals |
NO962264A NO962264L (en) | 1993-12-02 | 1996-05-31 | Chemical connections |
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GB939324757A GB9324757D0 (en) | 1993-12-02 | 1993-12-02 | Chemical compounds |
GB9324757.5 | 1993-12-02 |
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PCT/GB1994/002485 WO1995015329A1 (en) | 1993-12-02 | 1994-11-11 | Amides of acids of phosphorus for the extraction of metals |
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EP (1) | EP0731805A1 (en) |
JP (1) | JPH09506349A (en) |
BR (1) | BR9408208A (en) |
CA (1) | CA2177064A1 (en) |
FI (1) | FI962306A (en) |
GB (1) | GB9324757D0 (en) |
NO (1) | NO962264L (en) |
PE (1) | PE1096A1 (en) |
PL (1) | PL314792A1 (en) |
WO (1) | WO1995015329A1 (en) |
ZA (1) | ZA949069B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997030181A1 (en) * | 1996-02-17 | 1997-08-21 | Zeneca Limited | Extraction of cobalt and/or nickel from an aqueous feed solution |
CN106140304A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of ethylene trimerization and four poly-carbon monoxide-olefin polymeric and preparation and application thereof |
CN115058597A (en) * | 2022-06-30 | 2022-09-16 | 盛隆资源再生(无锡)有限公司 | Method for recycling electroplating sludge containing calcium, iron, cobalt and nickel |
US11532806B2 (en) | 2014-04-01 | 2022-12-20 | The Research Foundation For The State University Of New York | Electrode materials that include an active composition of the formula MgzMxOy for group II cation-based batteries |
CN115058597B (en) * | 2022-06-30 | 2024-06-04 | 盛隆资源再生(无锡)有限公司 | Recovery treatment method of electroplating sludge containing calcium, iron, cobalt and nickel |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0210387A1 (en) * | 1985-07-24 | 1987-02-04 | American Cyanamid Company | Selective removal of metals from aqueous solutions with dithiophosphinic acids |
EP0400311A2 (en) * | 1989-05-31 | 1990-12-05 | Cyanamid Canada Inc. | Metal recovery with monothiophosphinic acids |
EP0573182A1 (en) * | 1992-06-05 | 1993-12-08 | Zeneca Limited | Process for extracting metal values |
-
1993
- 1993-12-02 GB GB939324757A patent/GB9324757D0/en active Pending
-
1994
- 1994-11-11 JP JP7515460A patent/JPH09506349A/en active Pending
- 1994-11-11 CA CA002177064A patent/CA2177064A1/en not_active Abandoned
- 1994-11-11 PL PL94314792A patent/PL314792A1/en unknown
- 1994-11-11 BR BR9408208A patent/BR9408208A/en not_active Application Discontinuation
- 1994-11-11 EP EP95900829A patent/EP0731805A1/en not_active Ceased
- 1994-11-11 WO PCT/GB1994/002485 patent/WO1995015329A1/en not_active Application Discontinuation
- 1994-11-15 ZA ZA949069A patent/ZA949069B/en unknown
- 1994-12-01 PE PE1994256237A patent/PE1096A1/en not_active Application Discontinuation
-
1996
- 1996-05-31 NO NO962264A patent/NO962264L/en unknown
- 1996-05-31 FI FI962306A patent/FI962306A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0210387A1 (en) * | 1985-07-24 | 1987-02-04 | American Cyanamid Company | Selective removal of metals from aqueous solutions with dithiophosphinic acids |
EP0400311A2 (en) * | 1989-05-31 | 1990-12-05 | Cyanamid Canada Inc. | Metal recovery with monothiophosphinic acids |
EP0573182A1 (en) * | 1992-06-05 | 1993-12-08 | Zeneca Limited | Process for extracting metal values |
Non-Patent Citations (1)
Title |
---|
NAVRATIL O ET AL: "Synthesis of tetraphenylesters of imidothio- and imidodithiophosphoric acids and their use for the extraction of some rare metals", Z. CHEM. (ZECEAL,00442402);84; VOL.24 (1); PP.30, J. E. PURKYNE UNIV.;FAK. NATURWISS.; BRNO; 61137; CZECH. (CS) * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997030181A1 (en) * | 1996-02-17 | 1997-08-21 | Zeneca Limited | Extraction of cobalt and/or nickel from an aqueous feed solution |
US11532806B2 (en) | 2014-04-01 | 2022-12-20 | The Research Foundation For The State University Of New York | Electrode materials that include an active composition of the formula MgzMxOy for group II cation-based batteries |
CN106140304A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of ethylene trimerization and four poly-carbon monoxide-olefin polymeric and preparation and application thereof |
CN115058597A (en) * | 2022-06-30 | 2022-09-16 | 盛隆资源再生(无锡)有限公司 | Method for recycling electroplating sludge containing calcium, iron, cobalt and nickel |
CN115058597B (en) * | 2022-06-30 | 2024-06-04 | 盛隆资源再生(无锡)有限公司 | Recovery treatment method of electroplating sludge containing calcium, iron, cobalt and nickel |
Also Published As
Publication number | Publication date |
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GB9324757D0 (en) | 1994-01-19 |
NO962264D0 (en) | 1996-05-31 |
AU8149094A (en) | 1995-06-19 |
BR9408208A (en) | 1997-08-26 |
PE1096A1 (en) | 1996-02-28 |
JPH09506349A (en) | 1997-06-24 |
FI962306A0 (en) | 1996-05-31 |
FI962306A (en) | 1996-05-31 |
PL314792A1 (en) | 1996-09-30 |
NO962264L (en) | 1996-07-30 |
EP0731805A1 (en) | 1996-09-18 |
ZA949069B (en) | 1995-08-28 |
CA2177064A1 (en) | 1995-06-08 |
AU685192B2 (en) | 1998-01-15 |
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