WO1999038615A1 - Colloides aqueux de metal precieux et leur utilisation - Google Patents
Colloides aqueux de metal precieux et leur utilisation Download PDFInfo
- Publication number
- WO1999038615A1 WO1999038615A1 PCT/EP1999/000290 EP9900290W WO9938615A1 WO 1999038615 A1 WO1999038615 A1 WO 1999038615A1 EP 9900290 W EP9900290 W EP 9900290W WO 9938615 A1 WO9938615 A1 WO 9938615A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- precious metal
- metal
- mmol
- sol
- noble metal
- Prior art date
Links
- 239000000084 colloidal system Substances 0.000 title claims abstract description 44
- 239000010970 precious metal Substances 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002923 metal particle Substances 0.000 claims abstract description 8
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 108010064470 polyaspartate Proteins 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 229960004106 citric acid Drugs 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008131 herbal destillate Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229940013688 formic acid Drugs 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N lysine Chemical compound NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229940045136 urea Drugs 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0026—Preparation of sols containing a liquid organic phase
- B01J13/003—Preparation from aqueous sols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
Definitions
- the invention relates to precious metal colloids, i.e. in the nanometer range, highly disperse, ultra-fine precious metal particles; They are used in a variety of ways as precursors to supported catalysts.
- J. Colloid Interface Sei. 131 (1989), 186 and in J. Colloid Interface Sci. HO (1986), 82 describes the preparation of stabilized colloids of precious metals, their application to ion exchange resins and their use as hydrogenation catalysts.
- dissolved noble metal salts are reduced with NaBH4 in the presence of surface-active detergents and the resulting noble metal hydrosols are brought onto the ion exchange resins.
- noble metal colloids with a noble metal concentration of at most 0.5 mmol / 1 can be produced.
- JP 1/100 545 describes the production of a palladium hydrosol likewise containing 0.5 mmol / l by reduction of dissolved PdCl2 with ascorbic acid in the presence of poly-N-vinylpyrrolidone.
- JP 2/179 881 describes the preparation of a Pd hydrosol containing up to 10 mmol / l, PdCl2 being reduced by reduction with NaBH4 in the presence of water-soluble polymers.
- hydrosols with more than 10 mmol / 1 cannot be produced. Furthermore, these hydrosols are produced in the presence of alkaline earth chlorides. From J. Phys. Chem.
- the invention relates to aqueous precious metal colloids in the form of a sol with metal particles of a size from 0.5 to 100 nm, which are obtained by reducing noble metal compounds with the aid of organic reducing agents and which are characterized by - 3 -
- the invention further relates to a process for producing aqueous precious metal colloids with metal particles with a size of 0.5 to 100 nm, which is characterized in that an aqueous solution of a precious metal salt or
- complex adds one or more water-soluble polymers and then the noble metal cation to the metallic state by adding an organic reducing agent from the group of C j -C 4 alcohols, C 1 -C 4 aldehydes, formic acid, ascorbic acid, citric acid, urea or others to the person skilled in the art known organic reducing agents or a mixture of several of them reduced, with a metal content of more than 10 mmol / 1 to 500 mmol / 1, calculated as elemental metal, an amount of the water-soluble polymer of 0.1 to 20 wt .-%, all based on the total weight of the aqueous solution.
- organic reducing agent from the group of C j -C 4 alcohols, C 1 -C 4 aldehydes, formic acid, ascorbic acid, citric acid, urea or others to the person skilled in the art known organic reducing agents or a mixture of several of them reduced, with a metal content of more than 10 mmol / 1 to 500 mmol
- the invention further relates to a process for the preparation of noble metal supported catalysts, which is characterized in that a catalyst support is brought into contact with a sol of the above type containing a noble metal colloid, the noble metal is drawn onto the support, so that the finished supported catalyst 1 to 20% by weight of precious metal, based on the total weight of the carrier - 4 -
- lysators contains, removes the precious metal-depleted sol and dries the supported catalyst.
- Precious metals in the sense of the invention are the elements of the so-called platinum group and group Ib of the periodic table (Mendeleev). The following may be mentioned in detail:
- the metal particles can also be doped with non-reducible metal components in the dispersion state.
- Such metals are, for example, Ti, Zn, Zr, Mo, Hf, Re, Ce, Lu, Ni, Cu.
- Ni 2+ or Cu + are preferred. These metals can be introduced as a solution of their salts. The amount of these doping metals is 0 to 100% by weight, preferably 0 to 30% by weight, based on the weight of the noble metal and calculated as metal.
- Suitable water-soluble polymers are, for example, polymers and copolymers of monomers with polar groups, such as the hydroxyl, the amino, the carboxyl and the sulfonic acid group. They can be copolymerized with monomers without a polar group or with a less polar group such as the ester group to such an extent that the water solubility of the copolymer is retained.
- Such monomers are for example N-vinyl-pyrrolidone, acrylic acid, methacrylic acid, aspartic acid, styrenesulfonic acid, (meth) acrylic acid-C j-C4 alkyl ester with a hydroxyl, amino or C j -C 4 - (di) alkylamino group, the fictional monomer vinyl alcohol, N-vinyl caprolactam, vinyl pyridine, vinylamine, N-vinyl imidazole, N-vinyl methylimidazole;
- Comonomers that can be used are, for example
- (Meth) acrylic acid -CC-C4-alkyl ester and vinyl acetate are known to the person skilled in the art.
- Preferred polymers are, for example, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polyaspartic acid, particularly preferably poly-N-vinylpyrrolidone.
- the polymers have molecular weights (weight average) of - 5 -
- Organic solvents which can be present in the noble metal colloid solutions according to the invention are water-soluble and are, for example, alcohols,
- Carboxylic acids, ketones and nitriles with up to 4 carbon atoms such as methanol, ethanol, propanol, i-propanol, butanol, acetic acid, propionic acid, acetone, methyl ethyl ketone, acetonitrile.
- solvents can be used if precious metal complexes which are sparingly soluble in water are used.
- the quantity range for the solvents therefore has zero as the lower limit and is 0 to 10% by weight, based on the total weight of the sol.
- some of the organic solvents in question can serve as organic reducing agents.
- the invention is furthermore preferably characterized by a content of polyvalent anions in the aqueous noble metal colloids.
- Polyvalent anions of this type are, for example: citrate, phosphate, polyphosphate.
- Such multivalent anions are present in an amount of 0.1 to 10%, based on the total weight of the aqueous noble metal colloids.
- the noble metal colloid solutions according to the invention are aqueous-based. The remainder is therefore 100% by weight and thus the predominant proportion of water.
- Organic reducing agents for the preparation of novel aqueous noble metal colloids are well known in the art and are, for example C1-C 4 - alcohols, particularly methanol or ethanol, C j -C 4 - aldehydes, especially formaldehyde or acetaldehyde, formic acid, ascorbic acid, citric acid, urea or a mixture of several from them.
- ascorbic acid Preferably used: ascorbic acid,
- Citric acid Citric acid, methanol, ethanol or a mixture of several of them. you will be - 6 -
- stoichiometric requirement is known to the person skilled in the art.
- aqueous noble metal colloids for example, an aqueous solution of a noble metal salt or a water-soluble noble metal complex is added, one or more water-soluble polymers and one or more salts with polyvalent anions are added, and the mixture is reduced with one of the reducing agents mentioned. If the solubility ratios require it, one or more of the organic solvents mentioned can also be used. The order of presence and addition can also be varied as desired, but the reducing agent is preferably used at the end.
- the noble metal is in the form of the halides (fluorides, chlorides, bromides, iodides), nitrates, sulfates or in the form of salts of carboxylic acids, which are also by
- Amino or halogen can be used; further possibilities of using the noble metals are the use of their metal alcoholates, metal phenolates, metal acetylacetonates and other noble metal compounds familiar to the person skilled in the art. Such noble metal compounds can also be used in the form of their complexes; Complexes range from simple double salts, such as
- Na2PdCl 4 or H 2 PtCl 6 up to complex compounds with organic ligands, such as palladium acetylacetonate.
- Carboxylic acids the noble metal salts of which can be used, as mentioned above, have 1 to 20 C atoms, are linear, branched or cyclic, are furthermore saturated or unsaturated and have 1 to 3 carboxyl groups.
- carboxylic acids are: formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, citric acid, lactic acid, amino acids, such as lysine or aspartic acid. - 7 -
- the metal particles are in a size of 0.5 to 100 nm, preferably 1 to 30 nm.
- the noble metal content in the aqueous noble metal colloids according to the invention is always above 10 mg-atom / 1, preferably above 50 mg-atom / 1, and reaches values of up to 250 mg-atom / 1, in many cases up to 500 mg Atom / 1.
- Such an aqueous noble metal colloid according to the invention can be brought into contact with a catalyst support, such as an ion exchange resin, activated carbon, Al 2 O 3 , SiO 2 and other supports familiar to the person skilled in the art.
- a catalyst support such as an ion exchange resin, activated carbon, Al 2 O 3 , SiO 2 and other supports familiar to the person skilled in the art.
- the precious metal colloid spontaneously pulls onto the catalyst carrier.
- the amount and concentration of the aqueous noble metal colloid in comparison to the amount of the offered carrier can be calculated in a simple and known manner so that the finished supported catalyst contains 0.1 to 20% by weight of noble metal, based on the total weight of the supported catalyst.
- the support can be brought into contact with the aqueous precious metal colloid by introducing the support into this aqueous precious metal colloid, but also by other methods known to the person skilled in the art, such as by spraying on or by adding the aqueous precious metal colloid to the catalyst support, which is moved in a pelletizing drum, until the support , recognizable by its moisture state, is saturated with precious metal colloid. After each of the described contacts, the precious metal-depleted sol is removed and the supported catalyst is dried.
- this noble metal colloid sol i.e. this Pt nanoparticle dispersion
- this Pt nanoparticle dispersion could be used for the production of heterogeneously supported catalysts.
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Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU26190/99A AU2619099A (en) | 1998-01-31 | 1999-01-19 | Aqueous precious metal colloids and the use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19803891.7 | 1998-01-31 | ||
DE19803891A DE19803891A1 (de) | 1998-01-31 | 1998-01-31 | Wäßrige Edelmetallkolloide und ihre Verwendung |
Publications (1)
Publication Number | Publication Date |
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WO1999038615A1 true WO1999038615A1 (fr) | 1999-08-05 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP1999/000290 WO1999038615A1 (fr) | 1998-01-31 | 1999-01-19 | Colloides aqueux de metal precieux et leur utilisation |
Country Status (3)
Country | Link |
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AU (1) | AU2619099A (fr) |
DE (1) | DE19803891A1 (fr) |
WO (1) | WO1999038615A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2491988C2 (ru) * | 2008-01-28 | 2013-09-10 | Басф Кэталистс Ллк | Способ получения водной суспензии коллоида благородного металла |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19911504B4 (de) * | 1999-03-16 | 2006-02-23 | Südzucker AG Mannheim/Ochsenfurt | Verfahren zur industriellen Oxidation von Alkoholen, Aldehyden oder Polyhydroxyverbindungen |
DE10037071A1 (de) | 2000-07-29 | 2002-02-21 | Omg Ag & Co Kg | Edelmetall-Nanopartikel, Verfahren zu ihrer Herstellung und Verwendung |
EP1236512A1 (fr) * | 2001-02-28 | 2002-09-04 | Council Of Scientific And Industrial Research | Catalyseur de métal précieux à taille nano et procédé de préparation sélective de 1,4 butènediol |
DE10116315A1 (de) * | 2001-04-02 | 2002-10-10 | Giesecke & Devrient Gmbh | Farbcodierung zur Kennzeichnung von Gegentänden |
WO2005007328A1 (fr) | 2003-07-17 | 2005-01-27 | Asahi Kasei Medical Co., Ltd. | Solution de colloide et de metal |
JP4763460B2 (ja) * | 2003-08-22 | 2011-08-31 | 株式会社コーセー | 一重項酸素消去剤、及びそれを用いた組成物 |
DE102006025148A1 (de) * | 2006-05-30 | 2007-12-06 | Süd-Chemie AG | Verfahren zur Herstellung eines geträgerten Metallkatalysators |
DE102013108664A1 (de) * | 2013-08-09 | 2015-02-12 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Oberflächenmodifizierte Metallkolloide und ihre Herstellung |
CN114797870B (zh) * | 2022-04-14 | 2023-06-09 | 浙江师范大学 | 一种用于间苯二甲腈加氢制备间苯二甲胺的催化剂及其制备方法和应用 |
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DE4443705A1 (de) * | 1994-12-08 | 1996-06-13 | Studiengesellschaft Kohle Mbh | Verfahren zur Herstellung von tensidstabilisierten Mono- und Bimetallkolloiden der Gruppe VIII und Ib des Periodensystems als isolierbare und in hoher Konzentration wasserlösliche Precursor für Katalysatoren |
WO1997024224A1 (fr) * | 1995-12-28 | 1997-07-10 | Heath James R | Nanocristaux de metal monodisperses organiquement fonctionnalises |
EP0879642A2 (fr) * | 1997-05-23 | 1998-11-25 | Hoechst Research & Technology Deutschland GmbH & Co. KG | Nanoparticules contenant du palladium et stabilisées par une polybétaine, leur procédé de préparation ainsi que le catalyseur ainsi préparé pour la production d'acétate de vinyle |
-
1998
- 1998-01-31 DE DE19803891A patent/DE19803891A1/de not_active Withdrawn
-
1999
- 1999-01-19 AU AU26190/99A patent/AU2619099A/en not_active Abandoned
- 1999-01-19 WO PCT/EP1999/000290 patent/WO1999038615A1/fr active Application Filing
Patent Citations (3)
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DE4443705A1 (de) * | 1994-12-08 | 1996-06-13 | Studiengesellschaft Kohle Mbh | Verfahren zur Herstellung von tensidstabilisierten Mono- und Bimetallkolloiden der Gruppe VIII und Ib des Periodensystems als isolierbare und in hoher Konzentration wasserlösliche Precursor für Katalysatoren |
WO1997024224A1 (fr) * | 1995-12-28 | 1997-07-10 | Heath James R | Nanocristaux de metal monodisperses organiquement fonctionnalises |
EP0879642A2 (fr) * | 1997-05-23 | 1998-11-25 | Hoechst Research & Technology Deutschland GmbH & Co. KG | Nanoparticules contenant du palladium et stabilisées par une polybétaine, leur procédé de préparation ainsi que le catalyseur ainsi préparé pour la production d'acétate de vinyle |
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ANTONIETTI M: "SYNTHESIS AND CHARACTERIZATION OF NOBLE METAL COLLOIDS IN BLOCK COPOLYMER MICELLES**", ADVANCED MATERIALS, vol. 7, no. 12, 1 December 1995 (1995-12-01), pages 1000 - 1005, XP000547224 * |
NAOKI TOSHIMA ET AL: "POLYMER-PROTECTED PALLADIUM-PLATINUM BIMETALLIC CLUSTERS: PREPARATION, CATALYTIC PROPERTIES AND STRUCTURAL CONSIDERATIONS", JOURNAL OF THE CHEMICAL SOCIETY. FARADAY TRANSACTIONS, vol. 89, no. 14, 21 July 1993 (1993-07-21), pages 2537 - 2543, XP000381461 * |
YUAN WANG ET AL: "IMMOBILIZATION OF POLYMER-PROTECTED METAL COLLOID CATALYSTS BY THE FORMATION OF POLYMER HYDROGEN BOND COMPLEXES", POLYMERS FOR ADVANCED TECHNOLOGIES, vol. 7, no. 8, 1 August 1996 (1996-08-01), pages 634 - 638, XP000623415 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2491988C2 (ru) * | 2008-01-28 | 2013-09-10 | Басф Кэталистс Ллк | Способ получения водной суспензии коллоида благородного металла |
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Publication number | Publication date |
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AU2619099A (en) | 1999-08-16 |
DE19803891A1 (de) | 1999-08-05 |
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