EP1718407A1 - Composition a base d'or et d' oxyde de cerium, procede de preparation et utilisation comme catalyseur, notamment pour l'oxydation du monoxyde de carbone - Google Patents
Composition a base d'or et d' oxyde de cerium, procede de preparation et utilisation comme catalyseur, notamment pour l'oxydation du monoxyde de carboneInfo
- Publication number
- EP1718407A1 EP1718407A1 EP05729335A EP05729335A EP1718407A1 EP 1718407 A1 EP1718407 A1 EP 1718407A1 EP 05729335 A EP05729335 A EP 05729335A EP 05729335 A EP05729335 A EP 05729335A EP 1718407 A1 EP1718407 A1 EP 1718407A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold
- cerium oxide
- composition according
- oxide
- composition
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 239000010931 gold Substances 0.000 title claims abstract description 58
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229910001922 gold oxide Inorganic materials 0.000 title description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- 150000002367 halogens Chemical class 0.000 claims abstract description 14
- 239000003637 basic solution Substances 0.000 claims abstract description 12
- -1 gold halide Chemical class 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000012429 reaction media Substances 0.000 claims abstract description 5
- 239000000779 smoke Substances 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 235000019504 cigarettes Nutrition 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 150000007514 bases Chemical class 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004887 air purification Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 1
- 239000000809 air pollutant Substances 0.000 claims 1
- 231100001243 air pollutant Toxicity 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 241000208125 Nicotiana Species 0.000 abstract description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 24
- 230000003197 catalytic effect Effects 0.000 description 21
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 20
- 239000012071 phase Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 14
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 229940005605 valeric acid Drugs 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 150000002344 gold compounds Chemical class 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 241000894007 species Species 0.000 description 3
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229940044927 ceric oxide Drugs 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000019506 cigar Nutrition 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011235 metanalysis Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
Definitions
- the present invention relates to a composition based on gold and cerium oxide, its preparation process and its use as a catalyst, in particular for the oxidation of carbon monoxide.
- Gold catalysts already exist which are used in particular in CO oxidation processes. Furthermore, a certain number of these oxidation processes take place at relatively low temperatures, for example below 250 ° C., in particular in gas-to-water conversion reactions. We even try to oxidize CO at room temperature, for example in air treatment processes, and / or under harsh conditions such as very high hourly volume velocities (hvv), this is the case for example treatment of cigarette smoke.
- the catalysts currently available and which can be used from an economic point of view do not have sufficient performance to meet this need.
- the object of the invention is to provide effective catalysts at low temperatures and / or high hvv.
- the composition of the invention is based on gold on a support based on cerium oxide and it is characterized in that its halogen content expressed by the halogen / gold molar ratio is at most 0.04 and in that the gold is in the form of particles of size at most 10 nm.
- the invention also relates to the process for the preparation of this composition which, according to a first embodiment, is characterized in that it comprises the following steps:
- a compound based on cerium oxide and a compound based on a gold halide is brought into contact by forming a suspension of these compounds, the pH of the medium thus formed being fixed at a value of at least 8 ; - The solid is separated from the reaction medium;
- the invention also relates to a method according to a second embodiment which is characterized in that it comprises the following steps:, - Gold is deposited on a compound based on cerium oxide by impregnation or by ion exchange;
- compositions of the invention are effective at low temperatures, at high temperatures and moreover with gold contents which are weak.
- Other characteristics, details and advantages of the invention will appear even more completely on reading the description which follows, as well as various concrete but nonlimiting examples intended to illustrate it.
- the periodic classification of the elements to which reference is made in this description is that published in the Supplement to the Bulletin of the departments Chimique de France No. 1 (January 1966). By rare earth is understood the elements of the group constituted by yttrium and the elements of the periodic classification with atomic number included inclusively between 57 and 71.
- specific surface is understood to mean the BET specific surface determined by nitrogen adsorption in accordance with ASTM standard D 3663-78 based on the BRUNAUER - EMMETT-TELLER method described in the periodical "The Journal of the American Chemical Society, 60, 309 (1938)".
- the composition of the invention comprises gold and cerium oxide. Cerium oxide forms a support.
- support must be taken in a broad sense to designate, in the composition of the invention, the constituent (s) which are predominant in the composition, the supported element being present essentially on the surface of these constituents.
- composition of the invention may contain gold with, in addition, at least one other metallic element chosen from silver, platinum, palladium and copper.
- this or these other metallic elements may be present for example in an amount of at most 400%, more particularly at most 120% and in particular between 5% and 50% relative to gold, this quantity being expressed in molar% metallic element (s) / gold.
- Compositions of this type in the case of use at high hvv, can reach their maximum effectiveness even more quickly.
- the contents of gold, or of gold and aforementioned metallic element, of the composition are not critical, they correspond to the contents generally used in catalysts to obtain a catalytic activity.
- this content is at most 5%, in particular at most 1%. It can more particularly be at most 0.5% and even at most 0.25%. Grades above 5% are generally of no economic interest.
- These contents are expressed as a percentage by mass of gold, possibly with the metallic element, relative to the cerium oxide (or to the oxides) which constitutes the support.
- the support use is made of a compound having a specific surface sufficiently high to allow a dispersion of the gold at its suitable surface so that the gold can have a sufficient catalytic activity.
- cerium oxides with a stabilized specific surface can be used.
- cerium oxides which have a high specific surface even after being exposed to high temperatures can be used.
- These oxides may have surfaces of at least 85m 2 / g, in particular at least 100m 2 / g, after calcination at a temperature between 350 and 450 ° C over a period of 6 hours for example. It is also possible to use the cerium oxide described in EP-A-300 852 which has a specific surface of at least 15 m 2 / g after calcination at a temperature between 800 ° C and 900 ° C for at least 2 hours or alternatively the cerium oxide described in EP-A-388567 which has a surface of at least 190 m / g after calcination at a temperature between 350 ° C and 450 ° C for at least 2 hours with also also a specific surface d '' at least 15m 2 / g after calcination at a temperature between 800 ° C and 900 ° C over the same period.
- compositions based on a cerium oxide and a zirconium oxide can vary over a wide range, for example in a mass ratio of cerium oxide / zirconium oxide of between 1/99 and 99/1. However, it is possible to use more particularly the compositions for which there is a cerium / zirconium atomic proportion of at least 1. Mention may thus be made of the cerium oxide described in EP-A-207857 which has a specific surface greater than 10 m 2 / g up to a temperature 900 ° C.
- This oxide may in particular have a zirconium oxide content of between 1 and 20% relative to the weight of the ceric oxide. Mention may also be made of the composition based on cerium oxide and zirconium oxide which is the subject of EP-A-605274 and in which the zirconium is in solid solution in cerium oxide. This composition can have a specific surface of at least 30 m 2 / g after calcination at 800 ° C for 6 hours. It is also possible to use, as support, compositions with high specific surface of the type based on a cerium oxide and a zirconium oxide and at least one oxide chosen from scandium oxide and earth oxides. rare other than cerium. Such compositions are in particular described in EP-A-906244.
- compositions have a cerium / zirconium atomic proportion of at least 1 as well as a specific surface of at least 35 m 2 / g after calcination for 6 hours at 900 ° C.
- This surface can more particularly be at least 40 m 2 / g. It can be even more particularly at least 45 m 2 / g.
- Usable supports are also those based on a cerium oxide and a praseodymium oxide. The amount of praseodymium can vary within wide limits.
- compositions of this type have after calcination for 6 hours at 400 ° C a surface area of at least 10m2 / g, an d preferably at least 60m2 / g and more preferably at least 80m 2 / g. Compositions of this type are described in EP-A-802824.
- a compound based on a cerium oxide and at least one oxide of another element metallic M chosen from bismuth and tin, this oxide preferably being in solid solution with cerium oxide Such compounds are described in EP-A-588691.
- the atomic ratio between the element M and the cerium can be between 1% and 50%.
- a compound based on a cerium oxide and titanium oxide can be used as support.
- the atomic ratio between the element Ti and the cerium is less than 50% and between 1% and 50% for example. It should be noted, however, that the compositions based on cerium oxide which have just been described above have been given only by way of examples.
- compositions having lower surfaces for example less than 80 m 2 / g after calcination at 350 ° C. insofar as, as indicated above, it is sufficient that these compositions have sufficient surfaces to allow gold to play its role of catalyst.
- the cerium which enters into the constitution of the support is in a form which consists essentially or solely of cerium oxide.
- amorphous species of the type for example cerium hydroxide or oxyhydroxide are present only in trace amounts, By defining by amorphous any product whose X-ray diffractogram does not have diffraction lines centered on the oxide phase or whose RX diffractogram has halos centered on the oxide phase but whose width at mid-height would make it possible to calculate, according to the Debye-Scherrer method, crystallite sizes less than 2 nm, we must hear, in the scope of the present invention, by the terms: the amorphous species are present only in trace amounts, the fact that the comparison of an RX diagram of a pure cerium oxide with that of an oxide of cerium containing these species does not show detectable differences and in particular does not show halos.
- the composition of the invention has two specific characteristics.
- the first is its halogen content.
- the halogen can more particularly be bromine or chlorine. This content, which is expressed by the halogen / gold molar ratio is at most 0.04. More particularly, it is at most 0.025 and preferably at most 0.01.
- the halogen determination can be carried out using the following method.
- the amount of catalyst required for analysis is vaporized in a flame of an oxyhydrogen torch (H 2/0 2 to about 2000 ° C).
- the resulting vapor is trapped in an aqueous solution containing hydrogen peroxide.
- a solid residue is obtained at the end of the treatment under an oxyhydrogen torch, this is suspended in the solution from which the combustion gases have been collected (water + H 2 0 2 ) and then filtered.
- the collected filtrate is then analyzed by ion chromatography and the halogen content calculated by integrating the appropriate dilution factor.
- the halogen content of the catalyst is calculated taking into account the mass of catalyst used for the analysis.
- the other characteristic is the size of the gold particles present in the composition. This size is at most 10 nm, preferably at most 3 nm.
- this size is determined from the analysis of the RX spectra of the composition, using the width (I) at half height of the gold diffraction peak.
- the size of the particles is proportional to the inverse (1/1) of the value of this width I. It will be noted that the X-ray analysis neither makes it possible to detect a phase corresponding to gold for particles whose size is smaller at 3nm nor to detect gold for gold contents lower than 0.25%. In these two cases, MET analysis can be used.
- the process for preparing the composition of the invention will now be described. This method can be implemented according to a first embodiment.
- the first step of the process consists in bringing a compound based on cerium oxide and a compound based on a gold halide and, if appropriate, a compound based on silver , platinum, palladium or copper.
- This contacting is done by forming a suspension which is generally an aqueous suspension.
- This starting suspension can be obtained from a preliminary dispersion of a support based on cerium oxide of the type described above, prepared by dispersing this support in a liquid phase, and by mixing with a solution or a dispersion of the gold compound.
- chlorine or bromine compounds of gold can be used, for example HAuCI 4 chlorauric acid or its salts like NaAuCI 4 which are the most common compounds.
- the starting suspension can be obtained for example by introducing the solution or dispersion of the gold compound into the dispersion of the support.
- the pH of the suspension thus formed is brought to a value of at least 8, more particularly at least 8.5 and even more particularly at least 9.
- a basic compound is added at the same time.
- the flow rate of basic compound can be adjusted so as to maintain the pH of the medium at a constant value, that is to say a value varying by plus or minus 0.3 pH units relative to the fixed value.
- products of the hydroxide or carbonate type Mention may be made of alkali or alkaline-earth hydroxides and ammonia. It is also possible to use secondary, tertiary or quaternary amines. Mention may also be made of urea.
- the basic compound is generally used in the form of a solution.
- a dispersion of the support and a solution or dispersion of the gold compound which have both been brought beforehand to a pH of at least 8 so that it is not necessary, when brought into contact, to add a basic compound.
- the contacting of the compound based on cerium oxide and the compound based on gold halide is generally done at room temperature but it is possible to do it hot for example at a temperature of at least 60 ° vs.
- the suspension formed during the first step of the process is generally kept under stirring for a period of a few minutes.
- the solid is separated from the reaction medium, by any known means. The solid thus obtained is then washed with a basic solution.
- this basic solution has a pH of at least 8, more particularly at least 9.
- the basic solution can be based on the same basic compounds as those which have been mentioned above.
- This washing can be carried out by any suitable method, for example using the piston washing technique or by redispersion. In the latter case, the solid is redispersed in the basic solution and then, generally after stirring, the solid is separated from the liquid medium. Washing with the basic solution can be repeated several times if necessary. It can be followed, possibly by washing with water. After washing, the solid obtained is generally dried. Drying can be done by any suitable method, for example in air or by freeze-drying. It is generally not necessary to carry out a calcination.
- the product can be subjected, in particular after drying, to a reduction treatment.
- This treatment is carried out in such a way that the whole of the gold element has a degree of oxidation lower than its degree of oxidation before treatment, this degree of oxidation before treatment generally being 3.
- the degree of oxidation of gold can be determined by techniques known to those skilled in the art, for example by the programmed temperature reduction method (RTP) or by X-ray photoelectron spectroscopy (XPS). Different types of reduction treatment can be considered.
- a chemical reduction by bringing the product into contact with a reducing agent such as ferrous, citrate or stannous ions, oxalic acid, citric acid, hydrogen peroxide, hydrides such as NaBH 4 , hydrazine (NH 2 -NH 2 ), formaldehyde in aqueous solution (H 2 CO), phosphorous reducers including tetrakis (hydroxymethyl) phosphonium chloride or NaH 2 P0 2 .
- This treatment can be done by suspending the product in an aqueous medium containing the reducing agent or also on the product in the reaction medium after the deposition of the gold.
- the treatment can be done, in this case, on a solution or suspension of the product or even on a powder.
- these treatments can be done before or after the washing step described above.
- the reduction treatment can be carried out by gas using a reducing gas which can be chosen from hydrogen, carbon monoxide or hydrocarbons, this gas can be used in any volume concentration. It is particularly possible to use hydrogen diluted in argon. In the case of a reduction treatment according to the latter type, this is done after the aforementioned washing step.
- the treatment is carried out at a temperature which is at most 200 ° C., preferably at most 180 ° C.
- the duration of this treatment can be between 0.5 and 6 hours in particular.
- calcination can optionally be carried out as described above.
- the method of the invention can also be implemented according to a second embodiment which will now be described.
- the first step consists in depositing gold and, where appropriate silver, platinum, palladium or copper, on the compound based on cerium oxide by impregnation or by ion exchange.
- the impregnation method is well known. Preferably dry impregnation is used.
- Dry impregnation consists in adding to the product to be impregnated, here the support based on cerium oxide, a volume of a solution of the gold compound which is equal to the pore volume of the solid to be impregnated.
- the gold compound is here of the same type as that which has been described above for the first embodiment. Ion exchange deposition is also a known method. The same type of gold compound can also be used there as above.
- the product from the previous step is then washed with a basic solution whose pH is at least 10, preferably at least 11. This washing can be done in the same way and with the same basic compounds as that which has been described for the method according to the first mode.
- compositions of the invention as obtained by the process described above are in the form of powders but they can optionally be shaped to be in the form of granules, beads, cylinders, extrusions or honeycombs. variable dimensions.
- compositions of the invention can be used in catalytic systems comprising a coating (wash coat) based on these compositions, on a substrate of the type, for example metallic or ceramic monolith.
- the coating may for example include alumina.
- the deposition of gold can also take place on a support previously put into a form of the type given above.
- the compositions of the invention as described above or obtained by the process detailed above, can be used more particularly, as catalysts, in the processes implementing an oxidation of carbon monoxide. They are very particularly effective for processes of this type which are carried out at low temperatures, by which is meant temperatures of at most 250 ° C. They are even effective at room temperature.
- ambient temperature is meant here and for the whole of the description, unless otherwise indicated, a temperature of at most 50 ° C., more particularly in a range from 10 ° C. to 40 ° C.
- they can also be effective under high hvv conditions which, for example, may be at least up to 600,000 cm 3 / g cata / h.
- the catalytic composition can be in the form of a powder. It can also undergo an adequate shaping, for example, it can be in the form of granules or flakes.
- the particle size of the composition can be between 1 ⁇ m and 200 ⁇ m. In the case of granules, this size can be between 700 ⁇ m and 1500 ⁇ m, for the pearls, the size can be between 200 ⁇ m and 700 ⁇ m and between 100 ⁇ m and 1500 ⁇ m for the flakes.
- the catalytic composition can be incorporated by mixing or bonding with the fiber which constitutes the filter of the cigarette (for example cellulose acetate) during the manufacture of the filter, in particular in the case of so-called “Dual filter” or “Triple filter” filters. ".
- the catalytic composition can also be deposited on the internal part of the paper wrapping the cable constituting the filter ("tipping paper") in the case of a filter of the "Patch filter” type.
- the catalytic composition may also be introduced into the cavity of a "Cavity filter” type filter.
- the reduction treatment of the composition can be carried out once it has been incorporated into the filter. The reduction treatment is then carried out according to the methods which have been described above.
- the amount of catalyst composition used is not critical. It is limited in particular by the dimensions of the filter and the pressure drop due to the presence of the composition in the filter. It is generally at most 350 mg per cigarette, preferably it is between 20 mg and 100 mg per cigarette.
- the invention therefore relates to a cigarette filter, which contains a composition as described above or obtained by the method detailed above.
- cigarette must be taken in the broad sense to cover any article intended to be smoked and containing tobacco wrapped in a tube for example based on paper or tobacco. This term therefore also applies here to cigars and cigarillos.
- results are given for the oxidation of CO. These results were obtained by implementing the catalytic CO oxidation test which is described below.
- the catalytic compound is tested in the form of flakes of 125 to 250 ⁇ m which are obtained by tableting, grinding and sieving the powder of catalytic compound.
- the catalytic compound is placed in the reactor on a frit which acts as a physical support for the powder.
- a synthetic mixture containing 1 to 10% vol of CO, 10% vol of C0 2 , 10% vol of 0 2 , 1.8% vol of H 2 0 in N 2 is passed over the catalyst.
- the gas mixture circulates continuously in a quartz reactor containing between 25 and 200 mg of catalytic compound with a flow rate of 30 L / h.
- silicon carbide SiC is added so that the sum of the masses of the catalytic compound and SiC is equal to 200 mg.
- SiC is inert with respect to the CO oxidation reaction and plays here the role of diluent making it possible to ensure the homogeneity of the catalytic bed.
- the gases leaving the reactor are analyzed by spectroscopy infrared at intervals of approximately 10s in order to measure the conversion of CO to C0 2 .
- T50% the temperature at which 50% of the CO present in the gas stream is converted to C0 2 .
- EXAMPLE 1 40 g of a Rhodia cerium oxide powder with a surface area of 170 m 2 / g are dispersed with stirring in 250 ml of water. The pH of the suspension is then adjusted to 9 by adding a solution of Na 2 C0 3 1 M. At the same time 0.8 g of HAuCI 4 .3H 2 0 (Sigma-Aldrich) are dissolved in
- the gold solution is then added in one hour to the suspension of cerium oxide.
- the pH of the suspension is maintained between pH 8.7 and 9.3 during the addition of the gold solution by adding a solution of Na 2 C0 3 1 M.
- the resulting suspension is kept stirring for 20 minutes before being filtered under vacuum.
- the cake obtained is redispersed in a solution of Na 2 C0 3 at pH 9 whose volume is equivalent to that of the mother liquors eliminated during the first filtration step.
- the suspension is kept stirring for 20 minutes. This basic washing procedure is repeated 2 more times.
- the cake obtained is finally redispersed in a volume of water equivalent to the volume of mother liquor eliminated during the first filtration and then filtered under vacuum.
- the washed cake is dried in air at 100 ° C for 2 hours and then treated
- EXAMPLE 2 The catalyst is prepared according to the same protocol as that described in Example 1 except that the washed cake is dried by lyophilization before the treatment under hydrogen. The analyzes carried out on the catalyst give the results which appear in Table 1 below.
- EXAMPLE 3 The catalyst is prepared according to the same protocol as that described in Example 1, except that the product is dried by lyophilization and is not treated under hydrogen after the drying step. The analyzes carried out on the catalyst give the results which appear in Table 1 below.
- COMPARATIVE EXAMPLE 4 The catalyst is prepared according to the same protocol as that described in Example 1 except that the product is not washed (nor washed with the solution of
- EXAMPLE 6 The catalyst is prepared according to the same protocol as that described in Example 1 except that 0.4 g of HAuCI 4 .3H 2 0 was added instead of 0.8 g and that the washed cake was freeze-dried before treatment with hydrogen. The analyzes carried out on the catalyst give the results which appear in Table 1 below.
- EXAMPLE 7 The catalyst is prepared according to the same protocol as that described in Example 1 except that 0.2 g of HAuCI .3H 2 0 was added instead of 0.8 g and that the washed cake was lyophilized before hydrogen treatment. The analyzes carried out on the catalyst give the results which appear in Table 1 below.
- COMPARATIVE EXAMPLE 8 This example describes a product for which the gold is deposited on the support by a process having pH conditions different from those of the invention and without basic washing. 3 g of the starting cerium oxide powder of Example 1 are dispersed in 300 ml of water at 60 ° C with stirring.
- COMPARATIVE EXAMPLE 9 This example describes a product for which the gold is deposited on the support by an impregnation process without basic washing.
- the catalyst is obtained by impregnating an aqueous solution of
- the aqueous solution is evaporated and dried.
- the powder obtained is then calcined for 2 hours in air at 500 ° C and then treated for 1 hour at 500 ° C under a mixture of hydrogen diluted to 5% in nitrogen.
- the analyzes carried out on the catalyst give the results which appear in Table 1 below.
- EXAMPLE 10 40 g of cerium oxide (starting powder of Example 1) are impregnated with 14 ml of a 0.15M aqueous solution of HAuCI 4 , 3H 2 0.
- the paste is suspended in 500 ml of an aqueous solution previously adjusted to pH 11 with Na 2 C0 3 .
- the suspension is kept stirring for 2 hours.
- the pH of the suspension is maintained at pH 11 by adding an aqueous solution of Na 2 C0 3 to 2 M.
- the suspension is then filtered under vacuum.
- the cake obtained is resuspended in a volume of pure water equivalent to the volume of mother liquors eliminated during the filtration step.
- the suspension is filtered and the cake obtained is lyophilized.
- the powder obtained is treated for 1 hour at 170 ° C. under a mixture of hydrogen diluted to 10% in argon.
- the analyzes carried out on the catalyst give the results which appear in Table 1 below.
- EXAMPLE 11 An example of the preparation of a catalyst in the form of granules is given here. 21 g of granules of cerium oxide (Ce0 2 ) / alumina (Al 2 0 3 ) 90/10 by weight of oxide and specific surface 140 m 2 / g are placed in a column. This column is connected by a circulation system to a reactor (1) containing 125 g of water. At the same time, 0.4 g of HAuCI 4 , 3H 2 0 is dissolved in a reactor (2) containing 125 g of water. The solution contained in the reactor (1) is circulated through the column containing the Ce0 2 / Al 2 0 3 granules with a flow rate of 10mL / min.
- the pH of the reactor (1) adjusted to 11 using a solution of Na 2 C0 3 1 M.
- the gold solution is introduced with stirring in the reactor (1) in 30 min.
- the pH is maintained at 11 in the reactor (1) with a solution of Na 2 C0 3 1 M.
- the solution is kept under stirring for 1 hour after the addition of the gold solution.
- the circulation is stopped between the reactor (1) and the column.
- the mother solution is drawn off, then replaced with 250 g of water (pH adjusted to 11 with 1 M Na 2 C0 3 at room temperature). Circulation is resumed between the reactor (1) and the column for 10 min. This operation is repeated twice before two new washes with 450 g of water.
- the granules are separated from the washing solution and then lyophilized. They are then reduced for 2 h at 170 ° C. by a gas mixture composed of 3 vol% of dihydrogen diluted in argon.
- the analyzes carried out on the catalyst give the results which appear in Table 1 below.
- EXAMPLE 12 40 g of a Rhodia cerium oxide powder with a surface area of 170 m 2 / g are dispersed with stirring in 250 ml of water. The pH of the suspension is then adjusted to 11 by adding a 1 M NaOH solution. At the same time, 0.8 g of HAuCI, 3H 2 0 (Sigma-Aldrich) are dissolved in 250 ml of water. The gold solution is then added in one hour to the suspension of cerium oxide. The pH of the suspension is maintained between pH 10.7 and 11.3 during the addition of the gold solution by adding a 1M NaOH solution. 27.3 g of sodium citrate (Sigma-Aldrich) are then added. The resulting suspension is kept stirring for 20 minutes before being filtered under vacuum.
- the cake obtained is redispersed in a NaOH solution at pH 11, the volume of which is equivalent to that of the mother liquors eliminated during the first filtration step.
- the suspension is kept stirring for 20 minutes. This basic washing procedure is repeated 2 more times.
- the cake obtained is finally redispersed in a volume of water equivalent to the volume of mother liquor eliminated during the first filtration and then filtered under vacuum.
- the washed cake is filtered under vacuum and then calcined for 2 hours at 200 ° C. in air.
- the analyzes carried out on the catalyst give the results which appear in Table 1 below.
- 100 mg of catalytic compound in powder form is introduced into the enclosure using a device avoiding any contact with the atmosphere outside the enclosure. The origin of the times is determined by the introduction of the catalyst into the enclosure.
- the gas phase is homogenized using a magnetic stirrer.
- the gaseous phase of the enclosure is removed through a septum using the sampling device with which a branded Micro GC HP M200 chromatograph is equipped. Hewlett Packard.
- a second step 200 mg of catalytic compound in powder form are introduced into the enclosure using a device avoiding any contact with the atmosphere outside the enclosure.
- the origin of the times is determined by the introduction of the catalyst into the enclosure.
- the gas phase is homogenized using a recirculation pump, the flow rate of which is fixed at 13.5 L / min.
- the gaseous phase of the enclosure is removed through a septum and then analyzed by gas chromatography.
- H 2 0, CO, C0 2 and CH 3 CH 2 SH are analyzed on a Hewlett Packard Micro GC HP M200 chromatograph using the sampling device with which this analyzer is equipped.
- EXAMPLE 15 The catalyst according to the example is used in the test which has been described above. The results obtained at room temperature for the conversion of valeric acid are given in table 6 below.
- EXAMPLE 16 The catalyst according to example 1 is used in the test which has been described above. The results obtained at table 7 are given at room temperature for the conversion of 200 vpm of trimethylamine.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0401615A FR2866249B1 (fr) | 2004-02-18 | 2004-02-18 | Composition a base d'or et d'oxyde de cerium, procede de preparation et utilisation comme catalyseur, notamment pour l'oxydation du monoxyde de carbone |
PCT/FR2005/000378 WO2005089937A1 (fr) | 2004-02-18 | 2005-02-17 | Composition a base d'or et d'oxyde de cerium, procede de preparation et utilisation comme catalyseur, notamment pour l'oxydation du monoxyde de carbone |
Publications (1)
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EP1718407A1 true EP1718407A1 (fr) | 2006-11-08 |
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EP05729335A Withdrawn EP1718407A1 (fr) | 2004-02-18 | 2005-02-17 | Composition a base d'or et d' oxyde de cerium, procede de preparation et utilisation comme catalyseur, notamment pour l'oxydation du monoxyde de carbone |
Country Status (4)
Country | Link |
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US (1) | US20070190347A1 (fr) |
EP (1) | EP1718407A1 (fr) |
FR (1) | FR2866249B1 (fr) |
WO (1) | WO2005089937A1 (fr) |
Families Citing this family (9)
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WO2006046145A2 (fr) * | 2004-10-25 | 2006-05-04 | Philip Morris Products S.A. | Catalyseur or-cerium permettant l'oxydation de monoxyde de carbone |
US10188140B2 (en) | 2005-08-01 | 2019-01-29 | R.J. Reynolds Tobacco Company | Smoking article |
US20070215167A1 (en) | 2006-03-16 | 2007-09-20 | Evon Llewellyn Crooks | Smoking article |
US9220301B2 (en) * | 2006-03-16 | 2015-12-29 | R.J. Reynolds Tobacco Company | Smoking article |
FR2914866B1 (fr) * | 2007-04-13 | 2012-07-20 | Rhodia Recherches & Tech | Composition a base d'or, d'oxyde de cerium et d'oxyde d'aluminium, de silicium, de tungstene, de vanadium, de molybdene ou de niobium, procede de preparation et utilisation comme catalyseur. |
US20090220697A1 (en) * | 2008-02-29 | 2009-09-03 | William Peter Addiego | Washcoat composition and methods of making and using |
CZ301720B6 (cs) * | 2008-10-17 | 2010-06-02 | Univerzita Karlova V Praze | Katalyzátor na bázi kov-CeO2 pro použití obzvlášte v palivových cláncích a zpusob jeho prípravy |
US9139433B2 (en) * | 2010-02-24 | 2015-09-22 | Corning Incorporated | Gold catalysts for co oxidation and water gas shift reactions |
CN103071492B (zh) * | 2012-12-07 | 2014-10-01 | 内蒙古大学 | 一种高效催化甲醛转化催化剂的制备方法 |
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US5446003A (en) * | 1993-01-12 | 1995-08-29 | Philip Morris Incorporated | Production of supported particulate catalyst suitable for use in a vapor phase reactor |
US6492298B1 (en) * | 1999-03-29 | 2002-12-10 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Ordinary-temperature purifying catalyst |
US6821923B1 (en) * | 1999-04-08 | 2004-11-23 | Dow Global Technologies Inc. | Method of preparing a catalyst containing gold and titanium |
-
2004
- 2004-02-18 FR FR0401615A patent/FR2866249B1/fr not_active Expired - Fee Related
-
2005
- 2005-02-17 US US10/588,642 patent/US20070190347A1/en not_active Abandoned
- 2005-02-17 EP EP05729335A patent/EP1718407A1/fr not_active Withdrawn
- 2005-02-17 WO PCT/FR2005/000378 patent/WO2005089937A1/fr active Application Filing
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WO2005089937A1 (fr) | 2005-09-29 |
FR2866249B1 (fr) | 2006-12-15 |
FR2866249A1 (fr) | 2005-08-19 |
US20070190347A1 (en) | 2007-08-16 |
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