CN1132115A - 基于过渡金属与膦的催化剂的电化学制备方法 - Google Patents
基于过渡金属与膦的催化剂的电化学制备方法 Download PDFInfo
- Publication number
- CN1132115A CN1132115A CN95120532A CN95120532A CN1132115A CN 1132115 A CN1132115 A CN 1132115A CN 95120532 A CN95120532 A CN 95120532A CN 95120532 A CN95120532 A CN 95120532A CN 1132115 A CN1132115 A CN 1132115A
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- Prior art keywords
- nickel
- acid
- oxide
- compound
- salt
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Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 34
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 150000003003 phosphines Chemical class 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 19
- -1 sulfophenyl Chemical group 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002841 Lewis acid Substances 0.000 claims description 10
- 150000007517 lewis acids Chemical class 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- 150000002816 nickel compounds Chemical class 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 6
- NLEUXPOVZGDKJI-UHFFFAOYSA-N nickel(2+);dicyanide Chemical compound [Ni+2].N#[C-].N#[C-] NLEUXPOVZGDKJI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000009954 braiding Methods 0.000 claims description 4
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000487 osmium oxide Inorganic materials 0.000 claims description 4
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 claims description 4
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 4
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 4
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims description 4
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 claims description 4
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 4
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 159000000000 sodium salts Chemical group 0.000 claims description 3
- YXTDAZMTQFUZHK-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;tin(2+) Chemical compound [Sn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O YXTDAZMTQFUZHK-ZVGUSBNCSA-L 0.000 claims description 2
- HXVJDHROZFWXHT-UHFFFAOYSA-N 2-diphenylphosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HXVJDHROZFWXHT-UHFFFAOYSA-N 0.000 claims description 2
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims description 2
- IHXNSHZBFXGOJM-UHFFFAOYSA-N 2-methylbut-2-enenitrile Chemical compound CC=C(C)C#N IHXNSHZBFXGOJM-UHFFFAOYSA-N 0.000 claims description 2
- QAUBDMDQJCBZJM-UHFFFAOYSA-N 2-phosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P QAUBDMDQJCBZJM-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910000497 Amalgam Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910021588 Nickel(II) iodide Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- PKYKNBXAHQHWCS-UHFFFAOYSA-N S(C#N)C#N.[Ni] Chemical compound S(C#N)C#N.[Ni] PKYKNBXAHQHWCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- YJHPAGMBPHQKCG-UHFFFAOYSA-N [Ni++].OP([O-])[O-] Chemical compound [Ni++].OP([O-])[O-] YJHPAGMBPHQKCG-UHFFFAOYSA-N 0.000 claims description 2
- RXGWEOPUMUXXTN-UHFFFAOYSA-N [Ni].P(O)(O)O Chemical compound [Ni].P(O)(O)O RXGWEOPUMUXXTN-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 159000000009 barium salts Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 2
- URMHSIWBWVSJBI-UHFFFAOYSA-N nickel sulfurous acid Chemical compound [Ni].S(O)(O)=O URMHSIWBWVSJBI-UHFFFAOYSA-N 0.000 claims description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 2
- AFYAQDWVUWAENU-UHFFFAOYSA-H nickel(2+);diphosphate Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AFYAQDWVUWAENU-UHFFFAOYSA-H 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229940007163 stannous tartrate Drugs 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 2
- NGOCMUBXJDDBLB-UHFFFAOYSA-N trifluoromethanesulfonic acid;zinc Chemical compound [Zn].OS(=O)(=O)C(F)(F)F NGOCMUBXJDDBLB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- IYFXESRMJKRSNZ-UHFFFAOYSA-L hydrogen carbonate;nickel(2+) Chemical compound [Ni+2].OC([O-])=O.OC([O-])=O IYFXESRMJKRSNZ-UHFFFAOYSA-L 0.000 claims 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims 1
- 239000000391 magnesium silicate Substances 0.000 claims 1
- 229910052919 magnesium silicate Inorganic materials 0.000 claims 1
- 235000019792 magnesium silicate Nutrition 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 150000003623 transition metal compounds Chemical class 0.000 abstract 1
- 238000005669 hydrocyanation reaction Methods 0.000 description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 7
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 3
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- DCYICVONOLZQJK-UHFFFAOYSA-N (4-chlorophenyl)phosphane Chemical compound PC1=CC=C(Cl)C=C1 DCYICVONOLZQJK-UHFFFAOYSA-N 0.000 description 2
- VXLQXFQDOGUAPA-UHFFFAOYSA-N (4-methoxyphenyl)phosphane Chemical compound COC1=CC=C(P)C=C1 VXLQXFQDOGUAPA-UHFFFAOYSA-N 0.000 description 2
- HUCQPHINKBNKRU-UHFFFAOYSA-N (4-methylphenyl)phosphane Chemical compound CC1=CC=C(P)C=C1 HUCQPHINKBNKRU-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
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- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- GKEZTSVAONCKHZ-UHFFFAOYSA-N 2-chloro-5-phosphanylbenzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(P)=CC(S(O)(=O)=O)=C1Cl GKEZTSVAONCKHZ-UHFFFAOYSA-N 0.000 description 1
- GDCJAPJJFZWILF-UHFFFAOYSA-N 2-ethylbutanedinitrile Chemical compound CCC(C#N)CC#N GDCJAPJJFZWILF-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- VEVZEWBWQKXGRE-UHFFFAOYSA-N S(=O)(=O)(O)C=1C=C(C=C(C1P)S(=O)(=O)O)C Chemical compound S(=O)(=O)(O)C=1C=C(C=C(C1P)S(=O)(=O)O)C VEVZEWBWQKXGRE-UHFFFAOYSA-N 0.000 description 1
- RELBRYJDPFWCIM-UHFFFAOYSA-N [K].[K].OS(O)(=O)=O Chemical compound [K].[K].OS(O)(=O)=O RELBRYJDPFWCIM-UHFFFAOYSA-N 0.000 description 1
- HJCUCLCJVVFBTD-UHFFFAOYSA-N [Na].[Na].S(O)(O)(=O)=O Chemical compound [Na].[Na].S(O)(O)(=O)=O HJCUCLCJVVFBTD-UHFFFAOYSA-N 0.000 description 1
- AZNJJXSPRLQRIC-UHFFFAOYSA-N [Ni].[Cl].C(O)(O)=O Chemical compound [Ni].[Cl].C(O)(O)=O AZNJJXSPRLQRIC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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Abstract
本发明涉及可被用作催化剂的化合物的电化学制备方法。预期被用于本发明方法的化合物含有更具体地至少一种氧化数为0或1的过渡金属以及与之结合的至少一种水溶性磺化膦。催化剂的电化学合成方法包含电解处理含有至少一种过渡金属化合物和磺化膦的水溶液，将其置于电解装置的电解池的阴极区。
Description
本发明涉及可被用作催化剂的化合物的电化学制备方法。
预期被用于本发明方法的化合物含有至少一种氧化数为0或1的过渡金属以及与之结合的至少一种水溶性磺化膦。
这类化合物可被用作，举例来说，专利FR-A-2,338,253中所述乙烯化合物氢氰化反应催化剂。在本文中，它们被称为催化剂，而对其应用领域未加以限制。
含有至少一种氧化数为0或1的过渡金属和与之结构的至少一种磺化膦的催化剂电化学合成方法包含将含有至少一种过渡金属化合物与磺化膦的水溶液置于电解装置中电解池的阴极区内进行电解处理。
式中：*Ar、Ar2和Ar3代表芳基，它们可以相同或不同；*Y1，Y2和Y3可以相同或不同，代表C1-4烷基、C1-4烷氧基、卤原子、CN基、NO2基、OH基、其中R1和R2可以相同或不同并且代表C1-4烷基的NR1R2；*M为选自下列基团从而促使化合物(I)呈水溶性的有机或无机阳离子部分：H+，由碱金属或碱土金属衍生的阳离子，其中R3、R4、R5和R6相同或不同并且代表C1-4烷基或氢原子的N(R3R4R5R6)+，由其苯磺酸盐可溶于水的金属衍生的其它阳离子；*m1、m2和m3为相同或不同的整数0-5，*n1、n2和n3为相同或不同的整数0-3，其中之一至少等于或大于1。
作为其苯磺酸盐呈水溶性的金属，可提及的为铅、锌和锡。
术语“水溶性”，本文中通常指每升水至少溶解0.01克的化合物。
作为优选使用的式(I)膦，其中：-Ar1、Ar2和Ar3为苯基；-Y1、Y2和Y3选自C1-2烷基、C1-2烷氧基；-M选自H+，由Na、K、Ca、Ba衍生的阳离子，NH+，四甲铵、四乙铵、四丙铵或四丁铵阳离子；-m1、m2和m3为整数0-3；-n1、n2和n3为整数0-3，至少其中之一大于1。
在这些膦中，最优选的是一(磺苯基)二苯膦、二(磺苯基)苯膦与三(磺苯基)膦的钠盐、钾盐、钙盐、钡盐、铵盐、四甲铵盐和四乙铵盐，其中SO3基以处于间位为佳。
作为可被用于本发明方法的式(I)所示膦的其它实例，可被提及的为下列物质的碱金属盐、或碱土金属盐、铵盐、季铵盐：(3-磺基-4-甲苯基)二(4-甲苯基)膦；(3-磺基-4-甲氧基苯基)二(4-甲氧苯基)膦；(3-磺基-4-氯苯基)二(4-氯苯基)膦；二(3-磺基苯基)苯基膦；二(4-磺基苯基)苯基膦；二(3-磺基-4-甲苯基苯基)(4-甲苯基)膦；二(3-磺基-4-甲氧苯)(4-甲氧苯基)膦，二(3-磺基-4-氯苯基)(4-氯苯基)膦；三(3-磺基苯基)膦；三(4-磺基苯基)膦；三(3-磺基-4-甲苯基)膦；三(3-磺基-4-甲氧苯基)膦；三(3-磺基-4-氯苯基)膦；(2-磺基-4-甲苯基)(3-磺基-4-甲苯基)(3，5-二磺基-4-甲苯基)膦；(3-磺基苯基)(3-磺基-4-氯苯基)(3，5-二磺基-4-氯苯基)膦。
当然，还可以选用这些膦的混合物。具体地，可以使用一、二和三焦磺化膦混合物。
作为过渡金属化合物，优选采用镍、钴、铁、钯、铂、铑和铱化合物。可以使用能够在反应条件下通入溶液的水溶性化合物。结合在金属上的剩余配位体并非至关重要，只要它们能够满足这些条件即可。
在上述化合物中，以镍化合物为最佳。作为非限制性实施例，可被提及的有羧酸镍(尤其是醋酸镍、甲酸镍和柠檬酸镍)、碳酸镍、碳酸氯镍、硼酸镍、溴化镍、氯化镍、碘化镍、硫氰酸镍、氰化镍、氢氧化镍、亚磷酸氢镍、亚磷酸镍、磷酸镍及其衍生物、硝酸镍、硫酸镍、亚硫酸镍、芳基磺酸镍和烷基磺酸镍。
镍化合物本身不必呈水溶性，举例来说，氰化镍在水中溶解能力并非很强，但是在磺化膦水溶液中很容易溶解。
用于本发明的电解装置中的电解池包括被隔离元件分开的一个阴极区和一个阳极区。
电解池的阴极由诸如铂、金、铱、钌、钯、镍、石墨、玻璃碳、铁、不锈钢、特种钢、铅、汞或汞齐之类材料制成。它还可以含有钛、钽、镍、或不锈钢，被涂敷一层铂、金、铱、钌、这些金属中数种的混合物、氧化铂、氧化钯、氧化铱、氧化铑、氧化钌、氧化锇或氧化钽或者这些氧化物中数种的混合物。
阴极可以具备平面结构，如板形或栅格或体积结构；尤其是可被穿透或开口。作为体积结构类型，可以采用上述材料的颗粒堆积、这些材料的毛毡或泡沫体。
可被用于制备阳极的材料有如铂、金、铱、钌、钯、镍、石墨、玻璃碳、不锈钢、特种钢或铅。还包括被一层铂、金、铱、钌、这些金属中数种的混合物、氧化铂、氧化钯、氧化铱、氧化铑、氧化钌、氧化锇或氧化钽或者这些氧化物中数种的混合物涂敷的钛和钽。
阳极的结构可以与阴极结构不同。
电解电池的隔离元件包括离子交换膜或多孔隔膜。
该膜可以是阴离子型，尤其是由具有酸基如磺酸基或羧酸基的阳离子交换树脂制得的类型。优选采用由磺酸树脂制备的膜。举例来说，可被提及的这类膜为以商标Nafion(过氟化磺酸膜)或Selemion出售的种类。
这些膜也可以是阴离子类型，但是通常优选阳离子膜，原因在于后者具备一些优点。具体地，后者强度较前者高，并且阳离子膜使用的电流强度较大。
多孔隔膜尤其可以是由多孔陶瓷、编织的或非编织合成纤维制成的隔膜或者基于合成纤维或石棉绒形成的沉积膜。
隔离元件被安置在阳极上或阴极上。
如上所述，含有磺化膦和过渡金属化合物的水溶液处在阴极区内。磺化膦的初始浓度通常为10-3摩尔/升-1摩尔/升。过渡金属化合物，特别是镍化合物的初始浓度通常为10-5-1摩尔/升。
其它能够使电解液的导电能力增强的化合物如可溶性盐类、举例来说，可被加入阴极区。
还可以添加能够改善过渡金属还原电势的配位剂。其可被列举的实例为氰化物。
此外，阴极区中的溶液可以包括对本发明方法制备的催化剂起补充作用的化合物，尤其是路易斯酸。
本文中提及的路易斯酸依据通用定义为可以接受电子对的化合物。
可以采用G.A.Olah所著《Friedel-Crafts and relatedreaction》卷1，P191-197(1963)中提及的路易斯酸。
可被用于阴极区的路易斯酸选自Ib、IIb、IIIa、IIIb、IVa、IVb、Va、Vb、VIb、VIIb和VIII族元素的化合物，所述化合物在水中或者更一般地在待电解处理的水溶液中至少部分地呈可溶性和稳定性。这些化合物通常为、但不仅限于盐类，尤其是卤化物、以氯化物和溴化物为佳，硫酸盐，硝酸盐，磺酸盐，尤其是三氟甲磺酸盐，羧酸盐，乙酰丙酮化物，四氟硼酸盐和磷酸盐。
可被提及的这些路易斯酸的非限制性实例为氯化锌、溴化锌、碘化锌、三氟甲磺酸锌、醋酸锌、硝酸锌、四氟硼酸锌、氯化锰、溴化锰、氯化镍、溴化镍、氰化镍、乙酰丙酮化镍、氯化镉、溴化镉、氯化亚锡、溴化亚锡、硫酸锡、酒石酸亚锡、稀土元素如镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、钇和镥的氯化物、溴化物、硫酸盐、硝酸盐、羧酸盐或三氟甲磺酸盐，氯化钴，氯化亚铁和氯化钇。
当然可采用数种路易酸的混合物。
在可被选用的路易斯酸中，最经常提及的有氯化锌、溴化锌、硫酸锌、四氟硼酸锌、氯化亚锡、溴化亚锡、氯化锌/氯化亚锡混合物、氯化镍、溴化镍和乙酰丙酮化镍。
相对于每摩尔过渡金属化合物，更具体地说为镍化合物，路易斯酸的用量通常为0-50摩尔，以0-10摩尔为佳。
阳极区含有阳极电解液水溶液，其中含有酸如尤其是硫酸、硝酸，水溶性羧酸如乙酸，这些酸的盐类尤其是钠、钾、铵或季铵盐或者碱如尤其是氢氧化钠或氢氧化钾。优选地，阳极电解液选自硫酸及其盐，尤其是硫酸二钾、硫酸氢钾、硫酸二钠和硫酸氢钠。
阳极电解液还可以含有一种或多种上述磺化膦。
阳极区溶液中阳极电解液的初始浓度一般在10-2-3摩尔/升。
用于本发明方法的电流由其强度与阴极电势限定。在电解全过程中，该电势保持恒定(静电位法)。还可以保持强度恒定(恒电流法)。在本发明的连续操作过程中，这两种变化形式是等同的。
当该法以恒定电势进行时，后者数值易于被本领域专业人员依据电流/电势曲线走向确定。
电流强度可以达到30安培/平方分米2。依据待还原过渡金属数量进行调节。
该法操作温度通常在0-95℃。
本发明方法的优选方案包括再生废催化剂，即再生经过使用并且至少部分钝化的催化剂。因此，基于磺化膦和氧化数为0或1的过渡金属、视需要而定可以含有一种或多种路易斯酸的催化剂在被用于丁二烯和/或戊烯腈氢氰化反应时会逐渐失活，过渡金属氧化后尤为如此。过渡金属、更具体地镍至少被部分地转化为氰化物。氢氰化反应终止时刻，含有尤其是磺化膦与过渡金属化合物的水相易于与有机相分离。该水相可以含有相对少量一开始被加入的化合物如丁二烯和/或戊烯腈或者反应期间形成的化合物如己二腈、甲基戊二腈、乙基丁二腈、戊烯腈与甲基丁烯腈。如上所述，水相经电化学处理再生催化剂。
下列实施例描述本发明。
使用设备
电解电池包括一个体积约为100毫升的圆柱形玻璃容器，其中阴极为铂栅，园柱形阳极被置于阴极栅板内，其底部含有由Nafion417R型树脂制成的膜，呈铂板形式的阳极被浸于其中。
该电解装置与一个电势恒定器连接从而保证了阴极电势相对于Ag/AgCl参考电极保持在-1.2伏。
缩略语：
TSTPP＝三磺化三苯膦的钠盐，
3PN＝3-戊烯腈
ADN＝己二腈
2M3＝2-甲基-3-丁烯腈
BD＝丁二烯
DC＝转化程度
RT＝相对于被转化的初始化合物所获得的化合物的选择性
t.o.＝产量＝相对于使用的每摩尔Ni(O)所形成的腈或二腈的毫摩尔数
COD＝环辛二烯
实施例1-5
通过电化学还原TSTPP水溶液中的Ni(CN)2合成Ni(O)/TSTPP催化剂。
将氰化镍(Ni(CN)2：10.6克/千克)和TSTPP(300克/千克水)的50毫升水溶液加入阴极区。
将20毫升阳极电解质(其组成如表1所示)放入阳极区。在电势被控制在-1.2伏、温度为25℃下进行电解。定期提取样品以便借助极谱法评估剩余Ni(II)。
| 实施例 | 阳极电解质 | 期间(分钟) | DC Ni(CN)2(％) |
| 1 | 0.6M TSTPP | 220 | 50 |
| 2 | 1.5M KHSO4 | 400 | 92 |
| 3 | 饱和K2SO4 | 400 | 48 |
| 4 | 饱和K2SO4 | 1350 | 75 |
| 5 | 0.1N H2SO4 | 75 | 77 |
表1对用电化学方法制备的催化剂的溶液1，2，4和5进行3-戊烯腈氢氰化反应试验(a、b、c和d)。
| 试验 | 催化剂： | Ni(O)(毫摩尔) | HCN(毫摩尔/小时) | RTADN(％) | t.o. |
| CT1* | Ni(COD)2/TSTPP | 5 | 67.4 | 61 | 30 |
| CT2** | Ni(CN)2(TSTPP)2 | 0 | 67.4 | 0 | 0 |
| a | 溶液1 | 3 | 55.7 | 64 | 38 |
| b | 溶液2 | 3.8 | 50.5 | 63 | 37 |
| c | 溶液4 | 3.2 | 54.7 | 63 | 35 |
| d | 溶液5 | 2.9 | 39.1 | 61 | 37 |
表2氢氰化试验的操作条件如下：
-3PN：320毫摩尔；ZnCl2：20毫摩尔；65℃；3小时。
CT1*＝借助通过用TSTPP替换Ni(COD)2中的COD配位体制备的催化剂进行对比试验；
CR2**＝借助未经电化学处理的Ni(CN)2(TSTPP)2溶液进行对比试验。
对用电化学方法制备的催化剂溶液1进行丁二烯氢氰化试验(e)。
| 试验 | 催化剂 | BD(毫摩尔) | Ni(O)(毫摩尔) | HCN(毫摩尔/小时) | RT3PM+2M3(％) | t.o. |
| CT3* | Ni(COD)2/TSTPP | 400 | 5.5 | 350 | 97 | 70 |
| CT4** | Ni(CN)2(TSTPP)2 | 400 | 0 | 350 | 0 | 0 |
| e | 溶液 | 530 | 4 | 386 | 90 | 60 |
表3
氢氰化试验操作条件：
TSTPP：25毫摩尔；90℃；1.2小时。
CT3**＝采用通过用TSTPP替代Ni(COD)2中COD配位体制成的催化剂进行对比试验；
CT4**＝采用未经电化学处理的Ni(CN)2(TSTPP)2溶液进行对比试验。
实施例6-通过还原TSTPP水溶液中的NiCl2合成Ni(O)/TSTPP。
将氯化镍(NiCl2：17.4克/千克)、TSTPP(300克/千克水)和氰化钠(NaCN：6.6克/千克)的50毫升水溶液加入阴极区。
将20毫升K2SO4的饱和水溶液放入阳极区。在电势被控制在-1.2伏、温度为25℃下进行电解。定期提取样品以便借助极谱法评估剩余Ni(II)。实施例 阳极电解质 期间(分钟) DCNi(II)％6 饱和K2SO4 1000 80
对以电化学方法再生的催化剂的溶液6进行3PN氢氰化试验(f)。试验 t.o. 催化剂 Ni(O) HCN RTADN
(毫摩尔) (毫摩尔/小时) (％)f 25 溶液6 4.45 57.5 59
实施例7-来自3-戊烯腈氢氰化反应的Ni/TSTPP水溶液的再生过程。
a)将下列组分置于150毫升玻璃反应器中并采用涡轮机进行搅拌：-38毫升含有5毫摩尔镍(O)、20毫摩尔TSTPP和20毫摩尔氯化锌的水溶液；-32.4毫升3PN(320毫摩尔)。
将整个体系加热至65℃，以67毫摩尔/小时的流速注入纯氢氰酸(在-10℃)冷凝，历时3.5小时。冷却后，经过排气与沉降，分离出两相。有机相借助气相色谱(GPC)进行评估，-3-戊烯腈：177毫摩尔，-乙基琥珀腈：13毫摩尔，-甲基戊二腈：35毫摩尔，-己二腈：92毫摩尔，相对于每毫摩尔镍形成28毫摩尔二腈。
b)采用-1.2伏的电势、以Ag/AgCl为参考电对完全非活性水相进行电解处理3小时。
c)在反应器中再加入：-29毫升如此再生的催化剂水溶液；-10毫升ZnCl2；-32.4毫升3PN(320毫升)。
整个体系被加热至65℃，氢氰酸以34毫摩尔/小时的流速被注入6小时。经过冷却与排气，借助GPC评估各种腈：-3-戊烯腈：183毫摩尔-乙基琥珀腈：14毫摩尔-甲基戊二腈：39毫摩尔-乙二腈：78毫摩尔相对于每毫摩尔镍形成32毫摩尔二腈。
这些结果表明催化剂被完全再生。
Claims (23)
1.含有至少一种氧化数为0或1的过渡金属并且结合至少一种磺化膦的催化剂的电化学合成制备方法，其特征在于电解处理含有至少一种过渡金属化合物和磺化膦的水溶液，该水溶液放置于电解装置中电解池的阴极区。
2.按照权利要求1的方法，其特征在于电解装置的电解池包含一个阴极区和一个阳极区，它们被由离子交换膜或多孔隔膜组成的分离元件分隔开来。
3.按照权利要求1或2的方法，其特征在于电解池的阴极由下列材料制成如铂、金、铱、钌、钯、镍、石墨、玻璃碳、铁、不锈钢、特种钢、铅、汞或汞齐，或者由下列材料组成：钛、钽、镍或不锈钢，它们被涂敷一层铂、金、铱、钌、这些金属中数种的混合物、氧化铂、氧化钯、氧化铱、氧化铑、氧化钌、氧化锇或氧化钽或这些氧化物中数种的混合物。
4.按照权利要求1-3中任一项的方法，其特征在于电解池的阴极和阳极具有平面结构，如板状或栅格，或者体积结构并且被穿孔或开口。
5.按照权利要求1-4中任一项的方法，其特征在于阴极或阳极具备选自它们构成材料粒状堆积、所述材料的毛毡或泡沫体的体积结构。
6.按照权利要求1-5中任一项的方法，其特征在于阳极材料有如铂、金、铱、钌、钯、镍、石墨、玻璃碳、不锈钢、特种钢或铅或者由被一层铂、金、铱、钌、这些金属中数种的混合物、氧化铂、氧化钯、氧化铱、氧化铑、氧化钌、氧化锇或氧化钽或者这些氧化物中数种的混合物涂敷的钛或钽所组成。
7.按照权利要求1-6中任一项的方法，其特征在于分离元件选自由具备酸基如磺酸基或羧酸基的阳离子交换树脂制备的阳离子型膜，以选自由磺酸树脂制备的膜为佳。
8.按照权利要求1-6中任一项的方法，其特征在于分离元件选自多孔陶瓷制成的隔膜、由编织或非编织合成纤维制得的隔膜、或基于石棉纤维或合成纤维的沉积隔膜。
9.按照权利要求1-8中任一项的方法，其特征在于所用的磺化膦如下列通式所示：
式中：*Ar、Ar2和Ar3代表芳基，它们可以相同或不同；*Y1，Y2和Y3可以相同或不同，代表C1-4烷基、C1-4烷氧基、卤原子、CN基、NO2基、OH基、其中R1和R2可以相同或不同并且代表C1-4烷基的NR1R2；*M为选自下列基团从而促使化合物(I)呈水溶性的有机或无机阳离子部分：H+，由碱金属或碱土金属衍生的阳离子，其中R3、R4、R5和R6相同或不同并且代表C1-4烷基或氢原子的N(R3R4R5R6)+，由其苯磺酸盐溶于水的金属衍生的其它阳离子，*m1、m2和m3为相同或不同的整数0-5，*n1、n2和n3为相同或不同的整数0-3，其中之一至少等于或大于1。
10.按照权利要求9的方法，其特征在于所用的磺化膦如通式(I)所示：式中-Ar1、Ar2和Ar3为苯基；-Y1、Y2和Y3选自C1-2烷基、C1-2烷氧基；-M选自H+，由Na、K、Ca、Ba衍生的阳离子，NH+，四甲铵、四乙铵、四丙铵或四丁铵阳离子；-m1、m2和m3为整数0-3；-n1、n2和n3为整数0-3，至少其中之一大于1。
11.按照权利要求1-10中任一项的方法，其特征在于所用的磺化膦选自一(磺苯基)二苯膦、二(磺苯基)苯膦与三(磺苯基)膦的钠盐、钾盐、钙盐、钡盐、铵盐、四甲铵盐和四乙铵盐，其中SO3基以处于间位为佳。
12.按照权利要求1-11中任一项的方法，其特征在于过渡金属化合物选自在反应条件下可溶于水或者可以通入溶液的镍、钴、铁、钯、铂、铑和铱化合物。
13.按照权利要求1-12中任一项的方法，其特征在于过渡金属化合物选自镍化合物如羧酸镍(尤其是醋酸镍、甲酸镍和柠檬酸镍)、碳酸镍、碳酸氢镍、硼酸镍、溴化镍、氯化镍、碘化镍、硫氰酸镍、氰化镍、氢氧化镍、亚磷酸镍、亚磷酸氢镍、磷酸镍及其衍生物、硝酸镍、硫酸镍、亚硫酸镍、芳基磺酸镍和烷基磺酸镍。
14.按照权利要求1-13中任一项的方法，其特征在于阴极区中磺化膦的初始浓度为10-3-1摩尔/升，过渡金属尤其是镍化合物的初始浓度为10-5-1摩尔/升。
15.按照权利要求1-14中任一项的方法，其特征在于阴极区含有其它能够提高电解质导电性的化合物如可溶性盐、能够改善过渡金属还原电势的配位剂如氰化物与路易斯酸。
16.按照权利要求15的方法，其特征在于阴极区所用的路易斯酸选自Ib、IIb、IIIa、IIIb、IVa、IVb、Va、Vb、VIb、VIIb和VIII族元素的化合物，所述化合物在水中或者更一般地在待电解处理的水溶液中至少部分地呈可溶性和稳定性，最好选自盐类，尤其是卤化物、以氯化物和溴化物为佳，硫酸盐，硝酸盐，磺酸盐，尤其是三氟甲磺酸盐，羧酸盐，乙酰丙酮化物，四氟硼酸盐和磷酸盐。
17.按照权利要求15和16的方法，其特征在于路易斯酸选自氯化锌、溴化锌、碘化锌、三氟甲磺酸锌、醋酸锌、硝酸锌、四氟硼酸锌、氯化锰、溴化锰、氯化镍、溴化镍、氰化镍、乙酰丙酮化镍、氯化镉、溴化镉、氯化亚锡、溴化亚锡、硫酸锡、酒石酸亚锡、稀土元素如镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、钇和镥的氯化物、溴化物、硫酸盐、硝酸盐、羧酸盐或三氟甲磺酸盐，氯化钴，氯化亚铁和氯化钇。
18.按照权利要求15-17中任一项的方法，其特征在于路易斯酸选自氯化锌、溴化锌、硫酸锌、四氟硼酸锌、氯化亚锡、溴化亚锡、氯化锌/氯化亚锡混合物、氯化镍、溴化镍和乙酰丙酮化镍。
19.按照权利要求15-18中任一项的方法，其特征在于，相对于每摩尔过渡金属化合物，更具体地说为镍化合物，路易斯酸的用量为0-50摩尔，以0-10摩尔为佳。
20.按照权利要求1-19中任一项的方法，其特征在于阳极区含有阳极电解液水溶液，其中含有酸如尤其是硫酸、硝酸，水溶性羧酸如乙酸，这些酸的盐类尤其是钠、钾、铵或季铵盐或者碱如氢氧化钠或氢氧化钾。阳极电解质以选自硫酸及其盐为佳。
21.按照权利要求1-19中任一项的方法，其特征在于阳极区含有由一种或多种磺化膦组成的阳极电解质水溶液。
22.按照权利要求1-21中任一项的方法，其特征在于阳极区溶液中阳极电解质初始浓度为10-2-3摩尔/升。
23.按照权利要求1-22中任一项的方法，其特征在于在阴极区使用基于磺化膦和过渡金属更具体地镍的废催化剂水溶液，至少部分地被转化为氰化物，所述废催化剂还含有视需要而定一种或多种路易斯酸，所述溶液可以含有相对少量的化合物如丁二烯和/或戊烯腈或己二腈、甲基戊二腈、乙基琥珀腈或甲基丁烯腈。
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| CN95120532A Expired - Fee Related CN1078496C (zh) | 1994-12-06 | 1995-12-06 | 基于过渡金属与膦的催化剂的电化学制备方法 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5679237A (zh) |
| EP (1) | EP0715890B1 (zh) |
| JP (1) | JP2914487B2 (zh) |
| KR (1) | KR100372376B1 (zh) |
| CN (1) | CN1078496C (zh) |
| AR (1) | AR000284A1 (zh) |
| BR (1) | BR9505666A (zh) |
| CA (1) | CA2164470C (zh) |
| DE (1) | DE69512357T2 (zh) |
| ES (1) | ES2136265T3 (zh) |
| FR (1) | FR2727637B1 (zh) |
| RU (1) | RU2154529C2 (zh) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099913C (zh) * | 1995-12-29 | 2003-01-29 | 罗狄亚纤维与树脂中间体公司 | 过渡金属和膦基催化剂的电化学制备方法 |
| CN102083788A (zh) * | 2008-06-17 | 2011-06-01 | 罗地亚管理公司 | 由烯属不饱和化合物生产腈化合物的方法 |
| CN105063659A (zh) * | 2015-09-15 | 2015-11-18 | 苏州市铂瑞工业材料科技有限公司 | 一种电解装置 |
| CN107406281A (zh) * | 2015-02-04 | 2017-11-28 | 喷雾系统公司 | 电解盒以及使用其的系统和方法 |
| CN110368966A (zh) * | 2019-08-01 | 2019-10-25 | 南方科技大学 | 一种纳米棒状亚磷酸钴水裂解催化剂的制备方法及其应用 |
| CN115125552A (zh) * | 2022-08-30 | 2022-09-30 | 江苏欣诺科催化剂股份有限公司 | 叔膦化合物的合成方法 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3816241B2 (ja) | 1998-07-14 | 2006-08-30 | 株式会社大和化成研究所 | 金属を還元析出させるための水溶液 |
| FR2787446B1 (fr) | 1998-12-22 | 2001-02-02 | Rhone Poulenc Fibres | Procede d'hydrocyanation de composes organiques a insaturations ethyleniques |
| FR2787349B1 (fr) * | 1998-12-22 | 2001-02-02 | Rhone Poulenc Fibres | Procede de fabrication d'un catalyseur d'hydrocyanation |
| RU2226228C2 (ru) * | 1999-08-20 | 2004-03-27 | Дю Пон Де Немур Энтернасьональ С.А. | Способ электрохимического получения ni(о) фосфитных и дифосфитных комплексов |
| US6428676B1 (en) | 2000-11-08 | 2002-08-06 | Enthone Inc. | Process for producing low alpha lead methane sulfonate |
| US20100087308A1 (en) * | 2006-09-21 | 2010-04-08 | Albemarte Corporation | Methods for conversion of methane to useful hydrocarbons, catalysts for use therein, and regeneration of the catalysts |
| JP7228411B2 (ja) * | 2019-03-06 | 2023-02-24 | 上村工業株式会社 | 無電解金めっき浴 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2007076C3 (de) * | 1970-02-17 | 1979-12-13 | Studiengesellschaft Kohle Mbh | Verfahren zur elektrochemischen Herstellung von CO-freien metallorganischen Komplexen von Übergangsmetallen der IV. bis VIII. Gruppe |
| US3887441A (en) * | 1971-12-29 | 1975-06-03 | Phillips Petroleum Co | Electro-chemical synthesis of organonickel compounds |
| FR2338253A1 (fr) * | 1976-01-13 | 1977-08-12 | Rhone Poulenc Ind | Procede d'hydrocyanation de composes organiques insatures comportant au moins une double liaison ethylenique |
| FR2616810B1 (fr) * | 1987-03-25 | 1989-08-18 | Rhone Poulenc Sante | Procede electrochimique pour recuperer le rhodium metallique a partir de solutions aqueuses de catalyseurs usages |
| JP2660284B2 (ja) * | 1988-02-16 | 1997-10-08 | 株式会社ササクラ | 触媒電極及びその製造法 |
| FR2635317B1 (fr) * | 1988-08-11 | 1990-10-19 | Norsolor Sa | Hydrures de platine de structure bimetallique pontee, leur procede de preparation et leur application a la catalyse de reactions chimiques |
| DE4242723A1 (de) * | 1992-12-17 | 1994-06-23 | Hoechst Ag | Verfahren zur Herstellung von Aldehyden |
-
1994
- 1994-12-06 FR FR9414884A patent/FR2727637B1/fr not_active Expired - Fee Related
-
1995
- 1995-12-01 ES ES95420339T patent/ES2136265T3/es not_active Expired - Lifetime
- 1995-12-01 EP EP95420339A patent/EP0715890B1/fr not_active Expired - Lifetime
- 1995-12-01 DE DE69512357T patent/DE69512357T2/de not_active Expired - Fee Related
- 1995-12-05 AR AR33450095A patent/AR000284A1/es unknown
- 1995-12-05 BR BR9505666A patent/BR9505666A/pt not_active IP Right Cessation
- 1995-12-05 CA CA002164470A patent/CA2164470C/fr not_active Expired - Fee Related
- 1995-12-05 RU RU95121108/04A patent/RU2154529C2/ru not_active IP Right Cessation
- 1995-12-05 JP JP7339920A patent/JP2914487B2/ja not_active Expired - Fee Related
- 1995-12-06 CN CN95120532A patent/CN1078496C/zh not_active Expired - Fee Related
- 1995-12-06 KR KR1019950047171A patent/KR100372376B1/ko not_active IP Right Cessation
- 1995-12-06 US US08/568,295 patent/US5679237A/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099913C (zh) * | 1995-12-29 | 2003-01-29 | 罗狄亚纤维与树脂中间体公司 | 过渡金属和膦基催化剂的电化学制备方法 |
| CN102083788A (zh) * | 2008-06-17 | 2011-06-01 | 罗地亚管理公司 | 由烯属不饱和化合物生产腈化合物的方法 |
| CN102083788B (zh) * | 2008-06-17 | 2014-12-31 | 因维斯塔技术有限公司 | 由烯属不饱和化合物生产腈化合物的方法 |
| CN107406281A (zh) * | 2015-02-04 | 2017-11-28 | 喷雾系统公司 | 电解盒以及使用其的系统和方法 |
| CN107406281B (zh) * | 2015-02-04 | 2021-07-20 | 喷雾系统公司 | 电解盒以及使用其的系统和方法 |
| CN105063659A (zh) * | 2015-09-15 | 2015-11-18 | 苏州市铂瑞工业材料科技有限公司 | 一种电解装置 |
| CN110368966A (zh) * | 2019-08-01 | 2019-10-25 | 南方科技大学 | 一种纳米棒状亚磷酸钴水裂解催化剂的制备方法及其应用 |
| CN110368966B (zh) * | 2019-08-01 | 2022-05-24 | 南方科技大学 | 一种纳米棒状亚磷酸钴水裂解催化剂的制备方法及其应用 |
| CN115125552A (zh) * | 2022-08-30 | 2022-09-30 | 江苏欣诺科催化剂股份有限公司 | 叔膦化合物的合成方法 |
| CN115125552B (zh) * | 2022-08-30 | 2022-11-22 | 江苏欣诺科催化剂股份有限公司 | 叔膦化合物的合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08257418A (ja) | 1996-10-08 |
| ES2136265T3 (es) | 1999-11-16 |
| JP2914487B2 (ja) | 1999-06-28 |
| EP0715890A1 (fr) | 1996-06-12 |
| DE69512357D1 (de) | 1999-10-28 |
| CN1078496C (zh) | 2002-01-30 |
| CA2164470C (fr) | 2000-02-15 |
| AR000284A1 (es) | 1997-06-18 |
| BR9505666A (pt) | 1997-11-04 |
| DE69512357T2 (de) | 2000-02-24 |
| CA2164470A1 (fr) | 1996-06-07 |
| FR2727637A1 (fr) | 1996-06-07 |
| EP0715890B1 (fr) | 1999-09-22 |
| FR2727637B1 (fr) | 1997-01-03 |
| KR100372376B1 (ko) | 2003-04-26 |
| US5679237A (en) | 1997-10-21 |
| KR960021146A (ko) | 1996-07-18 |
| RU2154529C2 (ru) | 2000-08-20 |
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