US3147154A - Method of depositing metal-containing material onto an extended surface - Google Patents
Method of depositing metal-containing material onto an extended surface Download PDFInfo
- Publication number
- US3147154A US3147154A US112508A US11250861A US3147154A US 3147154 A US3147154 A US 3147154A US 112508 A US112508 A US 112508A US 11250861 A US11250861 A US 11250861A US 3147154 A US3147154 A US 3147154A
- Authority
- US
- United States
- Prior art keywords
- metal
- solution
- containing material
- catalyst
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 26
- 238000000151 deposition Methods 0.000 title claims description 11
- 229910052751 metal Inorganic materials 0.000 title description 66
- 239000002184 metal Substances 0.000 title description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 230000006911 nucleation Effects 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 62
- 239000003054 catalyst Substances 0.000 description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- -1 ferrous metals Chemical class 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910000669 Chrome steel Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical class [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- WYOHYGGHYATVOZ-UHFFFAOYSA-L nickel(2+);sulfate;pentahydrate Chemical compound O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O WYOHYGGHYATVOZ-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent 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
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 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 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
Definitions
- this invention relates to a method for plating or depositing a substantially continuous film or layer of metal or metal-containing material upon an extended surface or substrate from a solution containing a soluble salt of the metal.
- this invention relates to a method for making a catalyst which comprises plating a metallic catalyst material on an extended surface from a solution containing a soluble metal salt or compound of the catalyst material.
- elemental metal may be a precipitated in particulate or discrete powder form from a solution containing a soluble salt of the metal by the action of a reducing agent on the solution.
- This general concept is employed in the hydrometallurgical precipitation of elemental metal powder, particularly non-ferrous metals, where hydrogen is employed as the reducing agent.
- Reduction of the metal compound or salt and precipitation of the metal powder normally is carried out at elevated temperatures and at superatmospheric pressures.
- This method of producing metal powder is useful where a salt of the metal forms with ammonia a soluble complex ion which may be reduced with a suitable agent, e.g. hydrogen, to yield elemental metal.
- the solution is generally stirred or otherwise agitated. More recently, it has been proposed to incorporate nucleating sites, for example, fine metal particles, in the solution of metal salt to further induce precipitation ofthe metal powder.
- elemental metal or its intermediate product of reduction, is deposited from a solution of its salt by reduction as a substantially continuous film on an extended surface or substrate in contact with the solution, and not precipitated as discrete particles or powder as in the prior art.
- a suitable metal salt solution is pressured with hydrogen at an effective reduction temperature in a sub stantially quiescent state, the elemental metal is de-' posited, or plated, as a substantially continuous film on an extended surface or' substrate in contact with the solution, as explained more fully hereinbelow.
- the extended surface or substrate as employed herein, and in the appended claims, is defined as a surface or substrate of extended dimensions and is particularly of a length and geometric surface area substantially greater than that of discrete particles.
- an extendedv surface having formed thereon a deposit of a metal in accordance with our invention is particularly suitable for use in a catalytic structure.
- our invention involves broadly depositing a substantially continuous film of elemental metal, or its intermediate product of reduction, on an extended surface from a solution containing a soluble salt of the metal by the action of hydrogen on the solution'while maintaining the system in a substantially quiescent state.
- the invention is particularly applicable to those metals whose compounds or salts in solution form a soluble complex with a suitable stabilizing agent such as complexing agents which form soluble complex ions of the co-ordinate complex type, sequestering agents, chelating agents, dispersants and detergents. Salts of numerous metals form with ammonia, for example, a soluble complex ion of the coordinate type.
- the metal complex may be readily reduced to the elemental form, or its intermediate product of reduction, with a suitable reducing agent, described in greater detail hereinbelow.
- a suitable reducing agent for example, copper, silver, gold, chromium, tungsten, molybdenum, iron, nickel, platinum,
- - palladium and osmium are generally suitable for use in the present process.
- Other elemental metals including many from Groups II, III, IV, V and VII of the Periodic Table, for example, zinc, aluminum, tin, zirconium, titanium, vanadium, tantalum and manganese can also be used.
- the non-metallic ion or anion of the metal compound or salt to be precipitated from the ammoniacal solution may be of the more common inorganic or organic acids which form soluble salts of the metal. Also, the anion should not be reduced under precipitation conditions. Those anions usually employed include, sulfate, chloride, nitrate, carbonate and acetate.
- the solvent generally used is Water to form an aqueous solution of the metal complex, but suitable organic solvents for the metal salts, including alcohols, aldehydes, ethers, ketones, toluene and pyridine may be useful, as may liquid ammonia.
- stabilizing agent may be ammonia or other stabilizing agents.
- suitable stabilizing agents include the organic primary, secondary and tertiary amines such as methyl amine, ethylenediamine and diethylenetriamine.
- stabilizing agents may include phosphates, especially pyrophosphate and metaphosphate, as well as citrate, acetate, oxalate, tartrate, o-phenanthroline, thiocyanate, thiosulfate, thiourea, pyridine, quinoline and cyano groups.
- Still further useful complex formations include the chloro, hydroxo and aquo complexes, such as the aquo-ammonia complexes.
- Olefin and olefin-like compounds are also useful, and may include, for example, ethylene, propylene, butadiene, etc., as well as the unsaturated cyclo compounds such as cyclohexene and styrene.
- the olefin and olefin-like compounds are desirably employed in a nonaqueous solvent, for example, benzene, toluene, pyridine, acetone and ether.
- concentration of the particular metal in solution will depend to a considerable extent upon the metal employed. Generally there appears to be no benefit from employing concentrations in excess of about 5 molar,
- the concentration of a metal in solution should be less than that at which a substantial amount will precipitate out in particulate form which may be deter-' rare or expensive elements, such as platinum, the con:
- centration may advantageously be as low as 0.04 molar.
- the element metal or its intermediate product of reduction is plated onto the extended surface from the solution.
- the extended surface is immersed or contacted with the solution containing a soluble compound of the metal, and the solution pressured with hydrogen atan effective reduction temperature, often at elevated temperatures and under superatmospheric pressures.
- the temperature and pressure employed in the reducing step depend to some extent upon the material undergoing reduction and may vary over a Wide range.
- platinum may be deposited from ethylene chloroplatinate by reduction with hydrogen at room temperature and atmospheric pressure.
- reduction proceeds advantageously at elevated temperatures which may range up to about 500 F. and under a partial pressure of hydrogen of as high as 4,000 pounds per square inch or higher. Although higher temperatures and pressures may increase slightly the plating phenomenon, this increase generally is not practical.
- Our invention is particularly suited for depositing or plating a substantially continuous film of elemental metal, or its intermediate product of reduction, which exhibits catalytic activity or which may be rendered active upon subsequent treatment on an extended surface or substrate for use in a catalytic structure.
- the substrate of the catalytic structure serves as the carrier or support member for the metal film deposited from a solution of its salt as explained above in detail.
- the deposit is calcined and activated by subsequent treatment which includes, for example, oxidizing or sulfiding of the catalyst material.
- the deposit as the catalyst material thus employed in the catalytic structure is selected from the group consisting of metals, metal oxides and metal sulfides of Groups I through VIII of the Periodic Table, and more preferably of Groups I, VI and VIII, numerous examples of which have been set forth above.
- the extended substrate employed in a catalytic structure formed in accordance with our invetion is not restricted to any particular configuration nor to any particular material.
- the substrate may be formed of a metal or non-metal suitable for use in a catalytic reactor and may include such materials as aluminum, steel, stainless steel or titanium, including sintered metal materials, or refractory materials including, for example, refractory metal oxides, e.g. alumina magnesia, silica, or refractory metal silicates or carbides.
- the configuration of the extended substrate may include bars, balls, chain, mesh, saddles, plates, sheet, tubes or the like, the members of the substrate not being less than about As-inch in its maximum dimension and more preferably A-inch, and of sufficient thickness to provide the required physical strength.
- elemental platinum useful as a reforming catalyst may be deposited on the substrate from an ammoniacal solution of a platinum salt, e.g. the chloride salt or chloroplatinic acid, by reducing the solution with hydrogen at elevated temperature and pressure as described above.
- a silver deposit useful as a catalyst in the oxidation of ethylene may be formed on the substrate from an ammoniacal solution of silver sulfate.
- a deposit of nickel or of molybdenum similarly formed may be sulfided with hydrogen sulfide gas at elevated temperature, and the resulting sulfide catalyst then used in hydrogenation processes.
- a deposit of chromium may be oxidized for use as a catalyst in polymerization of olefins, or a deposit of iron may be oxidized for use in reaction of carbon monoxide with hydrogen to produce hydrocarbons.
- a mixture of metal salts, all of which form complex ions with ammonia or other suitable stabilizing agents, may be used for forming a deposit of more than one catalytic element.
- a nickel-molybdenum catalyst or cobalt-molybdenum-nickel catalyst may be deposited on the substrate for use as hydrogenation catalysts.
- nickel-molybdenum or nickel-tungsten salts may be complexed in a sodium citrate solution, and the metals precipitated from solution with hydrogen as described above. The co-deposits may then be calcined, sulfided, or otherwise activated Where desired.
- the reactants are passed through a bed of porous catalyst particles, beads or pellets.
- a carbonaceous deposit accumulates in the pores and openings of the catalyst as the process proceeds under continuous operating conditions.
- This deposition of carbonaceous material commonly known as fouling of the catalyst, is a function of the reactants, the reaction products, the conditions of the process, and the catalyst, and certain types of reactions may be worse olfenders than others. Fouling may be particularly ex cessive when the reactants or products remain in contact With the catalyst for a relatively long time.
- the reactants diffuse into the interior or central portion of the catalyst particles and may be retained for an excessive period of time whereupon decomposition of the reactants and products result in fouling the catalyst. Fouling results not only in a decrease in catalyst activity and loss in selectivity but also results in intensification of the heat transfer problem in the catalyst bed thereby resulting in local overheating or hot spots, particularly during regeneration of the catalyst.
- the deposited film of metal as catalyst material formed on an extended substrate in accordance with our invention defines the depth of the catalyst layer, and therefore limits the extent of diffusion of the reactants through the pores or openings in the catalyst material to this shallow depth. As a consequence, substantially all of the active catalyst is exposed to the reactants, and excessive residence time, or entrapment, of the reactants is minimized or substantially eliminated. In this manner, we readily achieve with less catalyst material a reactive capacity equal to, or greater than, that accomplished by conventional catalysts.
- a solution of cupric ammonium sulfate was prepared by adding to 350 milliliters of distilled water, 47.5 grams of cupric sulfate, 22.5 grams of ammonium sulfate and 30 milliliters of ammonium hydroxide (28.7% by weight NH OH). The resulting solution was warmed on a hot plate and diluted by the addition of water to 500 milliliters. 35 milliliters of ammonium hydroxide was added, and the solution was boiled until the total volume of the solution measured 500 milliliters. The final solution was clear and had a pH of 9.
- a stainless steel strip measuring 1% by /2 by A was initially washed with acetone, then cleaned with 5% nitric acid solution and rinsed with water, dried and weighed.
- the strip was attached to the bottom end of an impeller in such a manner that the major plane of the strip lay horizontally.
- the impeller was rotatable by means of an electric motor. However, for the first run of this example the motor was not operated.
- a 500 milliliter glass beaker containing 250 milliliters of the above solution was placed in an autoclave, and the stainless steel strip attached to the impeller was submerged in the solution such that the strip was covered with solution to a depth of about 4 inches.
- the impeller extended beyond the top surface of the autoclave, and was connected to the motor means.
- the autoclave was flushed with hydrogen and pressured with hydrogen to 265 p.s.i.g. at F.
- the autoclave was heated to 305 F. at which temperature the pressure of the reactor was 420 p.s.i.g.
- the reactor was held at 305 F. for /2 hour, then cooled to room temperature, vented and the stainless steel strip removed from the autoclave.
- the strip was dried at 750 F. for two hours.
- the stainless steel strip exhibited a heavy deposit of black material, and showed a net gain in weight of 0.1528 gram.
- Example II The method of Example I was repeated except that zirconium strips measuring approximately 2" by /2" by were employed. In the one instance Where the process was carried under a substantially quiescent condition, the zirconium strip, exhibiting a black deposit, had a net gain in weight of 0.0577 gram. On the other hand, when the solution was subject to agitation by reason of rotation of the impeller having the zirconium strip attached thereto, the strip had a net gain of only 0.0011
- a plating solution was prepared by dissolving 112 grams of nickel sulfate hexahydrate, 73 grams of cobalt sulfate heptahydrate, 89 grams of ammonium molybdate tetrahydrate, and 100 grams of ammonium sulfate in 1500 milliliters of distilled water. The solution was warmed to 180 F., and 900 milliliters of ammonium hydroxide was added slowly. The resulting solution had a pH of 9.
- a nickel strip measuring approximately 4" by by was washed first with acetone, then benzene, and water rinsed, then dried and weighed.
- the nickel strip was mounted vertically by means of a transite holder having a slot to hold the strip, and the transite holder was placed on the bottom of the 2000 milliliter beaker.
- a sufficient quantity of the above prepared solution was added to the beaker to completely submerge the nickel strip to a depth of about 4-inch.
- An impeller having a horizontal stirrer blade measuring about 1%" by /2" was inserted in the solution beside the nickel strip, the distance between the impeller and the strip being about 1% inches. The assembly was placed in an autoclave.
- the impeller was rotatable by electric motor means as in Example I, but the impeller was not rotated during this run.
- the autoclave was flushed with hydrogen and then pressurized with hydrogen at 260 p.s.i.g., at 75 F and heated to 300 F. A pressure of 500 p.s.i.g. was secured.
- the reactor was held at 300 F. for 2 hours, cooled and vented.
- the nickel strip after being a calcined at 750 F., had a blue-gray color and showed a net gain in weight of 0.0396 gram.
- a copper vanadate solution was prepared by dissolving grams of potassium hydroxide in 350 milliliters of distilled water and adding thereto with stirring 70 grams of vanadium pentoxide. The solution was diluted to 1400 milliliters. 231 grams of citric acid was dissolved in 700 milliliters of water and then mixed with the basic solution of vanadium pentoxide. In another solution, 140 grams of copper sulfate pentahydrate was dissolved in 350 milliliters of water and 35 grams of nickel sulfate pentahydrate was dissolved therein. The latter solution was then thoroughly mixed with the other resulting solution having dissolved therein potassium hydroxide, vanadium pentoxide and citric acid. The final solution had a pH of 4.
- chrome steel pads prepared from metal mesh were employed as the base support. Each pad measured about 3%? along the sides and weighed approximately 20 grams.
- 12 pads were stacked in a glass lined stainless steel tower having a length of 57" and an inside diameter of 1%". A sufiicient quantity of the copper vanadate solution was added to the tower to completely immerse the pads, the top pad being submerged to a depth of about A three foot void space remained at the top of the tower.
- the tower was then heated to 350 F. at which the pressure was 1000 p.s.i.g.
- the tower was held for five hours at 350 F.
- the rate of flow of hydrogen was 2 standard cubic feet per hour and in Run No. 2, 0.4 standard cubic foot per hour.
- the pads were withdrawn from the tower, dried at 750 F. for two hours and weighed.
- the table below shows the net gain in weight of each pad, the pad represented by Sample No. 1 being the bottom pad and in the stack and Sample No. 12 being the top pad.
- a method of depositing metal-containing material onto an extended support which comprises forming a solution of a soluble complex of metal of the metal-containing material to be deposited on said support, immersing said support in said solution and reducing said metalcontaining material from said solution by pressuring said solution with hydrogen and maintaining said solution at an effective reduction temperature while maintaining the system in a substantially quiescent state whereby said metal-containing material is deposited without nucleation on said support as a substantially continuous film.
- a method of depositing metal-containing materials as co-deposits of more than one metal onto an extended support which comprises forming a soluble complex of metals of the metal-containing materials to be deposited on said support in an ammoniacal solution, immersing said support in said solution, the concentration of each of said metals in solution being 0.01 to 5 molar, reducing said metal-containing materials from solution by pressuring said solution with hydrogen and maintaining said solution at an eifective reduction temperature while maintaining the system in a substantially quiescent state whereby said metal-containing materials are co-deposited without nucleation onto said substrate as a substantially continuous metal film.
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Description
United States Patent 3,147,154 METHOD OF DEPOSITING METAL-CONTAWING MATERIAL ONTO AN EXTENDED SURFACE Edward L. Cole, Glenliam, and Edwin C. Knowles, Poughkeepsie, N.Y., assignors to Texaco Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed May 25, 1961, Ser. No. 112,508 8 Claims. (Cl. 148-631) This invention relates in general to a method for depositing metal-containing material onto a supporting surface. In one of its more specific aspects, this invention relates to a method for plating or depositing a substantially continuous film or layer of metal or metal-containing material upon an extended surface or substrate from a solution containing a soluble salt of the metal. In another of its more specific aspects, this invention relates to a method for making a catalyst which comprises plating a metallic catalyst material on an extended surface from a solution containing a soluble metal salt or compound of the catalyst material.
It is well known in the art that elemental metal may be a precipitated in particulate or discrete powder form from a solution containing a soluble salt of the metal by the action of a reducing agent on the solution. This general concept is employed in the hydrometallurgical precipitation of elemental metal powder, particularly non-ferrous metals, where hydrogen is employed as the reducing agent. Reduction of the metal compound or salt and precipitation of the metal powder normally is carried out at elevated temperatures and at superatmospheric pressures. This method of producing metal powder is useful where a salt of the metal forms with ammonia a soluble complex ion which may be reduced with a suitable agent, e.g. hydrogen, to yield elemental metal. To facilitate precipitation of the metal in particulate form, the solution is generally stirred or otherwise agitated. More recently, it has been proposed to incorporate nucleating sites, for example, fine metal particles, in the solution of metal salt to further induce precipitation ofthe metal powder.
In accordance with the method of the present invention, elemental metal, or its intermediate product of reduction, is deposited from a solution of its salt by reduction as a substantially continuous film on an extended surface or substrate in contact with the solution, and not precipitated as discrete particles or powder as in the prior art. We found, quite unexpectedly, that when a suitable metal salt solution is pressured with hydrogen at an effective reduction temperature in a sub stantially quiescent state, the elemental metal is de-' posited, or plated, as a substantially continuous film on an extended surface or' substrate in contact with the solution, as explained more fully hereinbelow. The extended surface or substrate as employed herein, and in the appended claims, is defined as a surface or substrate of extended dimensions and is particularly of a length and geometric surface area substantially greater than that of discrete particles. As explained below, an extendedv surface having formed thereon a deposit of a metal in accordance with our invention is particularly suitable for use in a catalytic structure.
Accordingly, our invention involves broadly depositing a substantially continuous film of elemental metal, or its intermediate product of reduction, on an extended surface from a solution containing a soluble salt of the metal by the action of hydrogen on the solution'while maintaining the system in a substantially quiescent state. The invention is particularly applicable to those metals whose compounds or salts in solution form a soluble complex with a suitable stabilizing agent such as complexing agents which form soluble complex ions of the co-ordinate complex type, sequestering agents, chelating agents, dispersants and detergents. Salts of numerous metals form with ammonia, for example, a soluble complex ion of the coordinate type. The metal complex may be readily reduced to the elemental form, or its intermediate product of reduction, with a suitable reducing agent, described in greater detail hereinbelow. Metals from Groups I, VI and VIII of the Periodic Table of Elements, for example, copper, silver, gold, chromium, tungsten, molybdenum, iron, nickel, platinum,
- palladium and osmium are generally suitable for use in the present process. Other elemental metals, including many from Groups II, III, IV, V and VII of the Periodic Table, for example, zinc, aluminum, tin, zirconium, titanium, vanadium, tantalum and manganese can also be used.
The non-metallic ion or anion of the metal compound or salt to be precipitated from the ammoniacal solution may be of the more common inorganic or organic acids which form soluble salts of the metal. Also, the anion should not be reduced under precipitation conditions. Those anions usually employed include, sulfate, chloride, nitrate, carbonate and acetate. The solvent generally used is Water to form an aqueous solution of the metal complex, but suitable organic solvents for the metal salts, including alcohols, aldehydes, ethers, ketones, toluene and pyridine may be useful, as may liquid ammonia.
Although ammonia is the preferred stabilizing agent and the invention is described in greater detail in connection with solutions of this type, certain other stabilizing agents may be employed. Other suitable stabilizing agents include the organic primary, secondary and tertiary amines such as methyl amine, ethylenediamine and diethylenetriamine. In addition, stabilizing agents may include phosphates, especially pyrophosphate and metaphosphate, as well as citrate, acetate, oxalate, tartrate, o-phenanthroline, thiocyanate, thiosulfate, thiourea, pyridine, quinoline and cyano groups. Still further useful complex formations include the chloro, hydroxo and aquo complexes, such as the aquo-ammonia complexes. Olefin and olefin-like compounds are also useful, and may include, for example, ethylene, propylene, butadiene, etc., as well as the unsaturated cyclo compounds such as cyclohexene and styrene. However, the olefin and olefin-like compounds are desirably employed in a nonaqueous solvent, for example, benzene, toluene, pyridine, acetone and ether.
The concentration of the particular metal in solution will depend to a considerable extent upon the metal employed. Generally there appears to be no benefit from employing concentrations in excess of about 5 molar,
but the concentration of a metal in solution should be less than that at which a substantial amount will precipitate out in particulate form which may be deter-' rare or expensive elements, such as platinum, the con:
centration may advantageously be as low as 0.04 molar.
The element metal or its intermediate product of reduction is plated onto the extended surface from the solution.
with hydrogen in the presence of the extended surface. In the preferred embodiment of our invention, the extended surfaceis immersed or contacted with the solution containing a soluble compound of the metal, and the solution pressured with hydrogen atan effective reduction temperature, often at elevated temperatures and under superatmospheric pressures. The temperature and pressure employed in the reducing step depend to some extent upon the material undergoing reduction and may vary over a Wide range. Thus, for example, platinum may be deposited from ethylene chloroplatinate by reduction with hydrogen at room temperature and atmospheric pressure. However, with numerous other metals, reduction proceeds advantageously at elevated temperatures which may range up to about 500 F. and under a partial pressure of hydrogen of as high as 4,000 pounds per square inch or higher. Although higher temperatures and pressures may increase slightly the plating phenomenon, this increase generally is not practical.
It is essential during the plating operation of our invention to maintain the system under a relatively quiescent state, or maintain the system substantially free from turbulence. Agitating the dissolved metal salt solution or extended surface resulting in relatively violent or irregular motion should be avoided so as not to induce nucleation which would result in precipitation of the metal as discrete particles. In maintaining a relatively quiescent state during deposition, the metal is plated on the extended surface as a substantially continuous and adherent film.
Our invention is particularly suited for depositing or plating a substantially continuous film of elemental metal, or its intermediate product of reduction, which exhibits catalytic activity or which may be rendered active upon subsequent treatment on an extended surface or substrate for use in a catalytic structure. The substrate of the catalytic structure serves as the carrier or support member for the metal film deposited from a solution of its salt as explained above in detail. Where desired, the deposit is calcined and activated by subsequent treatment which includes, for example, oxidizing or sulfiding of the catalyst material. The deposit as the catalyst material thus employed in the catalytic structure is selected from the group consisting of metals, metal oxides and metal sulfides of Groups I through VIII of the Periodic Table, and more preferably of Groups I, VI and VIII, numerous examples of which have been set forth above.
The extended substrate employed in a catalytic structure formed in accordance with our invetion is not restricted to any particular configuration nor to any particular material. The substrate may be formed of a metal or non-metal suitable for use in a catalytic reactor and may include such materials as aluminum, steel, stainless steel or titanium, including sintered metal materials, or refractory materials including, for example, refractory metal oxides, e.g. alumina magnesia, silica, or refractory metal silicates or carbides. The configuration of the extended substrate may include bars, balls, chain, mesh, saddles, plates, sheet, tubes or the like, the members of the substrate not being less than about As-inch in its maximum dimension and more preferably A-inch, and of sufficient thickness to provide the required physical strength.
By way of example, elemental platinum useful as a reforming catalyst may be deposited on the substrate from an ammoniacal solution of a platinum salt, e.g. the chloride salt or chloroplatinic acid, by reducing the solution with hydrogen at elevated temperature and pressure as described above. Similarly, a silver deposit useful as a catalyst in the oxidation of ethylene may be formed on the substrate from an ammoniacal solution of silver sulfate. On the other hand, a deposit of nickel or of molybdenum similarly formed may be sulfided with hydrogen sulfide gas at elevated temperature, and the resulting sulfide catalyst then used in hydrogenation processes. A deposit of chromium may be oxidized for use as a catalyst in polymerization of olefins, or a deposit of iron may be oxidized for use in reaction of carbon monoxide with hydrogen to produce hydrocarbons.
A mixture of metal salts, all of which form complex ions with ammonia or other suitable stabilizing agents, may be used for forming a deposit of more than one catalytic element. By such means, a nickel-molybdenum catalyst or cobalt-molybdenum-nickel catalyst may be deposited on the substrate for use as hydrogenation catalysts. Also, nickel-molybdenum or nickel-tungsten salts may be complexed in a sodium citrate solution, and the metals precipitated from solution with hydrogen as described above. The co-deposits may then be calcined, sulfided, or otherwise activated Where desired.
During catalytic processing by conventional methods with solid particulate catalysts, the reactants are passed through a bed of porous catalyst particles, beads or pellets. In many such reactions employing organic materials at elevated temperatures, a carbonaceous deposit accumulates in the pores and openings of the catalyst as the process proceeds under continuous operating conditions. This deposition of carbonaceous material, commonly known as fouling of the catalyst, is a function of the reactants, the reaction products, the conditions of the process, and the catalyst, and certain types of reactions may be worse olfenders than others. Fouling may be particularly ex cessive when the reactants or products remain in contact With the catalyst for a relatively long time. When a porous catalyst is used, the reactants diffuse into the interior or central portion of the catalyst particles and may be retained for an excessive period of time whereupon decomposition of the reactants and products result in fouling the catalyst. Fouling results not only in a decrease in catalyst activity and loss in selectivity but also results in intensification of the heat transfer problem in the catalyst bed thereby resulting in local overheating or hot spots, particularly during regeneration of the catalyst.
It will be observed that the deposited film of metal as catalyst material formed on an extended substrate in accordance with our invention defines the depth of the catalyst layer, and therefore limits the extent of diffusion of the reactants through the pores or openings in the catalyst material to this shallow depth. As a consequence, substantially all of the active catalyst is exposed to the reactants, and excessive residence time, or entrapment, of the reactants is minimized or substantially eliminated. In this manner, we readily achieve with less catalyst material a reactive capacity equal to, or greater than, that accomplished by conventional catalysts.
The following examples will further illustrate our invention.
EXAMPLE I A solution of cupric ammonium sulfate was prepared by adding to 350 milliliters of distilled water, 47.5 grams of cupric sulfate, 22.5 grams of ammonium sulfate and 30 milliliters of ammonium hydroxide (28.7% by weight NH OH). The resulting solution was warmed on a hot plate and diluted by the addition of water to 500 milliliters. 35 milliliters of ammonium hydroxide was added, and the solution was boiled until the total volume of the solution measured 500 milliliters. The final solution was clear and had a pH of 9.
A stainless steel strip, measuring 1% by /2 by A was initially washed with acetone, then cleaned with 5% nitric acid solution and rinsed with water, dried and weighed. The strip was attached to the bottom end of an impeller in such a manner that the major plane of the strip lay horizontally. The impeller was rotatable by means of an electric motor. However, for the first run of this example the motor was not operated.
A 500 milliliter glass beaker containing 250 milliliters of the above solution was placed in an autoclave, and the stainless steel strip attached to the impeller was submerged in the solution such that the strip was covered with solution to a depth of about 4 inches. The impeller extended beyond the top surface of the autoclave, and was connected to the motor means. The autoclave was flushed with hydrogen and pressured with hydrogen to 265 p.s.i.g. at F. The autoclave was heated to 305 F. at which temperature the pressure of the reactor was 420 p.s.i.g. The reactor was held at 305 F. for /2 hour, then cooled to room temperature, vented and the stainless steel strip removed from the autoclave. The strip was dried at 750 F. for two hours. The stainless steel strip exhibited a heavy deposit of black material, and showed a net gain in weight of 0.1528 gram.
In a separate run to illustrate the advantages of our invention, the above procedure was repeated under agitation whereby only a relatively small amount of deposit resulted. Thus, the above procedure was repeated with the exception that during the hydrogen pressure step the motor was operated, and the impeller with the stainless steel strip attached thereto was rotated at 2,000 r.p.m. The strip had a stainless appearance and a net gain in weight of 0.0024 gram. It thus will be observed that employing the method of our invention rendered substantially superior results.
EXAMPLE II The method of Example I was repeated except that zirconium strips measuring approximately 2" by /2" by were employed. In the one instance Where the process was carried under a substantially quiescent condition, the zirconium strip, exhibiting a black deposit, had a net gain in weight of 0.0577 gram. On the other hand, when the solution was subject to agitation by reason of rotation of the impeller having the zirconium strip attached thereto, the strip had a net gain of only 0.0011
gram.
EXAMPLE III A plating solution was prepared by dissolving 112 grams of nickel sulfate hexahydrate, 73 grams of cobalt sulfate heptahydrate, 89 grams of ammonium molybdate tetrahydrate, and 100 grams of ammonium sulfate in 1500 milliliters of distilled water. The solution was warmed to 180 F., and 900 milliliters of ammonium hydroxide was added slowly. The resulting solution had a pH of 9.
A nickel strip measuring approximately 4" by by was washed first with acetone, then benzene, and water rinsed, then dried and weighed. The nickel strip was mounted vertically by means of a transite holder having a slot to hold the strip, and the transite holder was placed on the bottom of the 2000 milliliter beaker. A sufficient quantity of the above prepared solution was added to the beaker to completely submerge the nickel strip to a depth of about 4-inch. An impeller having a horizontal stirrer blade measuring about 1%" by /2" was inserted in the solution beside the nickel strip, the distance between the impeller and the strip being about 1% inches. The assembly was placed in an autoclave. The impeller was rotatable by electric motor means as in Example I, but the impeller was not rotated during this run. The autoclave was flushed with hydrogen and then pressurized with hydrogen at 260 p.s.i.g., at 75 F and heated to 300 F. A pressure of 500 p.s.i.g. was secured. The reactor was held at 300 F. for 2 hours, cooled and vented. The nickel strip, after being a calcined at 750 F., had a blue-gray color and showed a net gain in weight of 0.0396 gram.
The above procedure was repeated except the impeller was rotated at 2,000 r.p.m. during the hydrogen pressurizing step thereby agitating the solution. In this instance, the nickel strip actually showed a loss in weight of 0.0277 gram.
6 EXAMPLE v A copper vanadate solution was prepared by dissolving grams of potassium hydroxide in 350 milliliters of distilled water and adding thereto with stirring 70 grams of vanadium pentoxide. The solution was diluted to 1400 milliliters. 231 grams of citric acid was dissolved in 700 milliliters of water and then mixed with the basic solution of vanadium pentoxide. In another solution, 140 grams of copper sulfate pentahydrate was dissolved in 350 milliliters of water and 35 grams of nickel sulfate pentahydrate was dissolved therein. The latter solution was then thoroughly mixed with the other resulting solution having dissolved therein potassium hydroxide, vanadium pentoxide and citric acid. The final solution had a pH of 4.
In two separate runs, chrome steel pads prepared from metal mesh were employed as the base support. Each pad measured about 3%? along the sides and weighed approximately 20 grams. For both runs, 12 pads were stacked in a glass lined stainless steel tower having a length of 57" and an inside diameter of 1%". A sufiicient quantity of the copper vanadate solution was added to the tower to completely immerse the pads, the top pad being submerged to a depth of about A three foot void space remained at the top of the tower. The tower, in both runs, was flushed with hydrogen and pressured to 650 p.s.i.g. at room temperature. Hydrogen was introduced through an appropriate conduit at the bottom section of the tower and vented through a regulator at the top of the tower. The tower was then heated to 350 F. at which the pressure was 1000 p.s.i.g. The tower was held for five hours at 350 F. However, in Run No. 1, the rate of flow of hydrogen was 2 standard cubic feet per hour and in Run No. 2, 0.4 standard cubic foot per hour. After cooling and depressuring the pads were withdrawn from the tower, dried at 750 F. for two hours and weighed. The table below shows the net gain in weight of each pad, the pad represented by Sample No. 1 being the bottom pad and in the stack and Sample No. 12 being the top pad.
Table PLATING ON CHROME STEEL PADS Run No. 1 Run N o. 2
Pad Sample N o. Wt. gain, Pad Sample No. Wt. gain,
grams grams From the table it will be observed that those pads positioned near the top of the tower, and thereby farthest removed from the point of introduction of the hydrogen gas showed a greater gain in weight than the bottommost pad or pads. In addition, when the rate of flow of hydrogen was reduced in Run No. 2, there was a significant gain in weight for each pad. Consequently, a substantially greater amount of material was plated on those pads undergoing treatment in a relatively quiescent environment.
Having described our invention and certain embodiments thereof, we claim:
1. A method of depositing metal-containing material onto an extended support which comprises forming a solution of a soluble complex of metal of the metal-containing material to be deposited on said support, immersing said support in said solution and reducing said metalcontaining material from said solution by pressuring said solution with hydrogen and maintaining said solution at an effective reduction temperature while maintaining the system in a substantially quiescent state whereby said metal-containing material is deposited without nucleation on said support as a substantially continuous film.
2. A method according to claim 1 wherein the concentration of said metal in solution is not less than 0.01 molar.
3. A method according to claim 1 wherein said support is a metal.
4. A method according to claim 1 wherein said metal of said metal-containing material is formed as a soluble complex by complexing with an ammoniacal solution.
5. A method according to claim 1 wherein the concentration of said metal in solution is 0.5 to 2 molar.
6. A method according to claim 1 wherein said deposit of metal-containing material is activated for use as a catalyst by oxidizing said deposit to convert the metal to its corresponding oxide.
7. A method according to claim 1 wherein said deposit of metal-containing material is activated for use as a catalyst by sulfiding said deposit to convert the metal to its corresponding sulfide.
8. A method of depositing metal-containing materials as co-deposits of more than one metal onto an extended support which comprises forming a soluble complex of metals of the metal-containing materials to be deposited on said support in an ammoniacal solution, immersing said support in said solution, the concentration of each of said metals in solution being 0.01 to 5 molar, reducing said metal-containing materials from solution by pressuring said solution with hydrogen and maintaining said solution at an eifective reduction temperature while maintaining the system in a substantially quiescent state whereby said metal-containing materials are co-deposited without nucleation onto said substrate as a substantially continuous metal film.
References Cited in the file of this patent UNITED STATES PATENTS 1,880,741 Boswell Oct. 4, 1932 2,402,683 Signaigo June 25, 1946 2,734,821 Schaufelberger Feb. 14, 1956 2,740,708 Papee Apr. 3, 1956 2,767,083 Machiw Oct. 16, 1956 2,819,188 Metheny Jan. 7, 1958 2,827,400 Eisenberg et a1 Mar. 8, 1958 2,994,369 Carlin Aug. 1, 1961 2,994,577 Silverman Aug. 1, 1961 3,062,680 Meddings Nov. 6, 1962
Claims (2)
1. A METHOD OF DEPOSITING METAL-CONTAINING MATERIAL ONTO AN EXTENDED SUPPORT WHICH COMPRISES FORMING A SOLUTION OF A SOLUBLE COMPLES OF METAL OF THE METAL-CONTAINING MATERIAL TO BE DEPOSITED ON SAID SUPPORT, IMMERSING SAID SUPPORT IN SAID SOLUTION AND REDUCING SAID METALCONTAINING MATERIAL FROM SAID SOLUTION BY PRESSUREING SAID SOLUTION WITH HYDROGEN AND MAINTAINING SADI SOLUTION AT AN EFFECTIVE REDUCTION TEMPERATURE WHILE MAINTAINING THE SYSTEM IN A SUBSTANTIALLY QUIESCENT STATE WHEREBY SAID METAL-CONTAINING MATERIAL IS DEPOSITED WITHOUT NUCLEATION ON SAID SUPPORT AS A SUBSTANTIALLY CONTINUOUS FILM.
7. A METHOD ACCORDING TO CLAIM 1 WHEREIN SAID DEPOSIT OF METAL-CONTAINING MATERIAL IS ACTIVATED FOR USE AS A CATAYLST BY SULFIDING SAID DEPOSIT TO CONVERT THE METAL TO IT CORRESPONDING SULFIDE.
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US3231520A (en) * | 1962-12-26 | 1966-01-25 | Texaco Inc | Catalyst and method of making same |
US3271135A (en) * | 1963-12-26 | 1966-09-06 | Davidoff Charles | Gold recovery process using an alkali metal hydrosulfite with a water soluble oxygen containing compound |
US3271136A (en) * | 1964-07-08 | 1966-09-06 | Davidoff Charles | Gold recovery process using an alkali metal hydrosulfite with a water soluble alkalimetal alkanoate |
US3301688A (en) * | 1965-10-11 | 1967-01-31 | Modine Mfg Co | Bonding compositions |
US3325733A (en) * | 1960-12-27 | 1967-06-13 | Jerome H Lemelson | Measuring device using variable thickness thin film tunneling layer |
US3326725A (en) * | 1962-12-12 | 1967-06-20 | Bbc Brown Boveri & Cie | Catalyst electrode insensitive to oxidation for electrochemical processes |
US3336160A (en) * | 1963-11-06 | 1967-08-15 | Gen Motors Corp | Method of making contacts on semiconductors |
US3338725A (en) * | 1964-05-14 | 1967-08-29 | M & T Chemicals Inc | Novel plating process and composition |
US3338740A (en) * | 1963-11-06 | 1967-08-29 | Gen Motors Corp | Electroless nickel plating |
US3348969A (en) * | 1963-11-06 | 1967-10-24 | Gen Motors Corp | Electroless nickel plating |
US3362783A (en) * | 1963-12-23 | 1968-01-09 | Texaco Inc | Treatment of exhaust gases |
US3364075A (en) * | 1965-04-05 | 1968-01-16 | Allis Chalmers Mfg Co | Method of producing a nickel-silver-phosphorus alloy fuel cell electrode catalyst |
US3402067A (en) * | 1965-09-24 | 1968-09-17 | Engelhard Ind Inc | Method for depositing aluminum film |
US3411953A (en) * | 1965-02-05 | 1968-11-19 | Allis Chalmers Mfg Co | Method of producing a fuel cell electrode containing a nickel-phosphorus alloy as the catalyst |
US3437605A (en) * | 1965-01-26 | 1969-04-08 | Engelhard Ind Inc | Method of preparing a supported catalyst |
US3471413A (en) * | 1965-07-22 | 1969-10-07 | Universal Oil Prod Co | Formation of a catalyst carrying alumina surface on a base element |
US3486928A (en) * | 1965-10-21 | 1969-12-30 | Int Nickel Co | Bath and process for platinum and platinum alloys |
US3489602A (en) * | 1965-05-25 | 1970-01-13 | Hughes Aircraft Co | Method of impregnating porous tungsten and resulting article |
US3494785A (en) * | 1962-12-07 | 1970-02-10 | Teledyne Inc | Process for applying metal and metallic alloy coatings on sieve size discrete nuclear fuel particles |
US3505095A (en) * | 1967-04-05 | 1970-04-07 | Atomic Energy Commission | Preplating treatment for maraging steels |
US3506462A (en) * | 1966-10-29 | 1970-04-14 | Nippon Electric Co | Electroless gold plating solutions |
US3516850A (en) * | 1966-09-16 | 1970-06-23 | Texas Instruments Inc | Process for metal coating a hydrogen permeable material |
US3535149A (en) * | 1968-06-13 | 1970-10-20 | Sylvania Electric Prod | Process for producing particulate nickel coated alkaline earth carbonates |
US3622367A (en) * | 1970-03-24 | 1971-11-23 | Mobil Oil Corp | Contact deposition of platinum and other metals |
US3635761A (en) * | 1970-05-05 | 1972-01-18 | Mobil Oil Corp | Electroless deposition of metals |
DE2159346A1 (en) * | 1970-12-02 | 1972-06-08 | Shell Int Research | New silver catalysts and their manufacture and use, especially in the manufacture of ethylene oxide |
US3770500A (en) * | 1969-09-16 | 1973-11-06 | Tdk Electronics Co Ltd | Magnetic materials and method of making same |
US3850732A (en) * | 1970-12-02 | 1974-11-26 | Amchem Prod | Zirconium rinse for phosphate coated metal surfaces |
DE2418712A1 (en) * | 1974-04-18 | 1975-10-30 | Nischne Tagil | Silver catalyst for oxidation of methanol to formaldehyde - prepd. by impregnating carrier with complex silver ion soln. and reducing |
US3928663A (en) * | 1974-04-01 | 1975-12-23 | Amp Inc | Modified hectorite for electroless plating |
US3962494A (en) * | 1971-07-29 | 1976-06-08 | Photocircuits Division Of Kollmorgan Corporation | Sensitized substrates for chemical metallization |
EP0055311A1 (en) * | 1980-12-30 | 1982-07-07 | Exxon Research And Engineering Company | Catalysts and hydrocarbon treating processes utilizing the same |
US4486233A (en) * | 1982-07-30 | 1984-12-04 | Office National D'etudes Et De Recherche Aerospatiales | Nickel and/or cobalt chemical plating bath using a reducing agent based on boron or phosphorous |
US4758025A (en) * | 1985-06-18 | 1988-07-19 | Mobil Oil Corporation | Use of electroless metal coating to prevent galling of threaded tubular joints |
US5091223A (en) * | 1989-06-27 | 1992-02-25 | Henkel Corporation | Process for forming a blackened layer on a zinciferous surface by contacting the surface with an aqueous solution containing nickel and cobalt ions |
US5256441A (en) * | 1992-08-04 | 1993-10-26 | Amp-Akzo Corporation | Ductile copper |
US20060035101A1 (en) * | 2004-08-16 | 2006-02-16 | Jikang Yuan | Multinary bulk and thin film alloys and methods of making |
US20110152069A1 (en) * | 2008-09-02 | 2011-06-23 | Diaz Velasquez Jose De Jesus | Process for making a catalyst suitable for direct coal liquefaction and the catalyst thereof |
US20110308356A1 (en) * | 2009-01-11 | 2011-12-22 | Izabella Alekseevna Logvinenko | Method for sorption recovery of precious metals |
US9187702B2 (en) | 2009-07-01 | 2015-11-17 | Chevron U.S.A. Inc. | Hydroprocessing catalyst and method of making the same |
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Cited By (44)
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US3325733A (en) * | 1960-12-27 | 1967-06-13 | Jerome H Lemelson | Measuring device using variable thickness thin film tunneling layer |
US3494785A (en) * | 1962-12-07 | 1970-02-10 | Teledyne Inc | Process for applying metal and metallic alloy coatings on sieve size discrete nuclear fuel particles |
US3326725A (en) * | 1962-12-12 | 1967-06-20 | Bbc Brown Boveri & Cie | Catalyst electrode insensitive to oxidation for electrochemical processes |
US3231520A (en) * | 1962-12-26 | 1966-01-25 | Texaco Inc | Catalyst and method of making same |
US3348969A (en) * | 1963-11-06 | 1967-10-24 | Gen Motors Corp | Electroless nickel plating |
US3338740A (en) * | 1963-11-06 | 1967-08-29 | Gen Motors Corp | Electroless nickel plating |
US3336160A (en) * | 1963-11-06 | 1967-08-15 | Gen Motors Corp | Method of making contacts on semiconductors |
US3338741A (en) * | 1963-11-06 | 1967-08-29 | Gen Motors Corp | Electroless nickel plating |
US3362783A (en) * | 1963-12-23 | 1968-01-09 | Texaco Inc | Treatment of exhaust gases |
US3271135A (en) * | 1963-12-26 | 1966-09-06 | Davidoff Charles | Gold recovery process using an alkali metal hydrosulfite with a water soluble oxygen containing compound |
US3338725A (en) * | 1964-05-14 | 1967-08-29 | M & T Chemicals Inc | Novel plating process and composition |
US3271136A (en) * | 1964-07-08 | 1966-09-06 | Davidoff Charles | Gold recovery process using an alkali metal hydrosulfite with a water soluble alkalimetal alkanoate |
US3437605A (en) * | 1965-01-26 | 1969-04-08 | Engelhard Ind Inc | Method of preparing a supported catalyst |
US3411953A (en) * | 1965-02-05 | 1968-11-19 | Allis Chalmers Mfg Co | Method of producing a fuel cell electrode containing a nickel-phosphorus alloy as the catalyst |
US3364075A (en) * | 1965-04-05 | 1968-01-16 | Allis Chalmers Mfg Co | Method of producing a nickel-silver-phosphorus alloy fuel cell electrode catalyst |
US3489602A (en) * | 1965-05-25 | 1970-01-13 | Hughes Aircraft Co | Method of impregnating porous tungsten and resulting article |
US3471413A (en) * | 1965-07-22 | 1969-10-07 | Universal Oil Prod Co | Formation of a catalyst carrying alumina surface on a base element |
US3402067A (en) * | 1965-09-24 | 1968-09-17 | Engelhard Ind Inc | Method for depositing aluminum film |
US3301688A (en) * | 1965-10-11 | 1967-01-31 | Modine Mfg Co | Bonding compositions |
US3486928A (en) * | 1965-10-21 | 1969-12-30 | Int Nickel Co | Bath and process for platinum and platinum alloys |
US3516850A (en) * | 1966-09-16 | 1970-06-23 | Texas Instruments Inc | Process for metal coating a hydrogen permeable material |
US3506462A (en) * | 1966-10-29 | 1970-04-14 | Nippon Electric Co | Electroless gold plating solutions |
US3505095A (en) * | 1967-04-05 | 1970-04-07 | Atomic Energy Commission | Preplating treatment for maraging steels |
US3535149A (en) * | 1968-06-13 | 1970-10-20 | Sylvania Electric Prod | Process for producing particulate nickel coated alkaline earth carbonates |
US3770500A (en) * | 1969-09-16 | 1973-11-06 | Tdk Electronics Co Ltd | Magnetic materials and method of making same |
US3622367A (en) * | 1970-03-24 | 1971-11-23 | Mobil Oil Corp | Contact deposition of platinum and other metals |
US3635761A (en) * | 1970-05-05 | 1972-01-18 | Mobil Oil Corp | Electroless deposition of metals |
DE2159346A1 (en) * | 1970-12-02 | 1972-06-08 | Shell Int Research | New silver catalysts and their manufacture and use, especially in the manufacture of ethylene oxide |
US3850732A (en) * | 1970-12-02 | 1974-11-26 | Amchem Prod | Zirconium rinse for phosphate coated metal surfaces |
US3962494A (en) * | 1971-07-29 | 1976-06-08 | Photocircuits Division Of Kollmorgan Corporation | Sensitized substrates for chemical metallization |
US3928663A (en) * | 1974-04-01 | 1975-12-23 | Amp Inc | Modified hectorite for electroless plating |
DE2418712A1 (en) * | 1974-04-18 | 1975-10-30 | Nischne Tagil | Silver catalyst for oxidation of methanol to formaldehyde - prepd. by impregnating carrier with complex silver ion soln. and reducing |
EP0055311A1 (en) * | 1980-12-30 | 1982-07-07 | Exxon Research And Engineering Company | Catalysts and hydrocarbon treating processes utilizing the same |
US4486233A (en) * | 1982-07-30 | 1984-12-04 | Office National D'etudes Et De Recherche Aerospatiales | Nickel and/or cobalt chemical plating bath using a reducing agent based on boron or phosphorous |
US4758025A (en) * | 1985-06-18 | 1988-07-19 | Mobil Oil Corporation | Use of electroless metal coating to prevent galling of threaded tubular joints |
US5091223A (en) * | 1989-06-27 | 1992-02-25 | Henkel Corporation | Process for forming a blackened layer on a zinciferous surface by contacting the surface with an aqueous solution containing nickel and cobalt ions |
US5256441A (en) * | 1992-08-04 | 1993-10-26 | Amp-Akzo Corporation | Ductile copper |
US20060035101A1 (en) * | 2004-08-16 | 2006-02-16 | Jikang Yuan | Multinary bulk and thin film alloys and methods of making |
WO2006023521A2 (en) * | 2004-08-16 | 2006-03-02 | University Of Connecticut | Multinary bulk and thin film alloys and methods of making |
WO2006023521A3 (en) * | 2004-08-16 | 2006-11-09 | Univ Connecticut | Multinary bulk and thin film alloys and methods of making |
US20110152069A1 (en) * | 2008-09-02 | 2011-06-23 | Diaz Velasquez Jose De Jesus | Process for making a catalyst suitable for direct coal liquefaction and the catalyst thereof |
US8476182B2 (en) * | 2008-09-02 | 2013-07-02 | Jose De Jesus Diaz Velasquez | Process for making a catalyst suitable for direct coal liquefaction and the catalyst thereof |
US20110308356A1 (en) * | 2009-01-11 | 2011-12-22 | Izabella Alekseevna Logvinenko | Method for sorption recovery of precious metals |
US9187702B2 (en) | 2009-07-01 | 2015-11-17 | Chevron U.S.A. Inc. | Hydroprocessing catalyst and method of making the same |
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