US20090304569A1 - Activated ignition promoters for metal catalyzed reactions - Google Patents
Activated ignition promoters for metal catalyzed reactions Download PDFInfo
- Publication number
- US20090304569A1 US20090304569A1 US12/459,976 US45997609A US2009304569A1 US 20090304569 A1 US20090304569 A1 US 20090304569A1 US 45997609 A US45997609 A US 45997609A US 2009304569 A1 US2009304569 A1 US 2009304569A1
- Authority
- US
- United States
- Prior art keywords
- ignition
- catalyst
- platinum
- article
- catalysts
- 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.)
- Abandoned
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 123
- 239000002184 metal Substances 0.000 title claims abstract description 123
- 238000006555 catalytic reaction Methods 0.000 title description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 200
- 150000002739 metals Chemical class 0.000 claims abstract description 45
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000011282 treatment Methods 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 139
- 230000001737 promoting effect Effects 0.000 claims description 75
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 57
- 239000010948 rhodium Substances 0.000 claims description 55
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 53
- 229910052697 platinum Inorganic materials 0.000 claims description 53
- 238000000576 coating method Methods 0.000 claims description 36
- 229910052703 rhodium Inorganic materials 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 22
- 229910052737 gold Inorganic materials 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 22
- 229910052741 iridium Inorganic materials 0.000 claims description 22
- 229910052702 rhenium Inorganic materials 0.000 claims description 22
- 229910052684 Cerium Inorganic materials 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 21
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 21
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 21
- 229910000765 intermetallic Inorganic materials 0.000 claims description 19
- 229910002056 binary alloy Inorganic materials 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 18
- -1 platinum (II) halides Chemical class 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 2
- VBWYZPGRKYRKNV-UHFFFAOYSA-N 3-propanoyl-1,3-benzoxazol-2-one Chemical compound C1=CC=C2OC(=O)N(C(=O)CC)C2=C1 VBWYZPGRKYRKNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910018944 PtBr2 Inorganic materials 0.000 claims description 2
- 229910019032 PtCl2 Inorganic materials 0.000 claims description 2
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 2
- FXGFZZYDXMUETH-UHFFFAOYSA-L difluoroplatinum Chemical compound F[Pt]F FXGFZZYDXMUETH-UHFFFAOYSA-L 0.000 claims description 2
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 claims description 2
- INXLGDBFWGBBOC-UHFFFAOYSA-N platinum(2+);dicyanide Chemical compound [Pt+2].N#[C-].N#[C-] INXLGDBFWGBBOC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- VFKKSKGQZDULMV-UHFFFAOYSA-J tetrafluoroplatinum Chemical compound F[Pt](F)(F)F VFKKSKGQZDULMV-UHFFFAOYSA-J 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 2
- FDSBSAUFURGCAI-UHFFFAOYSA-N platinum dihydride Chemical class [PtH2] FDSBSAUFURGCAI-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 34
- 230000004913 activation Effects 0.000 abstract description 8
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 230000008901 benefit Effects 0.000 description 11
- 238000011068 loading method Methods 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 150000003058 platinum compounds Chemical class 0.000 description 8
- 230000001788 irregular Effects 0.000 description 7
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 4
- 238000009529 body temperature measurement Methods 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000010725 compressor oil Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- 229910001151 AlNi Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006189 Andrussov oxidation reaction Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010961 commercial manufacture process Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
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- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- C—CHEMISTRY; METALLURGY
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
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- C01B21/265—Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
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- C01B21/267—Means for preventing deterioration or loss of catalyst or for recovering lost catalyst
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/0216—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1023—Catalysts in the form of a monolith or honeycomb
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to promoting ignition of catalysts used in metal catalyzed reactions.
- the invention is directed to ignition promoting articles used in industrial scale metal catalyzed oxidation reactions including, but not limited to, the manufacture of hydrogen cyanide (Andrussov process), nitric acid (Ostwald process), synthesis gas (carbon monoxide and hydrogen), olefins, alkynes and formaldehyde.
- the invented ignition promoting articles improves catalytic converter light off efficiency, provides lowered temperatures for catalyst light off, provides light off of used, damaged and or contaminated catalysts, prevents multiple light off failures and increases the overall yields of products at constant reactant(s) conversion from a particular catalyst.
- the invention is further directed to methods for preparing activated metal ignition promoters and to metal catalyzed processes using the catalyst ignition promoters.
- a number of important chemical manufacturing processes are metal catalyzed oxidations. Examples include, but are not limited to, manufacture of hydrogen cyanide from methane and ammonia, acetylene from methane and oxygen, nitric acid from the oxidation of ammonia (Ostwald process), synthesis gas from steam reforming of methane, ethylene from ethane, propylene from propane, and formaldehyde from methanol.
- the commercial manufacture of hydrogen cyanide is a metal catalyzed oxidative coupling of methane and ammonia. Ignition of reactants occurs by passing preheated feed gases on platinum/rhodium gauzes at temperatures greater than 270° C.
- Catalyst ignition also referred to as catalyst light off
- Catalyst ignition at relatively low temperature is highly desirable.
- U.S. Pat. No. 4,863,893 describes one approach to lowering the ignition temperature of ammonia oxidation in the manufacture of nitric acid, which involves use of platinum-rhodium and platinum-palladium-rhodium gauzes bearing a platinum coating in excess of 4.0 g/m 2 of platinum loading to the bulk area of the gauze (considered a sheet) to lower the ignition temperature required for light off in ammonia oxidation, especially if hydrogen is used as ignition fuel.
- plating large or entire areas of woven catalyst gauzes with platinum black is expensive, cumbersome and not commercially feasible.
- One impediment to a commercially viable catalyst ignition promotion process is the identification of one or more optimal ignition promoters that provide adequate catalyst ignition, including catalyst ignition in the presence of one or more contaminants, ignition of used catalysts, ignition of damaged catalysts, catalyst ignition coupled to good product(s) conversion at constant reactant(s) conversion, including suitable product selectivity.
- catalyst ignition promoters comprising one or more activated metals that are easily prepared from a number of metal sources, including spent catalysts, new catalysts, damaged catalysts, contaminated catalysts and combinations thereof.
- the metals are activated quickly and are prepared in the form of ignition promoting articles that are placed in contact with the catalysts to provide effective catalyst ignition, independent of the quality of the metals that comprise the catalytic converter.
- the one or more activated metals comprising the ignition promoter are prepared by contacting them with one or more chemical treatments or combinations of one or more chemical and physical treatments.
- the activated metal components are fabricated into suitable ignition promoting articles, referred to as ignition strips, that are placed in contact with one or more catalysts.
- the ignition promoters reduce the activation energy for catalyst ignition (also referred to “light off”), enabling ignition of catalyst gauzes that are new, used, contaminated, damaged and combinations thereof at a relatively low auto-ignition temperatures.
- a catalyst ignition promoting article comprising: one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, the article further comprising less than 1 percent by weight of a metal coating, based on the weight of the article, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; wherein the metal is deposited on the article using one or more chemical treatments or a combination of one or more chemical and physical treatments.
- a process for preparing one or more catalyst ignition promoters comprising the step of treating one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, with one or more chemical treatments or a combination of one or more chemical and physical treatments; wherein each section of the catalyst is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the catalyst, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- a process for preparing one or more catalyst ignition promoting articles comprising the steps of: (a) preparing one or more articles from one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; (b) contacting each article with one or more chemical treatments or a combination of one or more chemical and physical treatments, wherein each article is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the article, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- a process for igniting one or more catalysts selected from the group consisting of new catalysts, used catalysts, recycled catalysts, reconditioned catalysts, damaged catalysts, contaminated catalysts and combinations thereof comprising the step of contacting each catalyst with one or more ignition promoting articles.
- a process for reconstructing catalytic sites in a catalyst comprising the step of contacting the catalyst with one or more ignition promoting articles or treating one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, with one or more chemical treatments or a combination of one or more chemical and physical treatments; wherein each section of the catalyst is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the catalyst, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- a process for increasing catalytic sites in a catalyst comprising the step of contacting the catalyst with one or more ignition promoting articles or treating one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, with one or more chemical treatments or a combination of one or more chemical and physical treatments; wherein each section of the catalyst is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the catalyst, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- the present invention provides one or more catalyst ignition promoting articles for industrial scale metal catalyzed reactions.
- the catalyst ignition promoting articles are easily prepared from a number of metal sources, including but not limited to for example, metals used to prepare catalysts, new catalysts, spent catalysts, damaged catalysts, recycled catalysts, reconditioned catalysts, contaminated catalysts and combinations thereof.
- a specific ignition promoting article is prepared from its corresponding catalyst as the metal source.
- the specific ignition promoting article is prepared from metal sources other than the corresponding catalyst.
- the ignition promoters reduce the activation energy for catalyst ignition (also referred to “light off”), enabling ignition of catalyst gauzes that are new, used, contaminated, damaged, recycled, reconditioned and combinations thereof at a relatively low auto-ignition temperatures.
- Suitable metals and metal sources used in accordance with the invention include, but are not limited to, nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, vanadium, niobium, indium, cerium and alloys thereof.
- Suitable alloys include, but are not limited to for example, binary alloys such as Pt/Rh, Pt/Ni, Pt/Co, Pt/Ag, Pt/Au, Pt/Cu, Pt/Ir, Pt/Re, Pt/Ru, Pt/Mo, Pt/Ce, Pd/Rh, Pd/Ni, Pd/Co, Pd/Ag, Pd/Cu, Rh/Co, Rh/Ni, Rh/Ag, Rh/Ru; ternary alloys such as Pt/Pd/Rh, Pt/Pd/Ni, Pt/Pd/Ag, Pt/Pd/Ru, and Pt/Pd/Co.
- binary alloys such as Pt/Rh, Pt/Ni, Pt/Co, Pt/Ag, Pt/Au, Pt/Cu, Pt/Ir, Pt/Re, Pt/Ru, Pt/Mo, Pt/Ce, Pd/Rh, P
- intermetallics refer to discrete intermediate compounds having stoichiometric or non-stoichiometric formulas, as compared to alloys (solid solutions of two or more metals).
- the ignition promoting article is prepared in a variety of three-dimensional forms.
- the three-dimensional form of a specific ignition promoting article corresponds to the three-dimensional form of a specific catalyst.
- the three-dimensional form of a specific ignition promoting article corresponds to a three-dimensional form different than a specific catalyst.
- Suitable forms of the ignition promoting article include, but are not limited to for example, fibers, wires, needles, foams, spongy masses, porous solids, porous particles, fibrous sheets, knitted gauzes, woven gauzes and combinations thereof.
- the ignition promoting articles takes the form of the catalyst used in a specific metal catalyzed reaction.
- the ignition promoting articles takes a form different from the catalyst used in a specific metal catalyzed reaction.
- the ignition promoting article further comprises less than 1 percent by weight of a metal coating, based on the weight of the article.
- the weight of the metal coating, based on the weight of the article is between 0.01 and 1 percent be weight, including from 0.05 to 0.75 percent by weight.
- the metal coating comprises one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, vanadium, niobium, indium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; wherein the metal is deposited on the article using one or more chemical treatments or a combination of one or more chemical and physical treatments.
- the metal coating comprises the same composition as the catalyst.
- the metal coating comprises a different composition as the catalyst.
- the amount of metal loading on the ignition promoting article is less than 0.5 g/m 2 of metal(s) per square meter of ignition promoting article. According to one embodiment the amount of metal loading is between 0.0003 g/cm 2 to 0.5 g/m 2 , including from 0.004 g/cm 2 to 0.001 g/m 2 .
- the process for preparing one or more catalyst ignition promoting articles comprises the steps of: (a) preparing one or more articles from one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; (b) contacting each article with one or more chemical treatments or a combination of one or more chemical and physical treatments, wherein each article is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the article, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- Activated metal is deposited on the ignition promoting article or sections of the catalyst using one or more chemical treatments or a combination of one or more chemical and physical treatments.
- activated metals refer to metals having a higher amount and proportion of catalytically active sites as compared to untreated metals.
- the activated metal components are prepared into ignition promoting articles, also referred to as ignition strips, that are placed in contact with a specific catalyst.
- activated metal components are incorporated in the treated sections of the catalyst.
- One advantage of the invention is that the ignition promoters in the form of small strips or treated sections of the catalyst have a large total surface area, as compared to completely coated, large area catalytic gauzes characterized by surface coatings in excess of 50 cm 2 /g to 500 cm 2 /g of metal required for ignition.
- a second advantage is that the metal loading in the ignition promoters of the present invention is small as to compared to conventional methods requiring at least 0.5 g metal/m 2 catalyst for ignition.
- a third advantage of the invention is that the catalyst ignition promoting articles are quickly prepared and contacted with the catalyst, minimizing reactor down time as compared to special operations required for coating large area catalysts, storing the coated catalysts safely and corresponding costs associated with the relatively large amounts of platinum coating required.
- a fourth advantage of the invention is that used catalysts, damaged catalysts, contaminated catalyst and combinations thereof are successfully ignited using the ignition promoting articles.
- One or more chemical treatments or combinations of one or more chemical and physical treatments are used to incorporate activated metals in the ignition promoters so that they contain higher amounts and proportions of catalytically active sites as compared to untreated metals.
- Suitable chemical treatments and physical treatments include, but are not limited to for example, contacting ignition promoting strip with one or more metal compounds.
- the one or more metal compounds are thermally and photochemically decomposed, including chemically and electrochemically reduced, to provide active catalytic metal sites on the ignition promoting strips.
- Other methods of incorporating activated metals on the ignition promoting strips include, but are not limited to for example, chemical vapor deposition of catalytically active metals on the surface of the ignition strip, precipitation of catalytically active metals on the surface of the ignition strip using electroless deposition, electroplating catalytically active metals on the surface of the ignition strip, sputtering catalytically active metals on the surface of the ignition strip, and physical vapor deposition of catalytically active metals on the surface of the ignition strip.
- Suitable metal compounds used to deposit activated metals on ignition promoting strips include, but are not limited to for example, contacting the ignition promoting article with metal compounds selected from the group consisting of: platinum black, Raney Ni, metal halides wherein the metal includes, but is not limited to for example, nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, vanadium, niobium, indium, cerium and combinations thereof and wherein the halides are selected from the group consisting of F, Cl, Br, I and combinations thereof, metal ammonia complexes, organometallic compounds, including but not limited to for example, metal carbonyls and metal olefins wherein the metal includes, but is not limited to for example, nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, vana
- a process for igniting one or more catalysts selected from the group consisting of new catalysts, used catalysts, recycled catalysts, reconditioned catalysts, damaged catalysts, contaminated catalysts and combinations thereof comprising the step of contacting each catalyst with one or more ignition promoting articles.
- ignition promoting articles of the invention reduce the activation energy for light off of a new catalyst, enabling the new catalyst to ignite at relatively lower temperatures, namely temperatures similar to that of corresponding used catalysts which have relatively higher surface areas. Ignition of reactants occurs at the sites where the ignition promoting articles contact the catalyst, subsequently leading to complete ignition of the catalyst, as confirmed by visual observations and by temperature measurements using thermocouple devices.
- ignition promoting articles of the invention afford light off of catalysts contaminated with one or more organic compounds that include, but are not limited to for example, lubricating oils, compressor oils, paraffin residues, C8-C22 hydrocarbons in reactants, oil residues, residues in reactants, reactor debris, soot, dust, product residues and combinations thereof.
- Ignition of reactants occurs at uncontaminated sites where the ignition promoting articles contact the catalyst, subsequently leading to complete ignition of the catalyst, as confirmed by visual observations and by temperature measurements using thermocouple devices.
- Ignition promoted light off is successful in contaminated catalysts using a short pre-heating period while admitting the feed into the catalytic converter for immediate light off.
- This method minimizes further contamination of the catalyst, as compared to conventional light off methods.
- ignition promoting articles of the invention afford light off of catalysts damaged by events that include, but are not limited to for example, high temperature flare off of reactants, oxidation of catalyst, destruction of catalytic sites, unfavorable reactions not leading to products and combinations thereof.
- Ignition promoting articles are used contact the catalyst at damaged sites, providing an additional advantage of repair of the damaged catalyst site. Ignition of reactants occurs at damaged sites where the ignition promoting articles contact the catalyst, subsequently leading to complete ignition of the catalyst, as confirmed by visual observations and by temperature measurements using thermocouple devices.
- ignition promoting articles of the invention afford light off of used catalysts, recycled catalysts and reconditioned catalysts by reconstructing catalytic sites.
- Generation of product specific catalytic sites is a dynamic process during catalysis and catalytic sites are continuously created and destroyed. In some cases, destruction of catalytic sites is so severe that product yields drop precipitously and the reaction is shut down.
- Ignition promoting articles are successfully used to reconstruct catalytic sites with immediate light off of the used, recycled or reconditioned catalyst. Ignition of reactants occurs at reconstructed catalytic sites where the ignition promoting articles contact the catalyst, subsequently leading to complete ignition of the catalyst, as confirmed by visual observations and by temperature measurements using thermocouple devices.
- the present invention provides one or more catalyst ignition promoting articles for industrial scale metal catalyzed reactions.
- the invention provides activated ignition promoting articles for the production of hydrogen cyanide from the oxidative coupling of methane and ammonia using Pt/Rh gauzes.
- gauzes typically consist of metal alloys, including but not limited to for example; Pt/Rh (90%/10%), Pt/Rh (95%/5%) and Pt/Rh/Pd (90%/5%/5%).
- Gauzes are typically flat woven meshes of metal wires having a minimum diameter of approximately 0.003 inch (0.008 cm) with at least 80 meshes per inch (31.5 meshes/cm).
- Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst gauze having a minimum area of 4 cm 2 .
- the gauzes were placed in an aqueous solution of a platinum compound and were calcined to decompose the platinum compound to a coating of Pt metal on each gauze.
- the metal loading on each article ranged from 0.01 to 1% by weight Pt, based on the weight of the article.
- the articles were placed in contact with Pt/Rh catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures between 230 to 260° C. and climbed to operating temperatures between 1100 and 1250° C. in a plant operating at an optimized reactant mass throughput. Ignition on first attempt occurred with a frequency greater than 95%.
- the catalytic activation of hydrogen cyanide occurs at crystalline cyanide sites on the surface of the multi-layered gauze.
- Suitable compounds used to chemically treat and to incorporate activated metals in ignition promoting strips include, but are not limited to for example, compounds selected from the group consisting of: platinum black, platinum sponge Raney Ni, platinum (II) halides (PtF 2 , PtCl 2 , PtBr 2 and PtI 2 ), platinum (IV) halides (PtF 4 , PtCl 4 , PtBr 4 and PtI 4 ), platinum(VI) halides (PtF 6 2 ⁇ , PtCl 6 2 ⁇ , PtBr 6 2 ⁇ and PtI 6 2 ⁇ ), Zeise salts, ammonia complexes of Pt(II), Pt(IV) and Pt(VI), chloroplatinic acid (H 2 PtCl 6 ), bromoplatinic acid (H 2 PtBr 6 ), organometallic Pt(0) compounds including but not limited to for example, bis(ethylene)platinum compounds and divinyltetralkylsi
- a catalytic form of platinum, platinum black is deposited on the ignition strips by thermal, photochemical decomposition of the platinum compounds listed above. Electrochemical and chemical reduction of platinum compounds also generates platinum black on the ignition strips. Platinum as well as other catalytic metals (e.g. Raney Ni) is also deposited on the ignition strips by chemical or combinations of chemical and physical treatments.
- the ignition promoters reduce the activation energy for catalyst ignition (also referred to “light off”), enabling ignition of catalyst gauzes that are new, used, contaminated, damaged and combinations thereof at a relatively low auto-ignition temperatures.
- the catalytic ignition promoters of the invention restores hydrogen cyanide catalytic sites to crystalline active forms.
- the ignition promoters moreover, enhance the activity of a spent catalyst, resulting in a net increase in the catalytic cyanide sites.
- the use of activated catalyst ignition promoters has resulted in an unexpected improvement in the reliability of catalyst light off in the manufacture of hydrogen cyanide from methane and ammonia, resulting in higher manufacturing production, reduction of ammonia and methane flaring which damages and or destroys the catalyst and increased catalyst lifetime.
- the invention provides activated ignition promoting articles for the metal catalyzed production of nitric acid from the oxidation of an ammonia-air mixture.
- Gauzes typically used for the production of nitric acid typically consist of platinum group metal alloys primarily 90% Pt:10% Rh and 90% Pt:5% Rh:5% Pd and are typically woven meshes of about 0.003 of an inch diameter wires at about 80 wires per lineal inch. Other combinations of mesh and wire diameter may be used to advantage.
- Roberts and Gillespie “Estimation of Platinum Catalyst Requirement for Ammonia Oxidation” 45 Advances in Chemistry Series No. 133, Chemical Reaction Engineering II page 600-611.
- Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst gauze having a minimum area of 4 cm 2 .
- the gauzes were placed in an aqueous solution of a platinum compound and were calcined to decompose the platinum compound to a coating of Pt metal on each gauze.
- the metal loading on each article ranged from 0.01 to 1% by weight Pt, based on the weight of the article.
- the articles were placed in contact with Pt/Rh catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures between 230 to 260° C. in a plant operating at a reactant mass throughput of 8500 lbs/ft 2 -hr. Ignition on first attempt occurred with a frequency greater than 90%.
- Activated ignition promoting articles are prepared from sections of the gauzes as described above and treated with chloroplatinic acid followed by thermal reduction to generate a high concentration of platinum black sites on the ignition strips as compared to the catalytic gauze.
- the ignition promoting articles of the invention have a number of advantages over completely coating conventional ammonia oxidation catalyst gauzes.
- One advantage is that the metal loading in the ignition promoters of the present invention is less than the 0.5 g metal/m 2 catalyst gauze required for ignition.
- a second advantage of the invention is that the catalyst ignition promoting articles are quickly prepared and contacted with the catalyst, minimizing reactor down time as compared to special operations required for coating large area catalysts, storing the coated catalysts safely and the expense associated with platinum coating required.
- a third advantage of the invention is that used catalysts, damaged catalysts, contaminated catalyst and combinations thereof are successfully ignited using the ignition promoting articles.
- the invention provides activated ignition promoting articles for the metal catalyzed production of acetylene from the oxidation of a methane-air mixture.
- Conventional ignition of reactants occurs by passing preheated feed gases on multiple layers of platinum gauze and Pt-coated monoliths (e.g. ⁇ -Alumina) or rhodium gauze at temperatures greater than 500 to 800° C.
- the catalytic activation of methane and subsequent coupling of methyl radicals occurs at crystalline sites on the surface of the catalyst.
- Activated ignition strips of the invention are prepared from articles made from the catalysts by depositing a coating of Pt black from platinum compounds described above, Pt/C, combinations of Pt black and Pt/C or by depositing a coating of Rh metal by thermally decomposing rhodium halides (e.g. RhCl 3 , (NH 3 ) 2 RhCl 6 ).
- Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst having a minimum area of 4 cm 2 . The metal loading on each article ranged from 0.01 to 1% by weight Pt or Rh, based on the weight of the article. The articles were placed in contact with the catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures less than 500° C. operating at space velocities of at least 105 h ⁇ 1 .
- the invention provides activated ignition promoting articles for the metal catalyzed production of C2-C8 alkenes from the oxidation of a C2-C8 alkanes-air mixture. Ignition of reactants occurs by passing preheated feed gases on multiple layers of supported and unsupported platinum or rhodium catalysts at temperatures greater than 500° C.
- Activated ignition strips of the invention are prepared from articles made from the catalysts by depositing a coating of Pt black from platinum compounds described above, Pt/C, combinations of Pt black and Pt/C or by depositing a coating of Rh metal by thermally decomposing rhodium halides (e.g. RhCl 3 , (NH 3 ) 2 RhCl 6 ).
- Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst having a minimum area of 4 cm 2 .
- the metal loading on each article ranged from 0.01 to 1% by weight Pt or Rh, based on the weight of the article.
- the articles were placed in contact with the catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures less than 500° C. operating at space velocities of at least 10 5 h ⁇ 1 .
- the invention provides activated ignition promoting articles for the metal catalyzed production of synthesis gas from the oxidation of methane by steam reforming. Ignition of reactants occurs by passing preheated feed gases on a Ni catalyst, including Ni supported on a ceramic monolith) at temperatures between 1000-1500° C. under pressure (20 bar to 85 bar).
- Activated ignition strips of the invention are prepared from articles made from the catalysts by depositing a coating of Ni from nickel compounds, including but not limited to for example Raney Ni from an AlNi alloy as described above, or by depositing a coating of Ni metal by chemically reducing or thermally decomposing nickel halides (e.g. NiCl 2 ), nickel carbonyl Ni(CO) 4 or organometallic Ni compounds.
- Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst having a minimum area of 4 cm 2 .
- the metal loading on each article ranged from 0.01 to 1% by weight Ni, based on the weight of the article.
- the articles were placed in contact with the catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures less than 1000° C. operating at space velocities of at least 10 4 h ⁇ 1 .
- the invention provides activated ignition promoting articles for the metal catalyzed production of formaldehyde from the oxidation of methanol using a silver catalyst and wet gas recycle (WGR) or a Pt-coated monolith at short contact times. Ignition of reactants occurs by passing preheated feed gases on crystalline needles of silver at temperatures greater than 600° C. under pressure. The catalytic activation of methane occurs at crystalline H 2 CO sites on the surface of the multi-layered gauze.
- Activated ignition strips of the invention are prepared from articles made from the Ag catalyst by depositing a coating of Ag from silver compounds, including but not limited to for example silver halides (e.g.
- Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst having a minimum area of 4 cm 2 .
- the metal loading on each article ranged from 0.01 to 1% by weight Ag, based on the weight of the article.
- the articles were placed in contact with the catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures less than 600° C. operating at space velocities of at least 10 4 h ⁇ 1 .
- Piece of spent or used platinum gauze strips were each cut into irregular sections (2.54 cm by 5.08 cm).
- the strips were activated by immersing them in an aqueous solution of chloroplatinic acid (13.7%, containing 6.5 wt. % Pt) for 2 hours at room temperature in a crucible.
- the chloroplatinic acid solution was decanted and the crucible was placed in to a furnace and heated to 450° C. under an argon atmosphere for 2 hours.
- the gauze strips were cooled to room temperature and stored in the dark under an argon atmosphere.
- the activated gauze strips incorporated an additional 0.20 wt. % Pt as a result of the chemical treatment.
- Ignition Ignition Catalyst Type Temp. (° C.) attempt Pt/Rh gauze (new) 260 1st Pt/Rh gauze (used) 234 1st Pt/Rh gauze (damaged) 270 1st Pt/Rh gauze (new, contaminated) 273 1st Pt/Rh gauze (contaminated) 230 1st Pt/Rh gauze new 267 1st
- the catalyst ignition promoter strips were effective also at igniting damaged and contaminated gauzes, significantly reducing costs associated with ignition failure. In all attempts catalyst light off has been successful on first attempts using the activated ignition promoter strips of the invention.
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Abstract
The inventors have discovered catalyst ignition promoters comprising one or more activated metals. The catalyst ignition promoters are easily prepared from a number of metal sources, including spent catalysts, are activated quickly and provide effective catalyst ignition independent of the quality of the metals that comprise the catalytic converter. The one or more activated metals comprising the ignition promoter are prepared by contacting them with one or more chemical treatments. The activated metal components are prepared into suitable articles, referred to as ignition strips, that are placed in contact with one or more oxidative coupling catalysts, typically in the form of gauzes. The ignition promoters reduce the activation energy for catalyst ignition (also referred to “light off”), enabling ignition of catalyst gauzes that are new, used, contaminated, damaged and combinations thereof at a relatively low auto-ignition temperatures.
Description
- The present invention relates to promoting ignition of catalysts used in metal catalyzed reactions. In particular, the invention is directed to ignition promoting articles used in industrial scale metal catalyzed oxidation reactions including, but not limited to, the manufacture of hydrogen cyanide (Andrussov process), nitric acid (Ostwald process), synthesis gas (carbon monoxide and hydrogen), olefins, alkynes and formaldehyde. The invented ignition promoting articles improves catalytic converter light off efficiency, provides lowered temperatures for catalyst light off, provides light off of used, damaged and or contaminated catalysts, prevents multiple light off failures and increases the overall yields of products at constant reactant(s) conversion from a particular catalyst. The invention is further directed to methods for preparing activated metal ignition promoters and to metal catalyzed processes using the catalyst ignition promoters.
- A number of important chemical manufacturing processes are metal catalyzed oxidations. Examples include, but are not limited to, manufacture of hydrogen cyanide from methane and ammonia, acetylene from methane and oxygen, nitric acid from the oxidation of ammonia (Ostwald process), synthesis gas from steam reforming of methane, ethylene from ethane, propylene from propane, and formaldehyde from methanol. The commercial manufacture of hydrogen cyanide is a metal catalyzed oxidative coupling of methane and ammonia. Ignition of reactants occurs by passing preheated feed gases on platinum/rhodium gauzes at temperatures greater than 270° C. Unfortunately, ignition start up problems, including failures to ignite new catalysts, used catalysts, contaminated catalysts and damaged catalysts results in significant production losses, including additional catalyst costs and reactor down time associated with subsequent failed attempts to restart catalyst ignition. In addition, overall yields of catalyzed products are negatively impacted as a result of one or more catalyst ignition failures. There are a number of possible causes for catalyst ignition failure including, but not limited to, contamination of the catalyst due to one or more organic residues from feed gases, one or more lubricating and/or compressor oils associated with the reactor and combinations thereof. Despite techniques known in the art to enhance the catalyzed ignition process, including increasing the flammability of the incoming reactant(s) feed, raising feed temperature, and increasing reactor pressure, catalyst ignition problems have provided a number of obstacles to overcome.
- Catalyst ignition (also referred to as catalyst light off) at relatively low temperature is highly desirable. U.S. Pat. No. 4,863,893 describes one approach to lowering the ignition temperature of ammonia oxidation in the manufacture of nitric acid, which involves use of platinum-rhodium and platinum-palladium-rhodium gauzes bearing a platinum coating in excess of 4.0 g/m2 of platinum loading to the bulk area of the gauze (considered a sheet) to lower the ignition temperature required for light off in ammonia oxidation, especially if hydrogen is used as ignition fuel. Unfortunately, plating large or entire areas of woven catalyst gauzes with platinum black is expensive, cumbersome and not commercially feasible. It would be highly desirable, therefore, to provide one or more catalyst ignition promoters which can initiate catalyst ignition at relatively low auto-ignition temperatures. One impediment to a commercially viable catalyst ignition promotion process is the identification of one or more optimal ignition promoters that provide adequate catalyst ignition, including catalyst ignition in the presence of one or more contaminants, ignition of used catalysts, ignition of damaged catalysts, catalyst ignition coupled to good product(s) conversion at constant reactant(s) conversion, including suitable product selectivity. Despite attempts to provide new and improved catalysts for metal catalyzed oxidations, no attempts have been made to identify catalyst ignition promoters or that utilize activated metals as igniter strips for catalyst ignition.
- The inventors have discovered catalyst ignition promoters comprising one or more activated metals that are easily prepared from a number of metal sources, including spent catalysts, new catalysts, damaged catalysts, contaminated catalysts and combinations thereof. The metals are activated quickly and are prepared in the form of ignition promoting articles that are placed in contact with the catalysts to provide effective catalyst ignition, independent of the quality of the metals that comprise the catalytic converter. The one or more activated metals comprising the ignition promoter are prepared by contacting them with one or more chemical treatments or combinations of one or more chemical and physical treatments. The activated metal components are fabricated into suitable ignition promoting articles, referred to as ignition strips, that are placed in contact with one or more catalysts. The ignition promoters reduce the activation energy for catalyst ignition (also referred to “light off”), enabling ignition of catalyst gauzes that are new, used, contaminated, damaged and combinations thereof at a relatively low auto-ignition temperatures.
- Accordingly, there is provided a catalyst ignition promoting article comprising: one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, the article further comprising less than 1 percent by weight of a metal coating, based on the weight of the article, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; wherein the metal is deposited on the article using one or more chemical treatments or a combination of one or more chemical and physical treatments.
- There is provided a process for preparing one or more catalyst ignition promoters comprising the step of treating one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, with one or more chemical treatments or a combination of one or more chemical and physical treatments; wherein each section of the catalyst is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the catalyst, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- There is provided a process for preparing one or more catalyst ignition promoting articles comprising the steps of: (a) preparing one or more articles from one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; (b) contacting each article with one or more chemical treatments or a combination of one or more chemical and physical treatments, wherein each article is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the article, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- There is provided a process for lowering the ignition temperature of one or more reactants using one or more metal catalysts comprising the step of contacting each catalyst with one or more ignition promoting articles.
- There is provided a process for igniting one or more catalysts selected from the group consisting of new catalysts, used catalysts, recycled catalysts, reconditioned catalysts, damaged catalysts, contaminated catalysts and combinations thereof, comprising the step of contacting each catalyst with one or more ignition promoting articles.
- There is provided a process for reconstructing catalytic sites in a catalyst comprising the step of contacting the catalyst with one or more ignition promoting articles or treating one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, with one or more chemical treatments or a combination of one or more chemical and physical treatments; wherein each section of the catalyst is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the catalyst, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- There is provided a process for increasing catalytic sites in a catalyst comprising the step of contacting the catalyst with one or more ignition promoting articles or treating one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, with one or more chemical treatments or a combination of one or more chemical and physical treatments; wherein each section of the catalyst is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the catalyst, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- There is provided a process for manufacturing hydrogen cyanide comprising the step of contacting a platinum/rhodium catalyst with one or more ignition promoting articles.
- Accordingly, the present invention provides one or more catalyst ignition promoting articles for industrial scale metal catalyzed reactions. The catalyst ignition promoting articles are easily prepared from a number of metal sources, including but not limited to for example, metals used to prepare catalysts, new catalysts, spent catalysts, damaged catalysts, recycled catalysts, reconditioned catalysts, contaminated catalysts and combinations thereof. According to one embodiment, a specific ignition promoting article is prepared from its corresponding catalyst as the metal source. According to a separate embodiment, the specific ignition promoting article is prepared from metal sources other than the corresponding catalyst. The ignition promoters reduce the activation energy for catalyst ignition (also referred to “light off”), enabling ignition of catalyst gauzes that are new, used, contaminated, damaged, recycled, reconditioned and combinations thereof at a relatively low auto-ignition temperatures.
- Suitable metals and metal sources used in accordance with the invention include, but are not limited to, nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, vanadium, niobium, indium, cerium and alloys thereof. Suitable alloys include, but are not limited to for example, binary alloys such as Pt/Rh, Pt/Ni, Pt/Co, Pt/Ag, Pt/Au, Pt/Cu, Pt/Ir, Pt/Re, Pt/Ru, Pt/Mo, Pt/Ce, Pd/Rh, Pd/Ni, Pd/Co, Pd/Ag, Pd/Cu, Rh/Co, Rh/Ni, Rh/Ag, Rh/Ru; ternary alloys such as Pt/Pd/Rh, Pt/Pd/Ni, Pt/Pd/Ag, Pt/Pd/Ru, and Pt/Pd/Co. Other suitable metals include intermetallics selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, and cerium. Examples include, but are not limited to, Pt0.1-1.99Rh0.99-0.01, Pt2Rh, Ni0.1-1.99Pt0.99-0.01, PtxRhy, PtxNiy, PtxCoy, PtxRhyIrz, and PtxRhyIrz, wherein x=0.1-100, y=0.1-100 and z=0.1-100. As used herein, intermetallics refer to discrete intermediate compounds having stoichiometric or non-stoichiometric formulas, as compared to alloys (solid solutions of two or more metals).
- The ignition promoting article is prepared in a variety of three-dimensional forms. According to one embodiment, the three-dimensional form of a specific ignition promoting article corresponds to the three-dimensional form of a specific catalyst. According to a separate embodiment, the three-dimensional form of a specific ignition promoting article corresponds to a three-dimensional form different than a specific catalyst. Suitable forms of the ignition promoting article include, but are not limited to for example, fibers, wires, needles, foams, spongy masses, porous solids, porous particles, fibrous sheets, knitted gauzes, woven gauzes and combinations thereof. According to one embodiment, the ignition promoting articles takes the form of the catalyst used in a specific metal catalyzed reaction. According to a separate embodiment, the ignition promoting articles takes a form different from the catalyst used in a specific metal catalyzed reaction.
- The ignition promoting article further comprises less than 1 percent by weight of a metal coating, based on the weight of the article. According to one embodiment, the weight of the metal coating, based on the weight of the article is between 0.01 and 1 percent be weight, including from 0.05 to 0.75 percent by weight. The metal coating comprises one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, vanadium, niobium, indium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; wherein the metal is deposited on the article using one or more chemical treatments or a combination of one or more chemical and physical treatments. According to one embodiment the metal coating comprises the same composition as the catalyst. According to separate embodiment, the metal coating comprises a different composition as the catalyst.
- The amount of metal loading on the ignition promoting article is less than 0.5 g/m2 of metal(s) per square meter of ignition promoting article. According to one embodiment the amount of metal loading is between 0.0003 g/cm2 to 0.5 g/m2, including from 0.004 g/cm2 to 0.001 g/m2.
- The process for preparing one or more catalyst ignition promoting articles comprises the steps of: (a) preparing one or more articles from one or more sections of a catalyst comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; (b) contacting each article with one or more chemical treatments or a combination of one or more chemical and physical treatments, wherein each article is coated with a metal coating comprising less than 1 percent by weight of a metal coating, based on the weight of the article, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof.
- Activated metal is deposited on the ignition promoting article or sections of the catalyst using one or more chemical treatments or a combination of one or more chemical and physical treatments. As used herein, activated metals refer to metals having a higher amount and proportion of catalytically active sites as compared to untreated metals. According to one embodiment of the invention, the activated metal components are prepared into ignition promoting articles, also referred to as ignition strips, that are placed in contact with a specific catalyst. According to a separate embodiment, activated metal components are incorporated in the treated sections of the catalyst. One advantage of the invention is that the ignition promoters in the form of small strips or treated sections of the catalyst have a large total surface area, as compared to completely coated, large area catalytic gauzes characterized by surface coatings in excess of 50 cm2/g to 500 cm2/g of metal required for ignition. A second advantage is that the metal loading in the ignition promoters of the present invention is small as to compared to conventional methods requiring at least 0.5 g metal/m2 catalyst for ignition. A third advantage of the invention is that the catalyst ignition promoting articles are quickly prepared and contacted with the catalyst, minimizing reactor down time as compared to special operations required for coating large area catalysts, storing the coated catalysts safely and corresponding costs associated with the relatively large amounts of platinum coating required. A fourth advantage of the invention is that used catalysts, damaged catalysts, contaminated catalyst and combinations thereof are successfully ignited using the ignition promoting articles.
- One or more chemical treatments or combinations of one or more chemical and physical treatments are used to incorporate activated metals in the ignition promoters so that they contain higher amounts and proportions of catalytically active sites as compared to untreated metals. Suitable chemical treatments and physical treatments include, but are not limited to for example, contacting ignition promoting strip with one or more metal compounds. The one or more metal compounds are thermally and photochemically decomposed, including chemically and electrochemically reduced, to provide active catalytic metal sites on the ignition promoting strips. Other methods of incorporating activated metals on the ignition promoting strips include, but are not limited to for example, chemical vapor deposition of catalytically active metals on the surface of the ignition strip, precipitation of catalytically active metals on the surface of the ignition strip using electroless deposition, electroplating catalytically active metals on the surface of the ignition strip, sputtering catalytically active metals on the surface of the ignition strip, and physical vapor deposition of catalytically active metals on the surface of the ignition strip.
- Suitable metal compounds used to deposit activated metals on ignition promoting strips include, but are not limited to for example, contacting the ignition promoting article with metal compounds selected from the group consisting of: platinum black, Raney Ni, metal halides wherein the metal includes, but is not limited to for example, nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, vanadium, niobium, indium, cerium and combinations thereof and wherein the halides are selected from the group consisting of F, Cl, Br, I and combinations thereof, metal ammonia complexes, organometallic compounds, including but not limited to for example, metal carbonyls and metal olefins wherein the metal includes, but is not limited to for example, nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, ruthenium, molybdenum, vanadium, niobium, indium, cerium and combinations thereof, and metal hydride complexes.
- There is provided a process for igniting one or more catalysts selected from the group consisting of new catalysts, used catalysts, recycled catalysts, reconditioned catalysts, damaged catalysts, contaminated catalysts and combinations thereof, comprising the step of contacting each catalyst with one or more ignition promoting articles.
- According to one embodiment, ignition promoting articles of the invention reduce the activation energy for light off of a new catalyst, enabling the new catalyst to ignite at relatively lower temperatures, namely temperatures similar to that of corresponding used catalysts which have relatively higher surface areas. Ignition of reactants occurs at the sites where the ignition promoting articles contact the catalyst, subsequently leading to complete ignition of the catalyst, as confirmed by visual observations and by temperature measurements using thermocouple devices.
- According to a separate embodiment, ignition promoting articles of the invention afford light off of catalysts contaminated with one or more organic compounds that include, but are not limited to for example, lubricating oils, compressor oils, paraffin residues, C8-C22 hydrocarbons in reactants, oil residues, residues in reactants, reactor debris, soot, dust, product residues and combinations thereof. Ignition of reactants occurs at uncontaminated sites where the ignition promoting articles contact the catalyst, subsequently leading to complete ignition of the catalyst, as confirmed by visual observations and by temperature measurements using thermocouple devices. Ignition promoted light off is successful in contaminated catalysts using a short pre-heating period while admitting the feed into the catalytic converter for immediate light off. One advantage is that this method minimizes further contamination of the catalyst, as compared to conventional light off methods.
- According to a separate embodiment, ignition promoting articles of the invention afford light off of catalysts damaged by events that that include, but are not limited to for example, high temperature flare off of reactants, oxidation of catalyst, destruction of catalytic sites, unfavorable reactions not leading to products and combinations thereof. Ignition promoting articles are used contact the catalyst at damaged sites, providing an additional advantage of repair of the damaged catalyst site. Ignition of reactants occurs at damaged sites where the ignition promoting articles contact the catalyst, subsequently leading to complete ignition of the catalyst, as confirmed by visual observations and by temperature measurements using thermocouple devices.
- According to a separate embodiment, ignition promoting articles of the invention afford light off of used catalysts, recycled catalysts and reconditioned catalysts by reconstructing catalytic sites. Generation of product specific catalytic sites is a dynamic process during catalysis and catalytic sites are continuously created and destroyed. In some cases, destruction of catalytic sites is so severe that product yields drop precipitously and the reaction is shut down. Ignition promoting articles are successfully used to reconstruct catalytic sites with immediate light off of the used, recycled or reconditioned catalyst. Ignition of reactants occurs at reconstructed catalytic sites where the ignition promoting articles contact the catalyst, subsequently leading to complete ignition of the catalyst, as confirmed by visual observations and by temperature measurements using thermocouple devices.
- The present invention provides one or more catalyst ignition promoting articles for industrial scale metal catalyzed reactions.
- According to one embodiment, the invention provides activated ignition promoting articles for the production of hydrogen cyanide from the oxidative coupling of methane and ammonia using Pt/Rh gauzes. Such gauzes typically consist of metal alloys, including but not limited to for example; Pt/Rh (90%/10%), Pt/Rh (95%/5%) and Pt/Rh/Pd (90%/5%/5%). Gauzes are typically flat woven meshes of metal wires having a minimum diameter of approximately 0.003 inch (0.008 cm) with at least 80 meshes per inch (31.5 meshes/cm). Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst gauze having a minimum area of 4 cm2. The gauzes were placed in an aqueous solution of a platinum compound and were calcined to decompose the platinum compound to a coating of Pt metal on each gauze. The metal loading on each article ranged from 0.01 to 1% by weight Pt, based on the weight of the article. The articles were placed in contact with Pt/Rh catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures between 230 to 260° C. and climbed to operating temperatures between 1100 and 1250° C. in a plant operating at an optimized reactant mass throughput. Ignition on first attempt occurred with a frequency greater than 95%. The catalytic activation of hydrogen cyanide occurs at crystalline cyanide sites on the surface of the multi-layered gauze.
- Suitable compounds used to chemically treat and to incorporate activated metals in ignition promoting strips include, but are not limited to for example, compounds selected from the group consisting of: platinum black, platinum sponge Raney Ni, platinum (II) halides (PtF2, PtCl2, PtBr2 and PtI2), platinum (IV) halides (PtF4, PtCl4, PtBr4 and PtI4), platinum(VI) halides (PtF6 2−, PtCl6 2−, PtBr6 2− and PtI6 2−), Zeise salts, ammonia complexes of Pt(II), Pt(IV) and Pt(VI), chloroplatinic acid (H2PtCl6), bromoplatinic acid (H2PtBr6), organometallic Pt(0) compounds including but not limited to for example, bis(ethylene)platinum compounds and divinyltetralkylsiloxanePt(0) compounds, platinum acetylacetonate, platinum cyanide, and platinum hydride complexes. A catalytic form of platinum, platinum black is deposited on the ignition strips by thermal, photochemical decomposition of the platinum compounds listed above. Electrochemical and chemical reduction of platinum compounds also generates platinum black on the ignition strips. Platinum as well as other catalytic metals (e.g. Raney Ni) is also deposited on the ignition strips by chemical or combinations of chemical and physical treatments.
- Generation of specific hydrogen cyanide catalytic sites is a dynamic process, with catalytic sites being continuously created and destroyed as the reaction proceeds. During the catalytic process, the surface area of the catalytic gauze increases considerably, restructuring to form facets, pits, whiskers and crystalline catalytic sites and amorphous regions which are catalytically inactive. The restructuring of catalytic sites in the gauze is anisotropic in nature and the crystalline catalytically active sites migrate to amorphous catalytically inactive sites. Towards the end of the lifetime of the gauze, the reaction sites reach the lower metal layers and the aged gauze stops generating new catalytic cyanide sites. Moreover, the population of catalytic sites is gradually reduced over the lifetime of the catalyst, which results in reduced yields of hydrogen cyanide and the catalytic gauze is replaced.
- The ignition promoters reduce the activation energy for catalyst ignition (also referred to “light off”), enabling ignition of catalyst gauzes that are new, used, contaminated, damaged and combinations thereof at a relatively low auto-ignition temperatures. The catalytic ignition promoters of the invention restores hydrogen cyanide catalytic sites to crystalline active forms. The ignition promoters, moreover, enhance the activity of a spent catalyst, resulting in a net increase in the catalytic cyanide sites. The use of activated catalyst ignition promoters has resulted in an unexpected improvement in the reliability of catalyst light off in the manufacture of hydrogen cyanide from methane and ammonia, resulting in higher manufacturing production, reduction of ammonia and methane flaring which damages and or destroys the catalyst and increased catalyst lifetime.
- According to a separate embodiment, the invention provides activated ignition promoting articles for the metal catalyzed production of nitric acid from the oxidation of an ammonia-air mixture. Gauzes typically used for the production of nitric acid typically consist of platinum group metal alloys primarily 90% Pt:10% Rh and 90% Pt:5% Rh:5% Pd and are typically woven meshes of about 0.003 of an inch diameter wires at about 80 wires per lineal inch. Other combinations of mesh and wire diameter may be used to advantage. For a detailed report, see Roberts and Gillespie, “Estimation of Platinum Catalyst Requirement for Ammonia Oxidation” 45 Advances in Chemistry Series No. 133, Chemical Reaction Engineering II page 600-611. See also U.S. Pat. No. 3,660,024. Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst gauze having a minimum area of 4 cm2. The gauzes were placed in an aqueous solution of a platinum compound and were calcined to decompose the platinum compound to a coating of Pt metal on each gauze. The metal loading on each article ranged from 0.01 to 1% by weight Pt, based on the weight of the article. The articles were placed in contact with Pt/Rh catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures between 230 to 260° C. in a plant operating at a reactant mass throughput of 8500 lbs/ft2-hr. Ignition on first attempt occurred with a frequency greater than 90%.
- Activated ignition promoting articles are prepared from sections of the gauzes as described above and treated with chloroplatinic acid followed by thermal reduction to generate a high concentration of platinum black sites on the ignition strips as compared to the catalytic gauze. The ignition promoting articles of the invention have a number of advantages over completely coating conventional ammonia oxidation catalyst gauzes. One advantage is that the metal loading in the ignition promoters of the present invention is less than the 0.5 g metal/m2 catalyst gauze required for ignition. A second advantage of the invention is that the catalyst ignition promoting articles are quickly prepared and contacted with the catalyst, minimizing reactor down time as compared to special operations required for coating large area catalysts, storing the coated catalysts safely and the expense associated with platinum coating required. A third advantage of the invention is that used catalysts, damaged catalysts, contaminated catalyst and combinations thereof are successfully ignited using the ignition promoting articles.
- According to a separate embodiment, the invention provides activated ignition promoting articles for the metal catalyzed production of acetylene from the oxidation of a methane-air mixture. Conventional ignition of reactants occurs by passing preheated feed gases on multiple layers of platinum gauze and Pt-coated monoliths (e.g. α-Alumina) or rhodium gauze at temperatures greater than 500 to 800° C. The catalytic activation of methane and subsequent coupling of methyl radicals occurs at crystalline sites on the surface of the catalyst. Activated ignition strips of the invention are prepared from articles made from the catalysts by depositing a coating of Pt black from platinum compounds described above, Pt/C, combinations of Pt black and Pt/C or by depositing a coating of Rh metal by thermally decomposing rhodium halides (e.g. RhCl3, (NH3)2RhCl6). Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst having a minimum area of 4 cm2. The metal loading on each article ranged from 0.01 to 1% by weight Pt or Rh, based on the weight of the article. The articles were placed in contact with the catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures less than 500° C. operating at space velocities of at least 105 h−1.
- According to a separate embodiment, the invention provides activated ignition promoting articles for the metal catalyzed production of C2-C8 alkenes from the oxidation of a C2-C8 alkanes-air mixture. Ignition of reactants occurs by passing preheated feed gases on multiple layers of supported and unsupported platinum or rhodium catalysts at temperatures greater than 500° C. Activated ignition strips of the invention are prepared from articles made from the catalysts by depositing a coating of Pt black from platinum compounds described above, Pt/C, combinations of Pt black and Pt/C or by depositing a coating of Rh metal by thermally decomposing rhodium halides (e.g. RhCl3, (NH3)2RhCl6). Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst having a minimum area of 4 cm2. The metal loading on each article ranged from 0.01 to 1% by weight Pt or Rh, based on the weight of the article. The articles were placed in contact with the catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures less than 500° C. operating at space velocities of at least 105 h−1.
- According to a separate embodiment, the invention provides activated ignition promoting articles for the metal catalyzed production of synthesis gas from the oxidation of methane by steam reforming. Ignition of reactants occurs by passing preheated feed gases on a Ni catalyst, including Ni supported on a ceramic monolith) at temperatures between 1000-1500° C. under pressure (20 bar to 85 bar). Activated ignition strips of the invention are prepared from articles made from the catalysts by depositing a coating of Ni from nickel compounds, including but not limited to for example Raney Ni from an AlNi alloy as described above, or by depositing a coating of Ni metal by chemically reducing or thermally decomposing nickel halides (e.g. NiCl2), nickel carbonyl Ni(CO)4 or organometallic Ni compounds. Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst having a minimum area of 4 cm2. The metal loading on each article ranged from 0.01 to 1% by weight Ni, based on the weight of the article. The articles were placed in contact with the catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures less than 1000° C. operating at space velocities of at least 104 h−1.
- According to a separate embodiment, the invention provides activated ignition promoting articles for the metal catalyzed production of formaldehyde from the oxidation of methanol using a silver catalyst and wet gas recycle (WGR) or a Pt-coated monolith at short contact times. Ignition of reactants occurs by passing preheated feed gases on crystalline needles of silver at temperatures greater than 600° C. under pressure. The catalytic activation of methane occurs at crystalline H2CO sites on the surface of the multi-layered gauze. Activated ignition strips of the invention are prepared from articles made from the Ag catalyst by depositing a coating of Ag from silver compounds, including but not limited to for example silver halides (e.g. AgCl, AgCl2 −), silver carbonyl Ag(CO) or organometallic Ag compounds. Ignition promoting articles are prepared by cutting 7-10 irregular or regular sized sections of a used catalyst having a minimum area of 4 cm2. The metal loading on each article ranged from 0.01 to 1% by weight Ag, based on the weight of the article. The articles were placed in contact with the catalyst and ignition temperatures were measured by thermocouple devices. Ignition of preheated feed gases occurred in the vicinity of the ignition promoting articles at temperatures less than 600° C. operating at space velocities of at least 104 h−1.
- The following illustrative examples are provided to further demonstrate the utility of the present invention and are not in any way construed to be limiting. Moreover, the examples provided are representative examples that broadly enable the claimed scope of the invention.
- Piece of spent or used platinum gauze strips were each cut into irregular sections (2.54 cm by 5.08 cm). The strips were activated by immersing them in an aqueous solution of chloroplatinic acid (13.7%, containing 6.5 wt. % Pt) for 2 hours at room temperature in a crucible. The chloroplatinic acid solution was decanted and the crucible was placed in to a furnace and heated to 450° C. under an argon atmosphere for 2 hours. The gauze strips were cooled to room temperature and stored in the dark under an argon atmosphere. The activated gauze strips incorporated an additional 0.20 wt. % Pt as a result of the chemical treatment. Several pieces of the activated catalyst ignition promoter strip were placed in contact with a platinum catalyst gauze used to manufacture acetone cyanohydrin. Converter light off was successful on the first attempt. Ignition occurred at feed ratios of between 7.0 to 11.5 air/NH3 and between 0.70-1.2 CH4/NH3 as the pressure was increased from between 0 psig to 36 psig. Temperature at ignition was 234° C. and increased to 360° C. (at 28 psig) as measured using a multiplexor temperature recording unit. Thermocouples were placed beneath each igniter strip and it appears that ignition events occurred at each strip before complete gauze ignition occurred within 1 hour, based on the thermocouple readings. The low ignition temperature indicates that the activated strips were unexpectedly effective in promoting complete ignition of the catalytic gauze. Ignition data are summarized in Table 1.
-
TABLE 1 Data for ignition promoted Pt-gauzes. Ignition Ignition Catalyst Type Temp. (° C.) attempt Pt/Rh gauze (new) 260 1st Pt/Rh gauze (used) 234 1st Pt/Rh gauze (damaged) 270 1st Pt/Rh gauze (new, contaminated) 273 1st Pt/Rh gauze (contaminated) 230 1st Pt/Rh gauze new 267 1st - The catalyst ignition promoter strips were effective also at igniting damaged and contaminated gauzes, significantly reducing costs associated with ignition failure. In all attempts catalyst light off has been successful on first attempts using the activated ignition promoter strips of the invention.
- It will be understood that the embodiments of the present invention described hereinabove are merely exemplary and that a person skilled in the art may make variations and modifications without departing from the spirit and scope of the invention. All such variations and modifications are intended to be included within the scope of the present invention.
Claims (5)
1-6. (canceled)
7. A process for lowering the ignition temperature of methane and ammonia in the manufacture of hydrogen cyanide comprising the step of contacting a catalyst with one or more ignition promoting articles for manufacture of compounds selected from the group consisting of: hydrogen cyanide, nitric acid, acetylene, C2-C8 alkenes, synthesis gas, and formaldehyde, said article comprising a gauze catalyst selected from the group consisting of: a used catalyst, a contaminated catalyst, a damaged catalyst, and combinations thereof, said gauze catalyst, said articles each comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, the article further comprising less than 1 percent by weight of a metal coating, based on the weight of the article, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; wherein the one or more metals is deposited on the article using one or more chemical treatments or a combination of one or more chemical and physical treatments.
8. A process for igniting one or more catalysts selected from the group consisting of new catalysts, used catalysts, recycled catalysts, reconditioned catalysts, damaged catalysts, contaminated catalysts and combinations thereof, comprising the step of contacting each catalyst with one or more ignition promoting articles for manufacture of compounds selected from the group consisting of: hydrogen cyanide, nitric acid, acetylene, C2-C8 alkenes, synthesis gas, and formaldehyde, said article comprising a gauze catalyst selected from the group consisting of: a used catalyst, a contaminated catalyst, a damaged catalyst, and combinations thereof, said gauze catalyst, said articles each comprising one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof, the article further comprising less than 1 percent by weight of a metal coating, based on the weight of the article, of one or more metals selected from the group consisting of nickel, platinum, palladium, cobalt, rhodium, silver, gold, copper, iridium, rhenium, cerium, alloys thereof, binary alloys thereof, ternary alloys thereof, intermetallics thereof, and combinations thereof; wherein the one or more metals is deposited on the article using one or more chemical treatments or a combination of one or more chemical and physical treatments.
9. The process according to claim 7 , wherein the metal coating on the ignition promoting article is prepared from one or more compounds selected from the group consisting of: platinum black, platinum sponge Raney Ni, platinum (II) halides (PtF2, PtCl2, PtBr2 and PtI2), platinum (IV) halides (PtF4, PtCl4, PtBr4 and PtI4), platinum(VI) halides (PtF62-, PtCl62-, PtBr62- and PtI62-), Zeise salts, ammonia complexes of Pt(II), Pt(IV) and Pt(VI), chloroplatinic acid (H2PtCl6), bromoplatinic acid (H2PtBr6), organometallic Pt(0) compounds, bis(ethylene)platinum compounds and divinyltetralkylsiloxanePt(0) compounds, platinum acetylacetonate, platinum cyanide, platinum hydride complexes and combinations thereof.
10. The process according to claim 7 , wherein the weight of the metal coating on the ignition promoting article is from 0.05 to 0.75 percent by weight, based on the weight of the article.
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US12/459,976 US20090304569A1 (en) | 2004-06-03 | 2009-07-10 | Activated ignition promoters for metal catalyzed reactions |
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US63087204P | 2004-11-24 | 2004-11-24 | |
US11/143,046 US7576030B2 (en) | 2004-06-03 | 2005-06-02 | Activated ignition promoters for metal catalyzed reactions |
US12/459,976 US20090304569A1 (en) | 2004-06-03 | 2009-07-10 | Activated ignition promoters for metal catalyzed reactions |
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US12/459,976 Abandoned US20090304569A1 (en) | 2004-06-03 | 2009-07-10 | Activated ignition promoters for metal catalyzed reactions |
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EP (1) | EP1602408A3 (en) |
JP (1) | JP4086861B2 (en) |
KR (1) | KR101175583B1 (en) |
CN (1) | CN1714929B (en) |
BR (1) | BRPI0502045B1 (en) |
TW (1) | TWI398297B (en) |
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US20100261929A1 (en) * | 2007-10-23 | 2010-10-14 | Yuichiro Kinoshita | Process and apparatus for production of cyanohydrin compound, and process for production of alpha-hydroxyester compound |
US10143998B2 (en) * | 2016-02-05 | 2018-12-04 | Rohm And Haas Company | Activation energy reducers for catalytic oxidation of gaseous mixtures |
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DE10309209A1 (en) * | 2003-02-28 | 2004-09-09 | Degussa Ag | Process for the production of hydrogen cyanide by the BMA process and catalyst for its implementation |
JP5027732B2 (en) * | 2008-05-13 | 2012-09-19 | 日本碍子株式会社 | Plasma processing equipment |
GB0816705D0 (en) * | 2008-09-12 | 2008-10-22 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
US8071504B2 (en) | 2008-12-19 | 2011-12-06 | Caterpillar Inc. | Exhaust system having a gold-platinum group metal catalyst |
MX2012013521A (en) | 2010-05-24 | 2013-04-08 | Siluria Technologies Inc | Nanowire catalysts. |
MY162772A (en) | 2011-05-24 | 2017-07-14 | Siluria Technologies Inc | Catalysts for oxidative coupling of methane |
US20130158322A1 (en) | 2011-11-29 | 2013-06-20 | Siluria Technologies, Inc. | Polymer templated nanowire catalysts |
US9446397B2 (en) | 2012-02-03 | 2016-09-20 | Siluria Technologies, Inc. | Method for isolation of nanomaterials |
CA2874043C (en) | 2012-05-24 | 2021-09-14 | Siluria Technologies, Inc. | Catalytic forms and formulations |
CA2902192C (en) | 2013-03-15 | 2021-12-07 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
US9956544B2 (en) | 2014-05-02 | 2018-05-01 | Siluria Technologies, Inc. | Heterogeneous catalysts |
AU2015317805B2 (en) | 2014-09-17 | 2019-11-14 | Lummus Technology Llc | Catalysts for oxidative coupling of methane and oxidative dehydrogenation of ethane |
WO2018151733A1 (en) * | 2017-02-20 | 2018-08-23 | Rohm And Haas Company | Activation energy reducers for catalytic oxidation of gaseous mixtures |
CN107573513B (en) * | 2017-08-28 | 2020-09-08 | 济南大学 | Silver-copper dissimilar metal cluster compound and preparation method and application thereof |
CN110152719A (en) * | 2019-04-22 | 2019-08-23 | 中海油天津化工研究设计院有限公司 | A method of Pt/KL alkane hydrocarbon aromatizing catalyst is prepared by platinum source of spongy platinum |
CN111482184B (en) * | 2020-04-22 | 2023-03-21 | 江苏大学 | Cu/Pd/Au ternary composite metal catalyst and preparation method and application thereof |
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Also Published As
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JP4086861B2 (en) | 2008-05-14 |
CN1714929B (en) | 2010-05-05 |
EP1602408A2 (en) | 2005-12-07 |
BRPI0502045B1 (en) | 2020-12-01 |
KR20060046134A (en) | 2006-05-17 |
JP2005342714A (en) | 2005-12-15 |
TW200613055A (en) | 2006-05-01 |
US20050271572A1 (en) | 2005-12-08 |
CN1714929A (en) | 2006-01-04 |
BRPI0502045A (en) | 2006-01-24 |
KR101175583B1 (en) | 2012-08-21 |
TWI398297B (en) | 2013-06-11 |
US7576030B2 (en) | 2009-08-18 |
EP1602408A3 (en) | 2006-03-01 |
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