US20100111789A1 - Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate - Google Patents
Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate Download PDFInfo
- Publication number
- US20100111789A1 US20100111789A1 US12/439,448 US43944807A US2010111789A1 US 20100111789 A1 US20100111789 A1 US 20100111789A1 US 43944807 A US43944807 A US 43944807A US 2010111789 A1 US2010111789 A1 US 2010111789A1
- Authority
- US
- United States
- Prior art keywords
- oxide
- catalyst
- cerium
- support
- suspension
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 166
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 36
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000758 substrate Substances 0.000 title description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000725 suspension Substances 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 51
- 238000001354 calcination Methods 0.000 claims abstract description 43
- 238000001246 colloidal dispersion Methods 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000889 atomisation Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 79
- 230000008569 process Effects 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- 229910052684 Cerium Inorganic materials 0.000 claims description 64
- 229910001868 water Inorganic materials 0.000 claims description 62
- 150000001875 compounds Chemical class 0.000 claims description 46
- 150000002910 rare earth metals Chemical class 0.000 claims description 46
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 43
- 239000002244 precipitate Substances 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 26
- 230000000087 stabilizing effect Effects 0.000 claims description 23
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 229910052788 barium Inorganic materials 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 20
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 20
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 18
- -1 aluminum compound Chemical class 0.000 claims description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims description 17
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 16
- 229910052712 strontium Inorganic materials 0.000 claims description 14
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- 150000001413 amino acids Chemical class 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 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 58
- 239000000243 solution Substances 0.000 description 48
- 239000006185 dispersion Substances 0.000 description 44
- 239000002609 medium Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 26
- 239000002585 base Substances 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 17
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 17
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 17
- 229910017604 nitric acid Inorganic materials 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 16
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical compound [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 description 15
- 239000007790 solid phase Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 229910002637 Pr6O11 Inorganic materials 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000006104 solid solution Substances 0.000 description 12
- 229910001593 boehmite Inorganic materials 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 7
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000001935 peptisation Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 6
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 6
- 238000010348 incorporation Methods 0.000 description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 229940044927 ceric oxide Drugs 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 229960002684 aminocaproic acid Drugs 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910001679 gibbsite Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 150000000703 Cerium Chemical class 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001785 cerium compounds Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000000604 cryogenic transmission electron microscopy Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 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
- 239000012535 impurity Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910001682 nordstrandite Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 2
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 229910020837 La—Pr Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 238000007710 freezing Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- JKAYFQPEIRPZPA-UHFFFAOYSA-N lanthanum neodymium Chemical compound [La][Nd] JKAYFQPEIRPZPA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002798 neodymium compounds Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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- 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
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to a composition having high reducibility based on a nanometric cerium oxide on a support, to its process of preparation and to its use as catalyst.
- Multifunctional catalysts are currently used for the treatment of exhaust gases for internal combustion engines (automobile afterburning catalysis).
- the term “multifunctional” is understood to mean catalysts capable of carrying out not only oxidation, in particular of carbon monoxide and hydrocarbons present in exhaust gases, but also reduction, in particular of nitrogen oxides also present in these gases (“three-way” catalysts).
- Zirconium oxide and cerium oxide today appear as two constituents which are particularly important and advantageous for catalysts of this type.
- these catalysts must exhibit good reducibility.
- reducibility is to be understood to mean, here and for the remainder of the description, the ability of the catalyst to be reduced in a reducing atmosphere and to be reoxidized in an oxidizing atmosphere. This reducibility can be measured, for example, by consumption of hydrogen in a given temperature range. It is due to the cerium, in the case of the compositions of the type of those of the invention, cerium having the property of being reduced or of being oxidized.
- a first subject matter of the invention is thus the development of such materials.
- a second subject matter of the invention is the provision of materials which satisfy the latter condition.
- the composition according to the invention comprises a supported oxide, based on a cerium oxide, on a support based on silica, alumina, titanium oxide or zirconium oxide, and it is characterized in that it comprises particles of said supported oxide, deposited on said support, which particles are separate or in the form of aggregates, with a size of at most 500 nm, and in that it exhibits, after calcination at a temperature of at least 800° C. for 6 hours, a reducibility measured between 30° C. and 900° C. of at least 80%.
- the composition comprises a supported oxide, based on a cerium oxide, on an alumina-based support, characterized in that it comprises particles of said supported oxide, deposited on said support, which particles are separate or in the form of aggregates, with a size of at most 500 nm, and in that it exhibits, after calcination at a temperature of at least 800° C. for 6 hours, a reducibility measured between 30° C. and 900° C. of at least 80%, the compositions in which the alumina support additionally comprises at least one element from the group consisting of barium and strontium being excluded.
- rare earth metal is to be understood to mean the elements of the group consisting of yttrium and the elements of the Periodic Table with an atomic number of between 57 and 71 inclusive.
- specific surface is to be understood to mean the BET specific surface determined by nitrogen adsorption in accordance with the ASTM D 3663-78 Standard, drawn up from the Brunauer-Emmett-Teller method described in the periodical “The Journal of the American Chemical Society, 60, 309 (1938)”.
- composition of the invention comprises a supported oxide in the form of particles of nanometric dimensions, these particles being deposited on a support.
- This supported oxide can be first of all an oxide of cerium alone, a simple oxide, generally in the form of ceric_oxide CeO 2 . It can also be a mixture of a cerium oxide and of at least one oxide of another element M which is chosen from zirconium and rare earth metals other than cerium. According to specific embodiments of the invention, this oxide mixture can correspond to the formula (1) Ce 1-x Zr x O 2 in which x is less than 1 or also to the formula (2) Ce 1-y-z Zr y Ln z O 2 in which y+z ⁇ 1, Ln denoting at least one rare earth metal.
- the Ce/Zr atomic ratio can vary within wide limits, for example from 0.1 to 0.9. However, more particularly, the value of x or of the sum y+z can be at most 0.5.
- the supported oxide is in the crystalline form.
- the mixture of oxides is provided in the form of a solid solution of the element M in the cerium or also in the form of a solid solution (mixed oxide) of the cerium and optionally of a rare earth metal in the zirconium, this being the case according to the respective amounts of the cerium and of the zirconium.
- the supported oxide exhibits a single phase which in fact corresponds to a crystal structure of fluorine type, just like crystalline ceric oxide CeO 2 , the unit cell parameters of which are more or less offset with respect to a pure ceric oxide, thus reflecting the incorporation of the element M in the crystal lattice of the cerium oxide.
- the supported oxide exhibits a single phase corresponding to that of a zirconium oxide crystallized in the tetragonal system in particular, thus reflecting the incorporation of the cerium and optionally of the other element in the crystal lattice of the zirconium oxide.
- the supported oxide is present in the composition of the invention in the form of particles of nanometric dimensions. This is to be understood to mean that the particles exhibit a size of at most 500 nm. It should be noted here that these particles can either be separate or in the form of aggregates. The value of 500 nm applies either to the size of the particles, when the latter are separate, or to the size of the aggregate, provided that there are aggregated particles. Furthermore, this size can more particularly be at most 50 nm and more particularly still at most 10 nm. The highest size values given above correspond to the cases where the particles are generally in an aggregated form, while the lowest values correspond to the cases where the particles are generally in a separate form.
- the particles are in the separate form with a size of approximately at most 50 nm, more particularly still of at most 10 nm, or also with a size of between 10 nm and 5 nm, and, in the case where the oxide is crystalline, they correspond to crystallites of this oxide.
- the particles are in the separate form with a size of at most 5 nm, this embodiment corresponding to the case where the content of supported oxide of the composition is relatively low, this low content being specified later.
- the size values given here and in the present description are determined either by transmission electron microscopy (TEM) or by X-ray diffraction (XRD), in particular when the oxide is crystalline.
- the particles are deposited on a support. This is to be understood to mean that the particles are predominantly present on the surface of the support, it being understood that the particles can be present inside the pores of the support but while remaining at the surface of these pores.
- the support is based on silica, on alumina, on titanium oxide or on zirconium oxide.
- this support should exhibit a high and stable specific surface, that is to say a specific surface which remains at a satisfactory value even after exposure to a high temperature.
- the silica in the case of a silica-based support, can be a precipitated silica or a pyrogenic silica.
- the silica can optionally be stabilized by a stabilizing element, such as aluminum.
- an alumina-based support use may be made here of any type of alumina capable of exhibiting a specific surface satisfactory for application in catalysis. Mention may be made of the aluminas resulting from the rapid dehydration of at least one aluminum hydroxide, such as bayerite, hydrargillite or gibbsite, or nordstrandite, and/or of at least one aluminum oxyhydroxide, such as boehmite, pseudoboehmite and diaspore.
- at least one aluminum hydroxide such as bayerite, hydrargillite or gibbsite, or nordstrandite
- at least one aluminum oxyhydroxide such as boehmite, pseudoboehmite and diaspore.
- a stabilized alumina use is made, as stabilizing element, of rare earth metals, barium, strontium, silicon and zirconium. Mention may very particularly be made, as rare earth metal, of cerium, lanthanum or the lanthanum-neodymium mixture. These elements can be used alone or in combination. Mention may be made, as advantageous combinations, of La—Ba, Ba—Pr, La—Pr—Ba and La—Pr.
- the stabilized alumina can be prepared in a way known per se, in particular by impregnation of the alumina with solutions of salts, such as nitrates, of the abovementioned stabilizing elements or also by codrying an alumina precursor and salts of these elements and then calcining.
- salts such as nitrates
- the maturing can be carried out by suspending the alumina in water and then heating at a temperature of, for example, between 70 and 110° C. After the maturing, the alumina is subjected to a heat treatment.
- Another preparation consists of a similar type of treatment but with barium or strontium.
- the content of stabilizing agent expressed as weight of stabilizing agent oxide with respect to the stabilized alumina, is generally between 1.5% and 35% or also between 1.5% and 25%, in particular between 1.5% and 15%. This content can more particularly be between 2.5% and 20%, more particularly between 2.5% and 11% or also between 5% and 20%.
- the stabilizing agent is barium and/or strontium in a content, expressed as weight of stabilizing agent oxide with respect to the stabilized alumina, of less than 10%.
- the support is based on alumina stabilized by a stabilizing element from the group consisting of barium, strontium and lanthanum and the supported oxide is, in the first case, a mixture of cerium oxide, of zirconium oxide and of oxide of a rare earth metal other than cerium which can more particularly be praseodymium or lanthanum.
- the supported oxide is a mixture of cerium oxide, of praseodymium oxide and of oxide of a rare earth metal other than cerium and praseodymium which can more particularly be lanthanum.
- the content of stabilizing element, expressed as oxide can be equal to at least 10% by weight, with respect to the stabilized alumina, and it can more particularly be between 10 and 30% by weight, in particular between 10 and 25% by weight.
- the support is essentially composed of alumina (first form) or is essentially composed of alumina stabilized by at least one element chosen from rare earth metals, silicon and zirconium (second form).
- first form alumina
- second form alumina stabilized by at least one element chosen from rare earth metals, silicon and zirconium
- the term “is essentially composed of” is understood to mean, in the case of the first form, that the support comprises only alumina and no other element capable of stabilizing the latter, it being possible for the alumina optionally to comprise the usual impurities.
- the support comprises only alumina and, as stabilizing agent, only one or more elements in combination chosen solely from the group consisting of rare earth metals, silicon and zirconium with, here again, the possible presence of impurities normally linked with the alumina and with the abovementioned element.
- a support based on alumina stabilized by a stabilizing element chosen from rare earth metals, barium and strontium or essentially composed of alumina stabilized with this same stabilizing element it may be noted here that the preparation of the stabilized alumina can be carried out during the actual preparation of the composition according to the invention. This preparation will be described later.
- the support can also be made of titanium oxide, more particularly of titanium oxide in the anatase form.
- titanium oxide can be prepared, for example, by the processes described in EP-A-319 365 or in EP-A-351 270 and it can also comprise a stabilizing agent of rare earth metal or alkaline earth metal type.
- the support can be a tetragonal or monoclinic zirconium oxide which is optionally stabilized, for example by a rare earth metal.
- the support can be composed of a combination of the abovementioned oxides, either in the form of mixtures of these oxides or in the form of mixed oxides (solid solutions), such as silica/alumina, titanium oxide/silica or zirconium oxide/silica mixed oxides.
- the content of supported oxide, for example cerium oxide, of the composition of the invention is generally at most 75% by weight of the whole of the composition. It can in particular be at most 60%, more particularly at most 50% and more particularly still at most 30%.
- the content of supported oxide can correspond to the values which have just been given and it can also be more particularly at most 55%.
- the minimum content of supported oxide is set according to the performances desired for the composition.
- this minimum content is generally at least 3% by weight, more particularly at least 4% by weight.
- the particles of the supported oxide can be in the separate form with a size of at most 5 nm.
- This embodiment preferably corresponds to the compositions in which the content of supported oxide is at most 20% by weight, more particularly at most 15% by weight and more particularly still at most 10% by weight.
- the content of supported oxides can more particularly be equal to or greater than 15%, more particularly between 15 and 30%.
- compositions of the invention are reducibility.
- the reducibility of the compositions is determined by the measurement of their hydrogen consumption, measured between 30° C. and 600° C. or 900° C. This measurement is carried out by programmed reduction in temperature using hydrogen diluted in argon. A signal is detected with a thermoconductivity detector. The consumption of hydrogen is calculated from the missing surface area of the hydrogen signal from the base line at 30° C. to the base line at 600° C. or 900° C.
- the degree of reducibility represents the percentage of reduced cerium, it being understood that 1 ⁇ 2 mol of H 2 consumed and measured by the method described above corresponds to 1 mol of reduced Ce(IV).
- the reducibility measured between 30° C. and 900° C. corresponds to the percentage of the total cerium present in the supported oxide which has been reduced, this percentage being measured by the method described above in the temperature range extending from 30° C. to 900° C.
- the reducibility measured between 30° C. to 600° C. corresponds to the same measurement but carried out in the temperature range from 30° C. to 600° C.
- the overall reducibility of the cerium and the praseodymium is calculated.
- the overall reducibility of the cerium and of the praseodymium is calculated by relating the experimental hydrogen consumption of the composition to the sum of the theoretical hydrogen consumptions corresponding to the complete reduction of the cerium and to the complete reduction of the praseodymium.
- the experimental hydrogen consumption is calculated from the missing surface area of the hydrogen signal from the base line at 30° C. to the base line at 900° C., when the reducibility is measured between 30° C. and 900° C.
- the theoretical hydrogen consumption for the complete reduction of the cerium is calculated as above on the assumption that all the cerium is initially at the +IV state and that 1 ⁇ 2 mol of H 2 is consumed to reduce 1 mol of Ce(IV).
- the theoretical hydrogen consumption for the complete reduction of the praseodymium is calculated analogously on the assumption that 2 ⁇ 3 of the praseodymium is present at the +IV oxidation state in Pr 6 O 11 and that 1 ⁇ 2 mol of H 2 is consumed to reduce 1 mol of Pr(IV).
- compositions of the invention exhibit a reducibility, measured between 30° C. and 900° C., of at least 80%. This reducibility thus measured can more particularly be at least 85% and more particularly still at least 90%.
- a more specific embodiment of the invention gives compositions having a high reducibility even in a relatively low temperature range, that is to say of at most 600° C.
- This embodiment corresponds to the case where the supported oxide is cerium oxide alone or a mixture of a cerium oxide and of a zirconium oxide, with optionally an oxide of a rare earth metal other than cerium, and with a zirconium content such that the Ce/Zr atomic ratio is at least 1.
- these compositions can exhibit a reducibility, measured between. 30° C. and 600° C. (also after calcination at a temperature of at least 800° C. for 6 hours), of at least 35%, more particularly of at least 40%.
- these compositions also exhibit the same values for reducibility measured between 30° C. and 900° C. as those which were given above.
- compositions of the invention can exhibit a high BET specific surface which can be, after calcination at 800° C. for 6 hours, at least 95 m 2 /g, more particularly at least 110 m 2 /g, this surface depending on the nature of the support used.
- the continuation of the description will comprise the description of a first preparation process (A), the description of a specific colloidal dispersion (B) which can be used more particularly in the case of the present invention and the description of three other processes (C), (D) and (E) for the preparation of compositions of the invention.
- This first process comprises the following stages:
- the first stage of this process thus consists in forming a mixture starting from a colloidal dispersion of the supported oxide, for example the cerium oxide.
- a colloidal dispersion of the supported oxide for example the cerium oxide.
- this mixture additionally comprises a colloidal dispersion of an oxide of this element. It is also possible to use a single colloidal dispersion in which the colloids are based on a mixed oxide of cerium and of the element M.
- colloidal dispersion denotes any system composed of fine solid particles of colloidal dimensions, that is to say dimensions of between approximately 1 nm and approximately 500 nm, based on a compound of cerium and/or the element M, this compound generally being an oxide and/or an oxide hydrate, in stable suspension in an aqueous liquid phase, it being possible for said particles in addition to optionally comprise residual amounts of bonded or adsorbed ions, such as, for example, nitrates, acetates, chlorides or ammoniums.
- the cerium or the element M can occur either completely in the form of colloids or simultaneously in the form of ions and in the form of colloids.
- cerium oxide dispersions of those described or obtained by the processes described in patent applications EP-A-206 906, EP-A-208 580, EP-A-208 581, EP-A-239 477 and EP-A-700 870.
- dispersions of mixed oxides use may be made of those described in patent application EP-A-1 246 777.
- Use may in particular be made of a colloidal dispersion of the cerium oxide, simple or mixed oxide, which comprises an amino acid.
- This acid can more particularly be an aliphatic amino acid.
- This can in particular be a C 4 -C 10 acid and preferably a C 4 -C 8 acid.
- Such a dispersion is described in patent application EP-A-1 301 435.
- a mixture of the dispersion with a suspension of the support is formed.
- This suspension is generally based on the support or on a precursor of the support, that is to say a compound which, after calcination, can result in alumina, silica, zirconium oxide or titanium oxide.
- Dried precursors that is to say exhibiting a loss on ignition of at most 50%, more particularly of at most 25%, may be concerned. These can in particular be hydroxides or oxyhydroxides.
- the suspension is generally an aqueous suspension.
- aqueous phase generally water and, for example, distilled or deionized water.
- the second stage of the process is a drying stage.
- This drying is carried out by atomization.
- drying by atomization is to be understood to mean drying by spraying the mixture into a hot atmosphere (spray drying).
- the atomization can be carried out by means of any sprayer known per se, for example by a spray nozzle of the shower head or other type. Use may also be made of “rotary” atomizers. Reference may in particular be made, with regard to the various spraying techniques capable of being employed in the present process, to the reference work by Masters entitled “Spray Drying” (second edition, 1976, published by George Godwin, London).
- the final stage of the process is a calcination stage.
- This calcination makes it possible to develop the crystallinity of the product formed and it can also be adjusted and/or chosen according to the subsequent operating temperature reserved for the composition according to the invention, this being done while taking into account the fact that the specific surface of the product decreases as the calcination temperature employed increases.
- a calcination is generally carried out under air but a calcination carried out, for example, under an inert gas or under a controlled atmosphere (oxidizing or reducing) is very clearly not excluded.
- the calcination temperature is generally restricted to a range of values of between 500° C. and 1000° C., preferably between 600° C. and 800° C.
- a double calcination it is possible to carry out a double calcination. It is thus possible to carry out a first calcination under an inert gas or under vacuum.
- the inert gas can be helium, argon or nitrogen.
- the vacuum is generally a low vacuum with an oxygen partial pressure of less than 10 ⁇ 1 mbar.
- the calcination temperature is at least 900° C. and generally at most 1000° C.
- the time for this first calcination is generally at least 2 hours, preferably at least 4 hours and in particular at least 6 hours. An increase in this time generally results in an increase in the degree of reducibility.
- the time can be set according to the temperature, a low calcination time requiring a higher temperature.
- a second calcination is subsequently carried out under an oxidizing atmosphere, for example under air.
- the calcination is generally carried out at a temperature of at least 600° C. over a time which is generally at least 30 minutes. It is preferable not to exceed a calcination temperature of 900° C.
- This dispersion is a colloidal dispersion, in a continuous phase, of a compound of cerium and of at least one other element M chosen from zirconium and rare earth metals (Ln) other than cerium and it is characterized in that the compound is in the form of a mixed oxide in which the cerium and the element M are in pure solid solution and in that the compound comprises cerium in the form of cerium(III) in an amount, expressed as cerium(III)/total cerium atomic ratio, of between 0.005 and 0.06.
- This dispersion can be prepared by a process which comprises the following stages:
- the liquid continuous phase of the dispersion described here is generally an aqueous phase, more particularly water.
- the abovementioned compound of which they are formed is in the form of a mixed oxide (Ce,M)O 2 in which the cerium and the element M are in solid solution.
- This term is to be understood to mean that one of the elements, generally the element M, is completely incorporated in the crystal lattice of the oxide of the other matrix-forming element, for example the cerium. This incorporation can be demonstrated by the X-ray diffraction technique on colloids after washing, in particular by ultrafiltration or also by ultracentrifugation, and drying at a temperature of 60° C.
- the X-ray diagrams reveal the presence of a crystal structure corresponding to the oxide of the matrix-forming element (generally cerium oxide), the unit cell parameters of which are more or less offset with respect to a pure oxide of this first matrix-forming element, which thus demonstrates the incorporation of the other element in the crystal lattice of the oxide of the first.
- the X-ray diagrams then reveal a crystal structure of fluorine type, just like crystalline ceric oxide CeO 2 , the unit cell parameters of which are more or less offset with respect to a pure ceric oxide, thus reflecting the incorporation of the element M in the crystal lattice of the cerium oxide.
- the solid solution is pure, that is to say that, for the colloidal particles, the total amount of an element is in solid solution in the other, for example all the element M is in solid solution in the cerium oxide.
- the X-ray diagrams show only the presence of the solid solution and do not comprise lines corresponding to an oxide such as oxide of the element other than the matrix-forming element, for example an oxide of the element M.
- the liquid continuous phase it is not out of the question for the liquid continuous phase to be able to comprise a certain amount of element M in the form of ions originating from a portion of the total amount of the element M introduced during the preparation of the dispersion.
- the element M is chosen from the group consisting of zirconium and rare earth metals (Ln) other than cerium, it being possible, of course, for these elements to be present as a mixture, as will be seen in the continuation of the description.
- cerium(III) is a characteristic of the dispersion described here.
- the amount of cerium(III), expressed by the cerium(III)/total cerium atomic ratio, is between 0.005 and 0.06. More particularly, this amount can be between 0.005 and 0.05 and more particularly still between 0.005 and 0.03.
- cerium(III) can be present in the compound as cation, either in the form adsorbed at the surface of the particles of the cerium compound or in the crystal unit cell of the compound. Of course, both these forms may coexist.
- cerium(III) in solution can be demonstrated by chemical quantitative determination. Use may thus be made of a technique for analysis by potentiometric titration by oxidation of cerium(III) to give cerium(IV) using potassium ferricyanide in potassium carbonate medium.
- cerium(III) at the surface of the particles of the dispersion can be demonstrated by the determination of the isoelectric point of the colloidal dispersions. This determination is carried out in a known way by measuring the variation in the zeta potential of the dispersions.
- this potential When the variation in this potential is measured, by varying the pH of a dispersion from an acidic value to a basic value, this potential changes from a positive value to a negative value, the transition at the zero value of the potential constituting the isoelectric point.
- the presence of cerium(III) at the surface increases the value of the isoelectric point with respect to a compound comprising only cerium(IV).
- the element M is zirconium. More particularly, in the case of this alternative form, the compound can correspond to the formula (3) Ce 1-x Zr x O 2 in which x is less than 1 and is at least equal to 0.01, preferably at least equal to 0.02.
- the element M is a combination of zirconium and of at least one rare earth metal Ln.
- This alternative form is particularly advantageous in the case where the rare earth metal is a trivalent rare earth metal.
- the rare earth metal can be in particular lanthanum, gadolinium, terbium, praseodymium or neodymium.
- the compound can correspond to the formula (4) Ce 1-x-y Zr x Ln y O 2 in which x+y ⁇ 1, x adheres to the condition 0.05 ⁇ x ⁇ 0.95 and y is at least equal to 0.01, the high value of y being chosen so that a solid solution is indeed obtained.
- x adheres to the condition 0.20 ⁇ x ⁇ 0.8 and more preferably still the condition 0.40 ⁇ x ⁇ 0.60.
- y is at least equal to 0.02 and more preferably still y is at least equal to 0.03.
- y is at most equal to 0.05 and more preferably still to at most 0.04.
- the element M can be a combination of at least two rare earth metals, at least one of which is praseodymium.
- M is terbium or praseodymium, optionally in combination with another rare earth metal, these elements can be present both in the Tb(III) and Pr(III) forms and the Tb(IV) and Pr(IV) forms.
- the compound of the dispersion described here can also be a compound in which M is a rare earth metal or a combination of rare earth metals. Again, a particularly advantageous case is that where the rare earth metal is a trivalent rare earth metal.
- the rare earth metal can in particular be lanthanum, gadolinium, terbium, praseodymium or neodymium.
- the compound can then correspond more particularly to the following formula (5) Ce 1-x Ln x O 2 in which x is at most equal to 0.15 and is at least equal to 0.01, preferably at least equal to 0.02 and more preferably still at least equal to 0.04.
- x is at most equal to 0.10 and more preferably still at most equal to 0.05.
- the rare earth metal can be present, at least in part, in the Ln(III) form and, here again, either in the crystal unit cell or in the form adsorbed at the surface of the particles of the cerium compound.
- the latter element can be present both in the Pr(III) and Pr(IV) forms and, in the same case, x is more particularly at least equal to 0.04 and more particularly still between 0.03 and 0.08.
- the compound of the dispersion can also correspond to the formula (6) Ce 1-x Ln′ x O 2 where Ln′ describes a combination of at least two rare earth metals and where x is at most equal to 0.30 and can preferably be at least equal to 0.01.
- the particles which constitute the compound of the dispersion exhibit a fine and narrow particle size distribution. This is because they have a size, measured by their mean diameter, which is preferably at most 10 nm and which can more particularly be between 2 and 8 nm. This size is conventionally determined by transmission electron microscopy (TEM) on a sample dried beforehand on a carbon membrane supported on a copper grid and over a mean of 50 measurements.
- TEM transmission electron microscopy
- cryo-TEM technique can be used to determine the state of aggregation of the particles. It makes it possible to observe, by transmission electron microscopy, samples kept frozen in their natural medium, which can, for example, be water.
- Freezing is carried out on thin films with a thickness of approximately 50 to 100 nm in liquid ethane for the aqueous samples.
- cryo-TEM demonstrates the well-separated aspect of the particles.
- the dispersion described here generally exhibits a pH which can be between 0.5 and 6.
- the dispersion generally exhibits a concentration of mixed oxide of at least 0.1M, preferably of at least 0.25M and advantageously of greater than 1M.
- a specific embodiment corresponds to dispersions having a basic pH.
- the compound of cerium and of at least one other element M exists in the form of particles additionally comprising citrate anions, these anions being adsorbed at the surface of the particles.
- the pH of the dispersions is at least 7, preferably at least 8.
- the compound of cerium and of at least one other element M exists in the form of particles comprising, at the surface, a bifunctional compound comprising a functional group R 1 of amine, sulfate, phenyl, alkylethoxy or succinate type and a functional group R 2 of carboxylic, dicarboxylic, phosphoric, phosphonic or sulfonic type, the functional groups R 1 and R 2 being separated by an organic chain of the —(CH 2 ) x — type, x preferably being at most equal to 6.
- this bifunctional compound is bonded at the surface by interactions of complexing type between the functional group R 2 and the cerium or M present at the surface of the colloidal particles.
- the bifunctional compound can be chosen from aliphatic amino acids, for example aminocaproic acid, aminated sulfonic acids, such as aminoethylsulfonic acid, or alkyl polyoxyethylene ether phosphates.
- colloidal dispersions described here are particularly stable, that is to say that separation by settling or phase separation is not observed over a period of time which can be greater than 1 year.
- this process comprises a first stage in which a liquid medium comprising cerium salts and salts of at least one element M is formed, the cerium salts being cerium(IV) and cerium(III) salts.
- the proportion of cerium(III) salts and of cerium(IV) salts, expressed by the Ce(III)/total Ce (Ce(III)+Ce(IV)) molar ratio, is generally at least 2% and at most 20%, preferably between 2% and 10%, this proportion being chosen according to the level of cerium(III) desired in the colloidal dispersion which it is desired to prepare.
- the liquid medium is generally water and the salts are usually introduced in the form of solutions.
- the salts can be salts of inorganic or organic acids, for example of the sulfate, nitrate, chloride or acetate type, it being understood that the starting medium must comprise at least one cerium(IV) salt.
- Use may more particularly be made, as Ce(IV) solution, of a ceric ammonium nitrate solution to which Ce(III) is added in the form of cerous nitrate or Ce(III) acetate or cerous chloride.
- Use may also be made of a ceric nitrate solution obtained by attack on CeO 2 by nitric acid, Ce(III) being added to this solution.
- Use may advantageously be made of a ceric nitrate solution obtained by electrolysis and comprising Ce(III).
- the solution of Zr(IV) can be of ZrOCl 2 or of ZrO(NO 3 ) 2 .
- the rare earth metals Ln are generally introduced in the form of Ln(III) salts, for example nitrates.
- the second stage of the process consists in bringing the medium formed above into contact with a base.
- Use may in particular be made, as base, of products of the hydroxide type. Mention may be made of alkali metal hydroxides, alkaline earth metal hydroxides and aqueous ammonia. Use may also be made of secondary, tertiary or quaternary amines. However, the amines and aqueous ammonia may be preferred insofar as they reduce the risks of contamination by alkali metal or alkaline earth metal cations.
- the addition of the base is carried out instantaneously or gradually but so as to obtain a pH of the medium of at least 9, preferably of at least 9.5 and more preferably still of at least 10.
- the addition of the base results in the formation of a precipitate.
- the precipitate can be separated from the liquid medium by any known process, for example by centrifuging.
- the precipitate resulting from the reaction can subsequently be washed.
- This washing can be carried out by putting the precipitate back into water and then, after stirring, by separating the solid from the liquid medium, for example by centrifuging. This operation can be repeated several times, if necessary.
- this washing is carried out so as to obtain a washing slurry, that is to say the water in which the precipitate is resuspended, with a pH of at most 8.75, preferably of at most 8, advantageously of at most 7.
- the final stage of the process is a stage of peptization of the precipitate obtained above.
- This peptization is carried out by treatment of the precipitate with an acid.
- This treatment is generally carried out by dispersing the precipitate in an acidic solution and stirring the medium thus formed.
- Use may be made, for example, of nitric acid, hydrochloric acid or acetic acid.
- Acetic acid can advantageously be used to obtain dispersions of compounds in which the content of trivalent rare earth metal is high.
- the peptization is generally carried out at a temperature between ambient temperature and 90° C., preferably at ambient temperature.
- the amount of acid used is such that the H + /(Ce+M) molar ratio is generally at most 1.5, preferably at most 1.25 and more preferably still at most 1.
- a colloidal dispersion is obtained directly and without another intermediate stage.
- the process described here comprises at least one washing stage, it being possible for this washing to take place under the conditions which have just been described, that is to say either on the precipitate or on the dispersion or also on both.
- the preparation process is of the type of that which has just been described but it is supplemented by a stage of bringing into contact with citric acid.
- the citric acid can be added to the dispersion obtained after peptization, for example in the form of a citric acid hydrate powder.
- the citric acid then dissolves with stirring.
- the citric acid/mixed oxide molar ratio is within the range of values given above, that is to say generally between 0.1 and 0.6. It is possible to leave the medium obtained standing for between 30 minutes and 24 hours at ambient temperature.
- a solution of a base is gradually added, this base being of the same type as that described above for the precipitation stage, so as to obtain the desired pH of at least 7, preferably of at least 8.
- the addition can be carried out for between 10 min and 2 hours at ambient temperature.
- the bifunctional compound is added to the dispersion obtained after peptization.
- compositions of the invention can also be prepared by a second process which will be described below.
- This process comprises the following stages:
- the starting material is also a colloidal suspension or dispersion of the support but it is mixed with a salt of cerium and, in the case of a composition where cerium oxide is a mixed oxide, of the element M.
- This mixing is carried out in an aqueous phase, generally water.
- the salts can be chosen from nitrates, sulfates, acetates, chlorides or ceric ammonium nitrate.
- Zirconyl sulfate zirconyl nitrate or zirconyl chloride.
- Zirconyl nitrate is most generally used.
- Mention may also in particular be made of cerium(IV) salts, such as the nitrate, or ceric ammonium nitrate, for example, which are particularly well suited here.
- ceric nitrate is used.
- the following stage of the process is the stage of heating the liquid mixture thus formed.
- the temperature at which the liquid mixture is heated is at least 100° C. and more particularly still at least 130° C.
- the heating operation can be carried out by introducing the liquid mixture into a closed chamber (closed reactor of the autoclave type). Under the temperature conditions given above and in an aqueous medium, it can thus be specified, by way of illustration, that the pressure in the closed reactor can vary between a value of greater than 1 bar (10 5 Pa) and 165 bar (1.65 ⁇ 10 7 Pa), preferably between 5 bar (5 ⁇ 10 5 Pa) and 165 bar (1.65 ⁇ 10 7 Pa).
- the heating can also be carried out in an open reactor for temperatures in the region of 100° C.
- the heating can be carried out either under air or under an inert gas atmosphere, preferably under nitrogen.
- the duration of the heating can vary within wide limits, for example between 1 and 48 hours, preferably between 2 and 24 hours.
- the rise in temperature takes place at a rate which is not critical and the set reaction temperature can thus be reached by heating the liquid mixture, for example, for between 30 minutes and 4 hours, these values being given entirely by way of indication.
- a solid precipitate is recovered which can be separated from its medium by any conventional solid/liquid separating technique, such as, for example, filtration, settling, draining or centrifuging.
- the product as recovered can subsequently be subjected to washing operations which are then carried out with water or optionally with a basic solution, for example an aqueous ammonia solution, or an acidic solution, for example a nitric acid solution.
- a basic solution for example an aqueous ammonia solution
- an acidic solution for example a nitric acid solution.
- the process comprises a maturing.
- This maturing is generally carried out on a suspension obtained after putting the precipitate back into water, in particular after the washing operation.
- the maturing is carried out by again heating this suspension.
- the temperature at which the suspension is heated is at least 40° C., more particularly at least 60° C. and more particularly still at least 100° C. Generally, this temperature is at most 200° C., more particularly at most 150° C.
- the medium is thus maintained at a constant temperature for a period of time which is usually at least 30 minutes and more particularly at least 1 hour.
- the maturing can be carried out at atmospheric pressure or optionally at a higher pressure.
- the final calcination stage of this second process can be carried out in the same way as for the first process and thus that which was described above for this calcination likewise applies here.
- compositions with a support based on or essentially composed of alumina stabilized by a stabilizing element chosen from rare earth metals, barium and strontium two other processes (third and fourth processes) can be employed, which processes will now be described.
- the third process according to the invention comprises the following stages:
- stage (a) is carried out in an aqueous phase, generally water.
- the compound of the stabilizing element can in particular be a salt, such as a nitrate, an acetate, a chloride or a sulfate, in the form of a solution.
- the aluminum compound is generally an alumina precursor, that is to say a compound which, after calcination, can result in alumina.
- This compound can thus be an aluminum hydroxide, such as bayerite, hydrargillite or gibbsite, or nordstrandite, or an aluminum oxyhydroxide, such as boehmite, pseudoboehmite and diaspore.
- the aluminum compound can be provided in the form of an aqueous suspension, in particular of an acidic suspension, for example comprising nitric acid. This suspension is then mixed with the dispersion of the supported oxide and the stabilizing element, the latter in the form of a solution, for example.
- the second stage of the process consists in bringing together the mixture obtained in stage (a) and a base.
- Use may be made, as base, of products of the hydroxide, carbonate or basic carbonate type, for example. Mention may be made of alkali metal or alkaline earth metal hydroxides, or secondary, tertiary or quaternary amines. However, amines and aqueous ammonia may be preferred insofar as they reduce the risks of pollution by alkali metal or alkaline earth metal cations. Urea may also be mentioned.
- the contacting operation can be carried out in any order in a liquid medium.
- the third stage is just an optional stage.
- This stage (c) consists in subjecting the suspension to a maturing.
- the maturing is carried out by heating the suspension at a temperature of at least 60° C., more particularly of at least 80° C. Generally, this temperature is at most 200° C., more particularly at most 150° C.
- the medium is thus maintained at a constant temperature for a time which is usually at least 30 minutes and more particularly at least 1 hour.
- the maturing can be carried out at atmospheric pressure or optionally at a higher pressure.
- stage (b) On conclusion of stage (b) or optionally of the maturing stage, when the latter is carried out, the abovementioned stages (d) and (e) are carried out. These two stages are similar to the final two stages of the first process of the invention and everything which was described above likewise applies to these stages (d) and (e). However, it should be noted that the drying can be carried out by a means other than atomization, for example in an oven.
- stage (b) An alternative form can be used in the context of this third process.
- This alternative form consists, on conclusion of stage (b) or optionally of the maturing stage, when the latter is carried out, in separating the precipitate from the suspension, in washing it and in redispersing it in water to form a second suspension. It is the latter suspension which is subsequently dried in stage (d).
- This process comprises the following stages:
- This process differs from the third process in that the compound of the stabilizing element is introduced in a different stage, on conclusion of stage (b) or optionally on the maturing stage, if the latter exists. Consequently, everything which was described for the third process likewise applies here.
- the compound of the stabilizing element is in particular of the same type as described above.
- the fourth process described here applies very particularly to the case where the stabilizing element is barium or strontium.
- compositions of the invention as described above or as obtained by the processes described above are provided in the form of powders but they can optionally be shaped in order to be provided in the form of granules, bulbs, cylinders or honeycombs of variable sizes.
- compositions of the invention can be used as catalysts or catalyst supports.
- the invention also relates to catalytic systems comprising the compositions of the invention.
- These systems comprise a coating (wash coat), with catalytic properties, based on these compositions and on a binder of known type, on a substrate of the metal or ceramic monolith type, for example.
- the coating can itself also comprise a support of the type of those mentioned above. This coating is obtained by mixing the composition with the binder, such as to form a suspension which can subsequently be deposited on the substrate.
- catalytic systems and more particularly the compositions of the invention can have a great many applications. They are therefore particularly well suited to, and thus useable in, the catalysis of various reactions, such as, for example, dehydration, hydrosulfurization, hydrodenitrification, desulfurization, hydrodesulfurization, dehydrohalogenat ion, reforming, steam reforming, cracking, hydrocracking, hydrogenation, dehydrogenation, isomerization, dismutation, oxychlorination, dehydrocyclization of hydrocarbons or other organic compounds, oxidation and/or reduction reactions, the Claus reaction, treatment of exhaust gases from internal combustion engines, in particular for automobile afterburning and in particular three-way catalysis, demetallation, methanation, the shift conversion or catalytic oxidation of the soot emitted by internal combustion engines, such as diesel engines or gasoline engines operating under lean burn conditions.
- the catalytic systems and the compositions of the invention can be used for the removal of NOx compounds by trapping the latter or as
- the compositions of the invention can be employed in combination with precious metals or also transition metals in the oxide, sulfide or other form and they thus act as support for these metals.
- the nature of these metals and the techniques for the incorporation of the latter in the support compositions are well known to a person skilled in the art.
- the metals can be gold, silver, platinum, rhodium, palladium, iridium, molybdenum, tungsten, nickel, cobalt, manganese or vanadium; they can in particular be incorporated in the compositions by impregnation.
- the treatment of exhaust gases from internal combustion engines is a particularly advantageous application.
- the invention also relates to a process for the treatment of exhaust gases from internal combustion engines which is characterized in that use is made, as catalyst, of a catalytic system as described above or of a composition according to the invention and as described above.
- compositions of the invention in which the support is based on stabilized alumina are particularly advantageous as NOx trap.
- the invention thus also relates to a process for the treatment of exhaust gases from internal combustion engines which is characterized in that use is made, as NOx trap, of a composition according to the invention in which the support is based on stabilized alumina or a catalytic system comprising such a composition.
- This composition can more particularly be that corresponding to one of the two embodiments described above in which the support is based on alumina stabilized by barium, strontium or lanthanum and the supported oxide mixtures of cerium oxide, of zirconium oxide and of oxide of a rare earth metal other than cerium or of cerium oxide, of praseodymium oxide and of oxide of a rare earth metal other than cerium and praseodymium.
- the abovementioned systems are, for the treatment of exhaust gases, fitted in a known way in the exhaust mufflers of motor vehicles.
- This example relates to a composition based on cerium oxide on a silica support which is prepared by the second process described above.
- a mixture comprising 70% of SiO 2 and 30% of CeO 2 is prepared by mixing, in a beaker with stirring, 35 g of SiO 2 powder (170 m 2 /g), dispersed in 500 ml of H 2 O at pH 0.5, with an acidic (pH 0.5) Ce(NO 3 ) 4 solution comprising 15 g of CeO 2 (CeO 2 80 g/l).
- the combined mixture is transferred into an autoclave and brought to 150° C. for 2 hours while stirring at 300 revolutions/min.
- the cooled mixture is separated by filtration and washed with 2 l of water at pH 9.
- the cake obtained is dispersed in water at a concentration of oxide of 50 g/l (oxide) and then matured at 100° C. for 2 hours with stirring. After cooling, the suspension is separated by centrifuging. The cake is subsequently calcined under air at 800° C. for 6 h.
- This example relates to a composition based on a mixed oxide of cerium and of zirconium on a silica support which is prepared by the first process described above.
- a colloidal dispersion of particles of a mixed oxide of formula Ce 0.5 Zr 0.5 O 2 is prepared beforehand.
- a first solution comprising 1.5 M/l of Ce(NO 3 ) 4 and 0.5 M of HNO 3
- a second solution comprising 3.3 M/l of ZrO(NO 3 ) 2
- the volume of the solution obtained is brought to 2300 ml by addition of water.
- the final pH is 1.9.
- the precipitate is filtered off and then washed with 2400 ml of deionized water. Washing is repeated 3 times in succession with an identical volume of washing solution.
- the pH of the final suspension is 7.5.
- the Ce+Zr concentration is equal to 0.29 mol/l.
- Aminocaproic acid is added to this dispersion so as to obtain a final pH of 4.5 (98% 6-aminocaproic acid, Aldrich).
- This suspension is atomized at 110° C. (outlet temperature 110° C., inlet temperature 220° C.) with a flow rate of 1 l/h.
- the powder is calcined under air at 800° C. for 6 h.
- This example relates to a composition based on a mixed oxide of cerium and of zirconium on an alumina support which is prepared by the first process described above.
- a boehmite sol is prepared in a beaker equipped with a magnetic bar by dispersing, with stirring, 78.6 g of an AlOOH powder (Pural B21 alumina comprising 71.25% of Al 2 O 3 ) in 700 ml of H 2 O brought to pH 2 using a 68% concentrated HNO 3 solution. After a few hours, a gel is obtained at pH 4.
- AlOOH powder Physical B21 alumina comprising 71.25% of Al 2 O 3
- a colloidal dispersion of particles of mixed oxide of formula Ce 0.5 Zr 0.5 O 2 is prepared as described in example 2.
- Aminocaproic acid is likewise added thereto, so as to obtain a final pH of 4.5.
- the powder is calcined under air at 800° C. for 6 h.
- the reducibility of the cerium is measured by temperature-programmed reduction in the following way.
- Use is made of a Micromeritics Autochem 2920 device with a quartz reactor and a 200 mg sample which has been calcined beforehand at 800° C. for 6 hours under air.
- the gas is hydrogen at 10% by volume in argon and with a flow rate of 25 ml/min.
- the temperature rise takes place from ambient temperature to 900° C. at the rate of 20° C./min.
- the signal is detected with a thermal conductivity detector.
- the temperature is measured in the sample using a thermocouple.
- the reducibility of the cerium is calculated from the hydrogen consumption, it being understood that 1 ⁇ 2 mol of H 2 consumed and measured by the method described above corresponds to 1 mol of reduced Ce(IV).
- the hydrogen consumption is calculated from the missing area of the hydrogen signal from the base line at 30° C. to the base line at 900° C. (respectively 600° C.) when the reducibility is measured between 30° C. and 900° C. (respectively 600° C.)
- the reducibility values are collated in table 2.
- Barium nitrate comprising 99% by weight of oxide
- Ceric nitrate solution comprising 256 g/l of oxide with a cerium(III) content of 0.11 mol/l and a Ce(III)/total cerium atomic ratio of 0.06
- This example relates to a composition based on cerium oxide on a support made of alumina stabilized by lanthanum, the proportions by weight of which, expressed as oxide, are 75%, 20% and 5% respectively for the aluminum, the lanthanum and the cerium.
- the solid phase is separated from the supernatant by centrifugation.
- the solid phase is redispersed in demineralized water so that the total volume is 600 ml.
- the powder obtained is calcined under air at 600° C. for 2 h.
- This example relates to a composition based on mixed oxide of cerium, of zirconium and of praseodymium comprising 25% by weight of oxides on a support formed of alumina stabilized by lanthanum in the overall proportions by weight, expressed as oxide, of 14%/6%/5%/15%/60% respectively for CeO 2 /ZrO 2 /Pr 6 O 11 /La 2 O 3 /Al 2 O 3 .
- a colloidal dispersion of particles of a CeO 2 —ZrO 2 —Pr 6 O 11 mixed oxide is prepared beforehand according to the specific process described above.
- the solution obtained is then made up with demineralized water in order to achieve a total volume of 950 ml.
- the concentration of the solution is then 112 g/l of oxides and the pH is 1.0.
- This dispersion is heated at 80° C. for 1 h and a colloidal dispersion is obtained.
- the powder obtained is calcined under air at 800° C. for 6 h.
- This example relates to a composition based on mixed oxide of cerium, of zirconium and of praseodymium charged with 25% by weight of oxides on support made of alumina stabilized with barium in overall proportions by weight, expressed as oxide, of 14%/6%/5%/15%/60% respectively for CeO 2 /ZrO 2 /Pr 6 O 11 /BaO/Al 2 O 3 .
- a dispersion of 38.5 g of boehmite and 1.5 g of 15.2 mol/l concentrated nitric acid is added, with stirring, to 125 g of the colloidal dispersion of CeO 2 —ZrO 2 —Pr 6 O 11 mixed oxide prepared in 1) of example 6.
- 515 ml of demineralized water are subsequently added with stirring in order to obtain a suspension comprising 50 g/l of oxides.
- This suspension is gradually introduced with stirring into a vessel heel comprising 21 g of aqueous ammonia and 176 ml of demineralized water.
- the final pH of the suspension is 9.3 at the end of the introduction.
- the medium is subsequently heated at 100° C.
- the powder obtained is calcined under air at 600° C. for 2 h.
- This example relates to a composition based on mixed oxide of cerium, of zirconium and of lanthanum comprising 25% by weight of oxides on a support formed of alumina stabilized with barium in overall proportions by weight, expressed as oxide, of 20.4/2.4/2.2/15/60% respectively for CeO 2 /ZrO 2 /La 2 O 3 /BaO/Al 2 O 3 .
- a colloidal dispersion of particles of a CeO 2 —ZrO 2 —La 2 O 3 mixed oxide is first prepared according to the process described in example 6.
- the solution obtained is then made up with demineralized water in order to achieve a total volume of 950 ml.
- the concentration of the solution is then 111.5 g/l of oxides and the pH is 0.9.
- This dispersion is heated at 80° C. for 1 h and a colloidal dispersion is obtained.
- a suspension of 38.5 g of boehmite and 8.5 ml of nitric acid (5M) is added to 126 g of the colloidal dispersion of CeO 2 —ZrO 2 —La 2 O 3 mixed oxide prepared in 1), followed by 535 ml of demineralized water.
- This mixture is gradually introduced with stirring into a vessel heel comprising 25 g of aqueous ammonia and 200 ml of demineralized water.
- the final pH of the suspension is 9.2.
- the medium is subsequently heated at 95° C. for 1 h and is then cooled before being filtered in order to recover the solid phase, which is then washed with demineralized water on a sintered glass filter.
- the solid is subsequently redispersed in a mixture of 13 g of barium nitrate and 160 ml of demineralized water.
- the mixture is subsequently made up with demineralized water in order to obtain a total volume of 500 ml for the suspension.
- the powder obtained is calcined under air at 600° C. for 2 h.
- This example relates to a composition based on mixed oxide of cerium, of lanthanum and of praseodymium comprising 25% by weight of oxides on a support made of alumina stabilized with lanthanum in the overall proportions by weight, expressed as oxide, of 19/18/3/60% respectively for CeO 2 /La 2 O 3 /Pr 6 O 11 /Al 2 O 3 .
- a colloidal dispersion of particles of a mixed oxide of CeO 2 —La 2 O 3 —Pr 6 O 11 mixed oxide is prepared beforehand.
- the solution obtained is then made up with demineralized water in order to achieve a total volume of 1 l.
- the concentration of the solution is then 102 g/l of oxides and the pH is 1.0.
- This dispersion is heated at 80° C. for 1 h and a colloidal dispersion is obtained.
- a suspension of 38.5 g of boehmite and 1.7 ml of nitric acid (15.2M) is added to 137 g of the colloidal dispersion of CeO 2 —La 2 O 3 —Pr 6 O 11 mixed oxide prepared in 1).
- the mixture is made up with demineralized water in order to obtain a total volume of 650 ml.
- the pH of the medium is 2.1. 28 g of lanthanum nitrate solution are then gradually introduced with stirring.
- the resulting mixture is gradually introduced with stirring into a vessel heel comprising 23 g of aqueous ammonia and 200 ml of demineralized water.
- the final pH of the suspension is 9.2.
- the medium is subsequently heated at 96° C.
- the powder obtained is calcined under air at 800° C. for 6 h.
- the reducibility of the compositions is measured by temperature-programmed reduction in the following way.
- Use is made of a Micromeritics Autochem 2920 device with a quartz reactor and a 200 mg sample which has been calcined beforehand at 800° C. for 6 hours under air.
- the gas is hydrogen at 10% by volume in argon and with a flow rate of 25 ml/min.
- the temperature rise takes place with ambient temperature to 900° C. at the rate of 20° C./min.
- the signal is detected with a thermal conductivity detector.
- the temperature is measured in the sample using a thermocouple.
- the reducibility of the cerium is calculated from the hydrogen consumption, it being understood that 1 ⁇ 2 mol of H 2 consumed and measured by the method described above corresponds to 1 mol of reduced Ce(IV).
- the hydrogen consumption is calculated from the missing area of the hydrogen signal from the base line at 30° C. to the base line at 900° C. when the reducibility is measured between 30° C. and 900° C.
- the reducibility values are collated in table 3.
- This example illustrates the effectiveness of these materials used as precious metal support with regard to their storage capacity for nitrogen oxides NOx for catalytic compositions comprising 1% by weight of platinum prepared from the compositions of the preceding examples and in the following way.
- the NOx storage capacity is measured under the following conditions:
- the catalytic composition as prepared above is introduced into a reactor and then pretreated at 300° C. for 12 hours under a gas stream with the following composition:
- the reactor is isolated and then cooled to ambient temperature under an N 2 stream.
- This catalytic composition thus sulfated, is introduced into a fresh reactor and heated from a temperature of 150° C. to a temperature of 600° C. under a reducing gas stream with the following composition:
- the catalytic composition as prepared above was subsequently maintained under this reducing stream for 20 minutes at a temperature of 600° C.
- the purpose of this treatment is to simulate a sulfation/desulfation cycle.
- the reactor is subsequently isolated and then cooled under static conditions to ambient temperature.
- the reaction stream with the composition: 10% O 2 +5% H 2 O+10% CO 2 +300 ppm NO in nitrogen, analyzed continuously by a Nicolet Magna 560 Fourier transform infrared (FT-IR) spectrometer, is introduced into the catalytic reactor, placed beforehand at the desired reaction temperature. After stabilization of the stream monitored by NO+NO 2 analysis, the respective concentrations of NO and NO 2 at the reactor outlet are continuously determined by the FTIR spectrometer.
- FT-IR Fourier transform infrared
- the integration of the NO and NO 2 concentrations during the minute following the arrival of the reaction stream over the catalytic composition makes it possible to calculate the amount of trapped NOx compounds.
- the results are expressed by the amount by weight of trapped NOx compounds (%) at 1 minute, with respect to the total amount of NOx compounds fed during this minute.
- the amounts of NOx compounds trapped at the temperatures of 200° C., 300° C., 350° C. and 400° C. are listed in table 4.
- the catalytic compositions of tests 1, 2 and 3 of this table correspond respectively to the products obtained after impregnation with platinum, according to the process described above, of the composition of example 5 (test 1), example 7 (test 2) and example 9 (test 3).
- compositions of the invention exhibit a high NOx storage efficiency in the temperature region between 200° C. and 400° C. They are very particularly effective in the region of low temperatures, at 300° C. or below, in particular at temperatures as low as 200° C.
- the catalytic compositions of the invention are therefore particularly effective over the entire temperature range and in particular at low temperatures, from 200° C. to 300° C. and more particularly still at 200° C. and 250° C.
Abstract
Catalyst/catalyst support compositions are characterized by a supported cerium oxide, deposited onto a silica, alumina, titanium or zirconium based support, including particles of said supported oxide deposited onto said support, individualized or in the form of aggregates, no greater than 500 nm in size and having, after 6 hours of calcination at a temperature of at least 800° C., a measured reducibility from 30° C. and 900° C. of at least 80%; such compositions are prepared by combining a colloidal dispersion of the supported oxide and a suspension of the support, drying the resulting mixture by atomization and drying the resulting product by calcination.
Description
- The present invention relates to a composition having high reducibility based on a nanometric cerium oxide on a support, to its process of preparation and to its use as catalyst.
- “Multifunctional” catalysts are currently used for the treatment of exhaust gases for internal combustion engines (automobile afterburning catalysis). The term “multifunctional” is understood to mean catalysts capable of carrying out not only oxidation, in particular of carbon monoxide and hydrocarbons present in exhaust gases, but also reduction, in particular of nitrogen oxides also present in these gases (“three-way” catalysts). Zirconium oxide and cerium oxide today appear as two constituents which are particularly important and advantageous for catalysts of this type.
- To be effective, these catalysts must exhibit good reducibility. The term “reducibility” is to be understood to mean, here and for the remainder of the description, the ability of the catalyst to be reduced in a reducing atmosphere and to be reoxidized in an oxidizing atmosphere. This reducibility can be measured, for example, by consumption of hydrogen in a given temperature range. It is due to the cerium, in the case of the compositions of the type of those of the invention, cerium having the property of being reduced or of being oxidized.
- Materials with an increasingly high reducibility are thus sought for for their effectiveness. A first subject matter of the invention is thus the development of such materials.
- Furthermore, materials having high reducibility even in a relatively low temperature range, that is to say of at most 600° C., are also sought for.
- A second subject matter of the invention is the provision of materials which satisfy the latter condition.
- With this aim, the composition according to the invention comprises a supported oxide, based on a cerium oxide, on a support based on silica, alumina, titanium oxide or zirconium oxide, and it is characterized in that it comprises particles of said supported oxide, deposited on said support, which particles are separate or in the form of aggregates, with a size of at most 500 nm, and in that it exhibits, after calcination at a temperature of at least 800° C. for 6 hours, a reducibility measured between 30° C. and 900° C. of at least 80%.
- According to a specific embodiment of the invention, the composition comprises a supported oxide, based on a cerium oxide, on an alumina-based support, characterized in that it comprises particles of said supported oxide, deposited on said support, which particles are separate or in the form of aggregates, with a size of at most 500 nm, and in that it exhibits, after calcination at a temperature of at least 800° C. for 6 hours, a reducibility measured between 30° C. and 900° C. of at least 80%, the compositions in which the alumina support additionally comprises at least one element from the group consisting of barium and strontium being excluded.
- Other characteristics, details and advantages of the invention will become even more fully apparent on reading the description which will follow and also the various concrete but non-limiting examples intended to illustrate it.
- The term “rare earth metal” is to be understood to mean the elements of the group consisting of yttrium and the elements of the Periodic Table with an atomic number of between 57 and 71 inclusive.
- The term “specific surface” is to be understood to mean the BET specific surface determined by nitrogen adsorption in accordance with the ASTM D 3663-78 Standard, drawn up from 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 a supported oxide in the form of particles of nanometric dimensions, these particles being deposited on a support.
- This supported oxide can be first of all an oxide of cerium alone, a simple oxide, generally in the form of ceric_oxide CeO2. It can also be a mixture of a cerium oxide and of at least one oxide of another element M which is chosen from zirconium and rare earth metals other than cerium. According to specific embodiments of the invention, this oxide mixture can correspond to the formula (1) Ce1-xZrxO2 in which x is less than 1 or also to the formula (2) Ce1-y-zZryLnzO2 in which y+z<1, Ln denoting at least one rare earth metal. The Ce/Zr atomic ratio can vary within wide limits, for example from 0.1 to 0.9. However, more particularly, the value of x or of the sum y+z can be at most 0.5.
- According to a specific embodiment, the supported oxide is in the crystalline form.
- According to another specific embodiment, the mixture of oxides is provided in the form of a solid solution of the element M in the cerium or also in the form of a solid solution (mixed oxide) of the cerium and optionally of a rare earth metal in the zirconium, this being the case according to the respective amounts of the cerium and of the zirconium. In the first case, the supported oxide exhibits a single phase which in fact corresponds to a crystal structure of fluorine type, just like crystalline ceric oxide CeO2, the unit cell parameters of which are more or less offset with respect to a pure ceric oxide, thus reflecting the incorporation of the element M in the crystal lattice of the cerium oxide. In the second case, the supported oxide exhibits a single phase corresponding to that of a zirconium oxide crystallized in the tetragonal system in particular, thus reflecting the incorporation of the cerium and optionally of the other element in the crystal lattice of the zirconium oxide.
- The supported oxide is present in the composition of the invention in the form of particles of nanometric dimensions. This is to be understood to mean that the particles exhibit a size of at most 500 nm. It should be noted here that these particles can either be separate or in the form of aggregates. The value of 500 nm applies either to the size of the particles, when the latter are separate, or to the size of the aggregate, provided that there are aggregated particles. Furthermore, this size can more particularly be at most 50 nm and more particularly still at most 10 nm. The highest size values given above correspond to the cases where the particles are generally in an aggregated form, while the lowest values correspond to the cases where the particles are generally in a separate form. More particularly, the particles are in the separate form with a size of approximately at most 50 nm, more particularly still of at most 10 nm, or also with a size of between 10 nm and 5 nm, and, in the case where the oxide is crystalline, they correspond to crystallites of this oxide. According to a specific embodiment, the particles are in the separate form with a size of at most 5 nm, this embodiment corresponding to the case where the content of supported oxide of the composition is relatively low, this low content being specified later. The size values given here and in the present description are determined either by transmission electron microscopy (TEM) or by X-ray diffraction (XRD), in particular when the oxide is crystalline.
- These size values for particles of the supported oxide are given for a composition which has been subjected to a calcination at a temperature of at least 500° C., more particularly of at least 800° C., for 6 hours.
- As indicated above, the particles are deposited on a support. This is to be understood to mean that the particles are predominantly present on the surface of the support, it being understood that the particles can be present inside the pores of the support but while remaining at the surface of these pores.
- The support is based on silica, on alumina, on titanium oxide or on zirconium oxide. Preferably, this support should exhibit a high and stable specific surface, that is to say a specific surface which remains at a satisfactory value even after exposure to a high temperature.
- The constituent oxides of the support which have just been mentioned are well known and are used in the field of catalysis. The description below relating to these supports is thus given purely by way of illustration and is not limiting.
- In the case of a silica-based support, the silica can be a precipitated silica or a pyrogenic silica. The silica can optionally be stabilized by a stabilizing element, such as aluminum.
- In the case of an alumina-based support, use may be made here of any type of alumina capable of exhibiting a specific surface satisfactory for application in catalysis. Mention may be made of the aluminas resulting from the rapid dehydration of at least one aluminum hydroxide, such as bayerite, hydrargillite or gibbsite, or nordstrandite, and/or of at least one aluminum oxyhydroxide, such as boehmite, pseudoboehmite and diaspore.
- According to a specific embodiment of the invention, use is made of a stabilized alumina. Mention may be made, as stabilizing element, of rare earth metals, barium, strontium, silicon and zirconium. Mention may very particularly be made, as rare earth metal, of cerium, lanthanum or the lanthanum-neodymium mixture. These elements can be used alone or in combination. Mention may be made, as advantageous combinations, of La—Ba, Ba—Pr, La—Pr—Ba and La—Pr.
- The stabilized alumina can be prepared in a way known per se, in particular by impregnation of the alumina with solutions of salts, such as nitrates, of the abovementioned stabilizing elements or also by codrying an alumina precursor and salts of these elements and then calcining.
- Mention may furthermore be made of another preparation of the stabilized alumina in which the alumina powder resulting from the rapid dehydration of an aluminum hydroxide or oxyhydroxide is subjected to a maturing operation in the presence of a stabilizing agent composed of a lanthanum compound and optionally a neodymium compound, it being possible for this compound to be more particularly a salt. The maturing can be carried out by suspending the alumina in water and then heating at a temperature of, for example, between 70 and 110° C. After the maturing, the alumina is subjected to a heat treatment.
- Another preparation consists of a similar type of treatment but with barium or strontium.
- The content of stabilizing agent, expressed as weight of stabilizing agent oxide with respect to the stabilized alumina, is generally between 1.5% and 35% or also between 1.5% and 25%, in particular between 1.5% and 15%. This content can more particularly be between 2.5% and 20%, more particularly between 2.5% and 11% or also between 5% and 20%.
- According to a specific embodiment, the stabilizing agent is barium and/or strontium in a content, expressed as weight of stabilizing agent oxide with respect to the stabilized alumina, of less than 10%.
- According to two other specific embodiments, the support is based on alumina stabilized by a stabilizing element from the group consisting of barium, strontium and lanthanum and the supported oxide is, in the first case, a mixture of cerium oxide, of zirconium oxide and of oxide of a rare earth metal other than cerium which can more particularly be praseodymium or lanthanum. In the second case, the supported oxide is a mixture of cerium oxide, of praseodymium oxide and of oxide of a rare earth metal other than cerium and praseodymium which can more particularly be lanthanum. For these two embodiments, the content of stabilizing element, expressed as oxide, can be equal to at least 10% by weight, with respect to the stabilized alumina, and it can more particularly be between 10 and 30% by weight, in particular between 10 and 25% by weight.
- According to other specific embodiments, the support is essentially composed of alumina (first form) or is essentially composed of alumina stabilized by at least one element chosen from rare earth metals, silicon and zirconium (second form). The term “is essentially composed of” is understood to mean, in the case of the first form, that the support comprises only alumina and no other element capable of stabilizing the latter, it being possible for the alumina optionally to comprise the usual impurities. In the case of the second form, it is understood that the support comprises only alumina and, as stabilizing agent, only one or more elements in combination chosen solely from the group consisting of rare earth metals, silicon and zirconium with, here again, the possible presence of impurities normally linked with the alumina and with the abovementioned element.
- In the case of a support based on alumina stabilized by a stabilizing element chosen from rare earth metals, barium and strontium or essentially composed of alumina stabilized with this same stabilizing element, it may be noted here that the preparation of the stabilized alumina can be carried out during the actual preparation of the composition according to the invention. This preparation will be described later.
- The support can also be made of titanium oxide, more particularly of titanium oxide in the anatase form. Such an oxide can be prepared, for example, by the processes described in EP-A-319 365 or in EP-A-351 270 and it can also comprise a stabilizing agent of rare earth metal or alkaline earth metal type.
- Finally, the support can be a tetragonal or monoclinic zirconium oxide which is optionally stabilized, for example by a rare earth metal.
- It should also be noted that the support can be composed of a combination of the abovementioned oxides, either in the form of mixtures of these oxides or in the form of mixed oxides (solid solutions), such as silica/alumina, titanium oxide/silica or zirconium oxide/silica mixed oxides.
- It should be noted that it is also possible to introduce the stabilizing elements of the various supports which have been mentioned after having prepared the composition (supported oxide on support free from stabilizing agent), for example by an impregnation technique.
- The content of supported oxide, for example cerium oxide, of the composition of the invention is generally at most 75% by weight of the whole of the composition. It can in particular be at most 60%, more particularly at most 50% and more particularly still at most 30%. In the specific case of a support made of zirconium oxide, the content of supported oxide can correspond to the values which have just been given and it can also be more particularly at most 55%.
- The minimum content of supported oxide is set according to the performances desired for the composition. By way of example only, this minimum content is generally at least 3% by weight, more particularly at least 4% by weight.
- As indicated above, the particles of the supported oxide can be in the separate form with a size of at most 5 nm. This embodiment preferably corresponds to the compositions in which the content of supported oxide is at most 20% by weight, more particularly at most 15% by weight and more particularly still at most 10% by weight.
- In the case of the specific embodiments described above for which the support is based on alumina stabilized by barium and the supported oxide mixtures of cerium oxide, of zirconium oxide and of oxide of a rare earth metal other than cerium or of cerium oxide, of praseodymium oxide and of oxide of a rare earth metal other than praseodymium, the content of supported oxides can more particularly be equal to or greater than 15%, more particularly between 15 and 30%.
- An advantageous characteristic of the compositions of the invention is their reducibility.
- The reducibility of the compositions is determined by the measurement of their hydrogen consumption, measured between 30° C. and 600° C. or 900° C. This measurement is carried out by programmed reduction in temperature using hydrogen diluted in argon. A signal is detected with a thermoconductivity detector. The consumption of hydrogen is calculated from the missing surface area of the hydrogen signal from the base line at 30° C. to the base line at 600° C. or 900° C. The degree of reducibility represents the percentage of reduced cerium, it being understood that ½ mol of H2 consumed and measured by the method described above corresponds to 1 mol of reduced Ce(IV).
- Within the meaning of the present invention and for the compositions comprising only cerium as a reducible element, the reducibility measured between 30° C. and 900° C. corresponds to the percentage of the total cerium present in the supported oxide which has been reduced, this percentage being measured by the method described above in the temperature range extending from 30° C. to 900° C. The reducibility measured between 30° C. to 600° C. corresponds to the same measurement but carried out in the temperature range from 30° C. to 600° C.
- In the case of the compositions comprising, in addition to the cerium, another reducible element, such as praseodymium, the overall reducibility of the cerium and the praseodymium is calculated. The overall reducibility of the cerium and of the praseodymium is calculated by relating the experimental hydrogen consumption of the composition to the sum of the theoretical hydrogen consumptions corresponding to the complete reduction of the cerium and to the complete reduction of the praseodymium. The experimental hydrogen consumption is calculated from the missing surface area of the hydrogen signal from the base line at 30° C. to the base line at 900° C., when the reducibility is measured between 30° C. and 900° C. The theoretical hydrogen consumption for the complete reduction of the cerium is calculated as above on the assumption that all the cerium is initially at the +IV state and that ½ mol of H2 is consumed to reduce 1 mol of Ce(IV). The theoretical hydrogen consumption for the complete reduction of the praseodymium is calculated analogously on the assumption that ⅔ of the praseodymium is present at the +IV oxidation state in Pr6O11 and that ½ mol of H2 is consumed to reduce 1 mol of Pr(IV).
- Furthermore, and for the whole of the description, the values which are given for the reducibility result from measurements carried out on compositions which have been subjected beforehand to a calcination at a temperature of at least 800° C. for 6 hours under air.
- As indicated above, the compositions of the invention exhibit a reducibility, measured between 30° C. and 900° C., of at least 80%. This reducibility thus measured can more particularly be at least 85% and more particularly still at least 90%.
- A more specific embodiment of the invention gives compositions having a high reducibility even in a relatively low temperature range, that is to say of at most 600° C. This embodiment corresponds to the case where the supported oxide is cerium oxide alone or a mixture of a cerium oxide and of a zirconium oxide, with optionally an oxide of a rare earth metal other than cerium, and with a zirconium content such that the Ce/Zr atomic ratio is at least 1. In this case, these compositions can exhibit a reducibility, measured between. 30° C. and 600° C. (also after calcination at a temperature of at least 800° C. for 6 hours), of at least 35%, more particularly of at least 40%. Of course, these compositions also exhibit the same values for reducibility measured between 30° C. and 900° C. as those which were given above.
- Finally, the compositions of the invention can exhibit a high BET specific surface which can be, after calcination at 800° C. for 6 hours, at least 95 m2/g, more particularly at least 110 m2/g, this surface depending on the nature of the support used.
- Processes for the preparation of the compositions of the invention will now be described.
- The continuation of the description will comprise the description of a first preparation process (A), the description of a specific colloidal dispersion (B) which can be used more particularly in the case of the present invention and the description of three other processes (C), (D) and (E) for the preparation of compositions of the invention.
- A First Process for the Preparation of the Compositions of the Invention
- This first process comprises the following stages:
-
- a colloidal dispersion of the supported oxide and, if appropriate, of the oxide of the element M and a colloidal suspension of the support are brought together;
- the mixture thus formed is dried by atomization;
- the dried product thus obtained is calcined.
- The first stage of this process thus consists in forming a mixture starting from a colloidal dispersion of the supported oxide, for example the cerium oxide. In the case of the preparation of a composition in which the supported oxide is a mixture of a cerium oxide and at least one oxide of another element M, this mixture additionally comprises a colloidal dispersion of an oxide of this element. It is also possible to use a single colloidal dispersion in which the colloids are based on a mixed oxide of cerium and of the element M.
- The term “colloidal dispersion” denotes any system composed of fine solid particles of colloidal dimensions, that is to say dimensions of between approximately 1 nm and approximately 500 nm, based on a compound of cerium and/or the element M, this compound generally being an oxide and/or an oxide hydrate, in stable suspension in an aqueous liquid phase, it being possible for said particles in addition to optionally comprise residual amounts of bonded or adsorbed ions, such as, for example, nitrates, acetates, chlorides or ammoniums. It should be noted that, in such a colloidal dispersion, the cerium or the element M can occur either completely in the form of colloids or simultaneously in the form of ions and in the form of colloids.
- Mention may thus be made, as suitable cerium oxide dispersions, of those described or obtained by the processes described in patent applications EP-A-206 906, EP-A-208 580, EP-A-208 581, EP-A-239 477 and EP-A-700 870. In the case of the dispersions of mixed oxides, use may be made of those described in patent application EP-A-1 246 777.
- Use may in particular be made of a colloidal dispersion of the cerium oxide, simple or mixed oxide, which comprises an amino acid. This acid can more particularly be an aliphatic amino acid. This can in particular be a C4-C10 acid and preferably a C4-C8 acid. Such a dispersion is described in patent application EP-A-1 301 435.
- A mixture of the dispersion with a suspension of the support is formed. This suspension is generally based on the support or on a precursor of the support, that is to say a compound which, after calcination, can result in alumina, silica, zirconium oxide or titanium oxide. Dried precursors, that is to say exhibiting a loss on ignition of at most 50%, more particularly of at most 25%, may be concerned. These can in particular be hydroxides or oxyhydroxides. The suspension is generally an aqueous suspension.
- Mixing is carried out in an aqueous phase, generally water and, for example, distilled or deionized water.
- The second stage of the process is a drying stage.
- This drying is carried out by atomization.
- The term “drying by atomization” is to be understood to mean drying by spraying the mixture into a hot atmosphere (spray drying). The atomization can be carried out by means of any sprayer known per se, for example by a spray nozzle of the shower head or other type. Use may also be made of “rotary” atomizers. Reference may in particular be made, with regard to the various spraying techniques capable of being employed in the present process, to the reference work by Masters entitled “Spray Drying” (second edition, 1976, published by George Godwin, London).
- The final stage of the process is a calcination stage.
- This calcination makes it possible to develop the crystallinity of the product formed and it can also be adjusted and/or chosen according to the subsequent operating temperature reserved for the composition according to the invention, this being done while taking into account the fact that the specific surface of the product decreases as the calcination temperature employed increases. Such a calcination is generally carried out under air but a calcination carried out, for example, under an inert gas or under a controlled atmosphere (oxidizing or reducing) is very clearly not excluded.
- In practice, the calcination temperature is generally restricted to a range of values of between 500° C. and 1000° C., preferably between 600° C. and 800° C.
- According to a first alternative form of this process, it is possible to carry out a simple calcination under H2 at a temperature of between 800 and 1000° C. for at least 2 h, more particularly at least 4 h and more particularly still at least 6 h.
- According to another alternative form of this process, it is possible to carry out a double calcination. It is thus possible to carry out a first calcination under an inert gas or under vacuum. The inert gas can be helium, argon or nitrogen. The vacuum is generally a low vacuum with an oxygen partial pressure of less than 10−1 mbar. The calcination temperature is at least 900° C. and generally at most 1000° C. The time for this first calcination is generally at least 2 hours, preferably at least 4 hours and in particular at least 6 hours. An increase in this time generally results in an increase in the degree of reducibility. Of course, the time can be set according to the temperature, a low calcination time requiring a higher temperature.
- A second calcination is subsequently carried out under an oxidizing atmosphere, for example under air. In this case, the calcination is generally carried out at a temperature of at least 600° C. over a time which is generally at least 30 minutes. It is preferable not to exceed a calcination temperature of 900° C.
- B Specific Colloidal Dispersion
- A more specific description will be given below of a dispersion which may be useable in the context of the invention, very particularly when it is desired to prepare a composition having a supported oxide which is a mixed oxide or solid solution.
- This dispersion is a colloidal dispersion, in a continuous phase, of a compound of cerium and of at least one other element M chosen from zirconium and rare earth metals (Ln) other than cerium and it is characterized in that the compound is in the form of a mixed oxide in which the cerium and the element M are in pure solid solution and in that the compound comprises cerium in the form of cerium(III) in an amount, expressed as cerium(III)/total cerium atomic ratio, of between 0.005 and 0.06.
- This dispersion can be prepared by a process which comprises the following stages:
-
- a liquid medium is formed comprising salts of cerium and of at least one element M, the cerium salts being cerium(IV) and cerium(III) salts:
- the medium is brought into contact with a base, so as to obtain a pH of at least 9, whereby a precipitate is obtained;
- said precipitate is separated from the medium;
- the precipitate is washed;
- the precipitate is peptized by treatment with an acid, whereby the dispersion is obtained; the process additionally comprising at least one washing stage, either after the stage of separation of the precipitate or after the peptization stage.
- The liquid continuous phase of the dispersion described here is generally an aqueous phase, more particularly water.
- One of the specific characteristics of the dispersion described here is that, in the colloidal particles, the abovementioned compound of which they are formed is in the form of a mixed oxide (Ce,M)O2 in which the cerium and the element M are in solid solution. This term is to be understood to mean that one of the elements, generally the element M, is completely incorporated in the crystal lattice of the oxide of the other matrix-forming element, for example the cerium. This incorporation can be demonstrated by the X-ray diffraction technique on colloids after washing, in particular by ultrafiltration or also by ultracentrifugation, and drying at a temperature of 60° C. The X-ray diagrams reveal the presence of a crystal structure corresponding to the oxide of the matrix-forming element (generally cerium oxide), the unit cell parameters of which are more or less offset with respect to a pure oxide of this first matrix-forming element, which thus demonstrates the incorporation of the other element in the crystal lattice of the oxide of the first. For example, in the case of a solid solution of the element M in cerium oxide, the X-ray diagrams then reveal a crystal structure of fluorine type, just like crystalline ceric oxide CeO2, the unit cell parameters of which are more or less offset with respect to a pure ceric oxide, thus reflecting the incorporation of the element M in the crystal lattice of the cerium oxide.
- The solid solution is pure, that is to say that, for the colloidal particles, the total amount of an element is in solid solution in the other, for example all the element M is in solid solution in the cerium oxide. In this case, the X-ray diagrams show only the presence of the solid solution and do not comprise lines corresponding to an oxide such as oxide of the element other than the matrix-forming element, for example an oxide of the element M. However, it is not out of the question for the liquid continuous phase to be able to comprise a certain amount of element M in the form of ions originating from a portion of the total amount of the element M introduced during the preparation of the dispersion.
- As indicated above, the element M is chosen from the group consisting of zirconium and rare earth metals (Ln) other than cerium, it being possible, of course, for these elements to be present as a mixture, as will be seen in the continuation of the description.
- Another characteristic of the dispersion described here is the presence of cerium in the form of cerium(III). The amount of cerium(III), expressed by the cerium(III)/total cerium atomic ratio, is between 0.005 and 0.06. More particularly, this amount can be between 0.005 and 0.05 and more particularly still between 0.005 and 0.03.
- It should be noted here that the cerium(III) can be present in the compound as cation, either in the form adsorbed at the surface of the particles of the cerium compound or in the crystal unit cell of the compound. Of course, both these forms may coexist.
- The presence of cerium(III) in solution can be demonstrated by chemical quantitative determination. Use may thus be made of a technique for analysis by potentiometric titration by oxidation of cerium(III) to give cerium(IV) using potassium ferricyanide in potassium carbonate medium. The presence of cerium(III) at the surface of the particles of the dispersion can be demonstrated by the determination of the isoelectric point of the colloidal dispersions. This determination is carried out in a known way by measuring the variation in the zeta potential of the dispersions. When the variation in this potential is measured, by varying the pH of a dispersion from an acidic value to a basic value, this potential changes from a positive value to a negative value, the transition at the zero value of the potential constituting the isoelectric point. The presence of cerium(III) at the surface increases the value of the isoelectric point with respect to a compound comprising only cerium(IV).
- Various alternative forms of the dispersion described here, depending on the nature of the cerium compound and more specifically on the nature of the element M, will now be described in more detail. It should be noted here that the formulae which are given below in the description of these alternative forms correspond to compositions which result from chemical analyses on colloids recovered either by ultracentrifuging at 50 000 rev/min for 6 hours or else after washing the dispersions, this washing being carried out by ultrafiltration or by dialysis with at least 10 equivalent volumes of water (1 volume of dispersion:10 volumes of water).
- According to a first alternative form, the element M is zirconium. More particularly, in the case of this alternative form, the compound can correspond to the formula (3) Ce1-xZrxO2 in which x is less than 1 and is at least equal to 0.01, preferably at least equal to 0.02.
- According to a second alternative form, the element M is a combination of zirconium and of at least one rare earth metal Ln. This alternative form is particularly advantageous in the case where the rare earth metal is a trivalent rare earth metal. The rare earth metal can be in particular lanthanum, gadolinium, terbium, praseodymium or neodymium. More particularly, in the case of this second alternative form, the compound can correspond to the formula (4) Ce1-x-yZrxLnyO2 in which x+y<1, x adheres to the condition 0.05≦x≦0.95 and y is at least equal to 0.01, the high value of y being chosen so that a solid solution is indeed obtained. Preferably, x adheres to the condition 0.20≦x≦0.8 and more preferably still the condition 0.40≦x≦0.60. Preferably also, y is at least equal to 0.02 and more preferably still y is at least equal to 0.03. Preferably, y is at most equal to 0.05 and more preferably still to at most 0.04. Still in the case of this alternative form, the element M can be a combination of at least two rare earth metals, at least one of which is praseodymium. Finally, it may be noted that, in the case where M is terbium or praseodymium, optionally in combination with another rare earth metal, these elements can be present both in the Tb(III) and Pr(III) forms and the Tb(IV) and Pr(IV) forms.
- The compound of the dispersion described here can also be a compound in which M is a rare earth metal or a combination of rare earth metals. Again, a particularly advantageous case is that where the rare earth metal is a trivalent rare earth metal. The rare earth metal can in particular be lanthanum, gadolinium, terbium, praseodymium or neodymium. The compound can then correspond more particularly to the following formula (5) Ce1-xLnxO2 in which x is at most equal to 0.15 and is at least equal to 0.01, preferably at least equal to 0.02 and more preferably still at least equal to 0.04. Preferably, x is at most equal to 0.10 and more preferably still at most equal to 0.05. The rare earth metal can be present, at least in part, in the Ln(III) form and, here again, either in the crystal unit cell or in the form adsorbed at the surface of the particles of the cerium compound. In the case of praseodymium, the latter element can be present both in the Pr(III) and Pr(IV) forms and, in the same case, x is more particularly at least equal to 0.04 and more particularly still between 0.03 and 0.08. Finally, the compound of the dispersion can also correspond to the formula (6) Ce1-xLn′xO2 where Ln′ describes a combination of at least two rare earth metals and where x is at most equal to 0.30 and can preferably be at least equal to 0.01.
- The particles which constitute the compound of the dispersion exhibit a fine and narrow particle size distribution. This is because they have a size, measured by their mean diameter, which is preferably at most 10 nm and which can more particularly be between 2 and 8 nm. This size is conventionally determined by transmission electron microscopy (TEM) on a sample dried beforehand on a carbon membrane supported on a copper grid and over a mean of 50 measurements.
- In addition, these particles are well separated. The cryo-TEM technique can be used to determine the state of aggregation of the particles. It makes it possible to observe, by transmission electron microscopy, samples kept frozen in their natural medium, which can, for example, be water.
- Freezing is carried out on thin films with a thickness of approximately 50 to 100 nm in liquid ethane for the aqueous samples.
- The state of dispersion of the particles is well preserved by cryo-TEM and representative of that present in the true medium. In the present case, cryo-TEM demonstrates the well-separated aspect of the particles.
- The dispersion described here generally exhibits a pH which can be between 0.5 and 6.
- The dispersion generally exhibits a concentration of mixed oxide of at least 0.1M, preferably of at least 0.25M and advantageously of greater than 1M.
- Other specific embodiments of the dispersion will now be described.
- A specific embodiment corresponds to dispersions having a basic pH. According to this embodiment, the compound of cerium and of at least one other element M exists in the form of particles additionally comprising citrate anions, these anions being adsorbed at the surface of the particles. The molar ratio r=citric acid/mixed oxide is generally between 0.1 and 0.6, preferably between 0.2 and 0.45. For this embodiment, the pH of the dispersions is at least 7, preferably at least 8.
- Another specific embodiment corresponds to dispersions which are functionalized. In this case, the compound of cerium and of at least one other element M exists in the form of particles comprising, at the surface, a bifunctional compound comprising a functional group R1 of amine, sulfate, phenyl, alkylethoxy or succinate type and a functional group R2 of carboxylic, dicarboxylic, phosphoric, phosphonic or sulfonic type, the functional groups R1 and R2 being separated by an organic chain of the —(CH2)x— type, x preferably being at most equal to 6. It may be thought that this bifunctional compound is bonded at the surface by interactions of complexing type between the functional group R2 and the cerium or M present at the surface of the colloidal particles. The molar ratio r′=bifunctional compound/mixed oxide is generally at most 0.6, preferably at most 0.4 and more preferably still at most 0.2.
- The bifunctional compound can be chosen from aliphatic amino acids, for example aminocaproic acid, aminated sulfonic acids, such as aminoethylsulfonic acid, or alkyl polyoxyethylene ether phosphates.
- Finally, it should be noted that the colloidal dispersions described here are particularly stable, that is to say that separation by settling or phase separation is not observed over a period of time which can be greater than 1 year.
- The process for the preparation of the dispersions described here will now be explained in detail.
- As indicated above, this process comprises a first stage in which a liquid medium comprising cerium salts and salts of at least one element M is formed, the cerium salts being cerium(IV) and cerium(III) salts. The proportion of cerium(III) salts and of cerium(IV) salts, expressed by the Ce(III)/total Ce (Ce(III)+Ce(IV)) molar ratio, is generally at least 2% and at most 20%, preferably between 2% and 10%, this proportion being chosen according to the level of cerium(III) desired in the colloidal dispersion which it is desired to prepare. The liquid medium is generally water and the salts are usually introduced in the form of solutions.
- The salts can be salts of inorganic or organic acids, for example of the sulfate, nitrate, chloride or acetate type, it being understood that the starting medium must comprise at least one cerium(IV) salt. Use may more particularly be made, as Ce(IV) solution, of a ceric ammonium nitrate solution to which Ce(III) is added in the form of cerous nitrate or Ce(III) acetate or cerous chloride. Use may also be made of a ceric nitrate solution obtained by attack on CeO2 by nitric acid, Ce(III) being added to this solution. Use may advantageously be made of a ceric nitrate solution obtained by electrolysis and comprising Ce(III). The solution of Zr(IV) can be of ZrOCl2 or of ZrO(NO3)2. The rare earth metals Ln are generally introduced in the form of Ln(III) salts, for example nitrates.
- The second stage of the process consists in bringing the medium formed above into contact with a base.
- Use may in particular be made, as base, of products of the hydroxide type. Mention may be made of alkali metal hydroxides, alkaline earth metal hydroxides and aqueous ammonia. Use may also be made of secondary, tertiary or quaternary amines. However, the amines and aqueous ammonia may be preferred insofar as they reduce the risks of contamination by alkali metal or alkaline earth metal cations.
- The addition of the base is carried out instantaneously or gradually but so as to obtain a pH of the medium of at least 9, preferably of at least 9.5 and more preferably still of at least 10. The addition of the base results in the formation of a precipitate.
- After the addition of the base, it is possible to carry out a maturing of the medium for a period of time which can vary, for example, between 10 minutes and 1 hour, generally at ambient temperature.
- The precipitate can be separated from the liquid medium by any known process, for example by centrifuging.
- The precipitate resulting from the reaction can subsequently be washed. This washing can be carried out by putting the precipitate back into water and then, after stirring, by separating the solid from the liquid medium, for example by centrifuging. This operation can be repeated several times, if necessary. Generally, this washing is carried out so as to obtain a washing slurry, that is to say the water in which the precipitate is resuspended, with a pH of at most 8.75, preferably of at most 8, advantageously of at most 7.
- The final stage of the process is a stage of peptization of the precipitate obtained above. This peptization is carried out by treatment of the precipitate with an acid. This treatment is generally carried out by dispersing the precipitate in an acidic solution and stirring the medium thus formed. Use may be made, for example, of nitric acid, hydrochloric acid or acetic acid. Acetic acid can advantageously be used to obtain dispersions of compounds in which the content of trivalent rare earth metal is high. The peptization is generally carried out at a temperature between ambient temperature and 90° C., preferably at ambient temperature. The amount of acid used is such that the H+/(Ce+M) molar ratio is generally at most 1.5, preferably at most 1.25 and more preferably still at most 1. On conclusion of the peptization, a colloidal dispersion is obtained directly and without another intermediate stage.
- It is possible to wash, by ultrafiltration or by dialysis, the dispersion thus obtained. This washing makes it possible to remove the element M which might occur in ionic form.
- It should be noted that the process described here comprises at least one washing stage, it being possible for this washing to take place under the conditions which have just been described, that is to say either on the precipitate or on the dispersion or also on both.
- For the specific embodiment described above in which the particles comprise citrate anions at the surface, the preparation process is of the type of that which has just been described but it is supplemented by a stage of bringing into contact with citric acid. More specifically, the citric acid can be added to the dispersion obtained after peptization, for example in the form of a citric acid hydrate powder. The citric acid then dissolves with stirring. The citric acid/mixed oxide molar ratio is within the range of values given above, that is to say generally between 0.1 and 0.6. It is possible to leave the medium obtained standing for between 30 minutes and 24 hours at ambient temperature.
- Subsequently, a solution of a base is gradually added, this base being of the same type as that described above for the precipitation stage, so as to obtain the desired pH of at least 7, preferably of at least 8.
- More specifically, the addition can be carried out for between 10 min and 2 hours at ambient temperature.
- Likewise, in order to obtain a functionalized dispersion according to the embodiment described above, the bifunctional compound is added to the dispersion obtained after peptization.
- After the description of the colloidal dispersions capable of being used as starting material in the preparation of the compositions of the invention, the description of other processes will be given below.
- C Second Process for the Preparation of the Compositions of the Invention
- The compositions of the invention can also be prepared by a second process which will be described below.
- This process comprises the following stages:
-
- a liquid mixture comprising a salt of cerium and, if appropriate, of the element M and a suspension of the support is formed;
- the mixture thus formed is heated at a temperature of at least 100° C.;
- the precipitate thus obtained is recovered;
- said precipitate is calcined.
- For the first stage, the starting material is also a colloidal suspension or dispersion of the support but it is mixed with a salt of cerium and, in the case of a composition where cerium oxide is a mixed oxide, of the element M. This mixing is carried out in an aqueous phase, generally water.
- The salts can be chosen from nitrates, sulfates, acetates, chlorides or ceric ammonium nitrate.
- Mention may thus be made, by way of examples, of zirconyl sulfate, zirconyl nitrate or zirconyl chloride. Zirconyl nitrate is most generally used. Mention may also in particular be made of cerium(IV) salts, such as the nitrate, or ceric ammonium nitrate, for example, which are particularly well suited here. Preferably, ceric nitrate is used.
- The following stage of the process is the stage of heating the liquid mixture thus formed.
- The temperature at which the liquid mixture is heated is at least 100° C. and more particularly still at least 130° C. The heating operation can be carried out by introducing the liquid mixture into a closed chamber (closed reactor of the autoclave type). Under the temperature conditions given above and in an aqueous medium, it can thus be specified, by way of illustration, that the pressure in the closed reactor can vary between a value of greater than 1 bar (105 Pa) and 165 bar (1.65×107 Pa), preferably between 5 bar (5×105 Pa) and 165 bar (1.65×107 Pa). The heating can also be carried out in an open reactor for temperatures in the region of 100° C.
- The heating can be carried out either under air or under an inert gas atmosphere, preferably under nitrogen.
- The duration of the heating can vary within wide limits, for example between 1 and 48 hours, preferably between 2 and 24 hours. Likewise, the rise in temperature takes place at a rate which is not critical and the set reaction temperature can thus be reached by heating the liquid mixture, for example, for between 30 minutes and 4 hours, these values being given entirely by way of indication.
- On conclusion of the heating stage, a solid precipitate is recovered which can be separated from its medium by any conventional solid/liquid separating technique, such as, for example, filtration, settling, draining or centrifuging.
- The product as recovered can subsequently be subjected to washing operations which are then carried out with water or optionally with a basic solution, for example an aqueous ammonia solution, or an acidic solution, for example a nitric acid solution.
- According to a specific alternative form of the invention, the process comprises a maturing.
- This maturing is generally carried out on a suspension obtained after putting the precipitate back into water, in particular after the washing operation. The maturing is carried out by again heating this suspension. The temperature at which the suspension is heated is at least 40° C., more particularly at least 60° C. and more particularly still at least 100° C. Generally, this temperature is at most 200° C., more particularly at most 150° C. The medium is thus maintained at a constant temperature for a period of time which is usually at least 30 minutes and more particularly at least 1 hour. The maturing can be carried out at atmospheric pressure or optionally at a higher pressure.
- The final calcination stage of this second process can be carried out in the same way as for the first process and thus that which was described above for this calcination likewise applies here.
- In the case of the preparation of compositions with a support based on or essentially composed of alumina stabilized by a stabilizing element chosen from rare earth metals, barium and strontium, two other processes (third and fourth processes) can be employed, which processes will now be described.
- D Third Process for the Preparation of the Compositions of the Invention
- The third process according to the invention comprises the following stages:
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- (a) a liquid mixture comprising a colloidal dispersion of the supported oxide and, if appropriate, of the oxide of the element M, an aluminum compound and a compound of the stabilizing element is formed;
- (b) the preceding mixture and a base are brought together, whereby a suspension comprising a precipitate is obtained;
- (c) the suspension is optionally subjected to a maturing;
- (d) the suspension thus obtained is dried;
- (e) the dried product thus obtained is calcined.
- The mixing of stage (a) is carried out in an aqueous phase, generally water.
- Use is made, for the supported oxide, of any colloidal dispersion of the type described above.
- The compound of the stabilizing element can in particular be a salt, such as a nitrate, an acetate, a chloride or a sulfate, in the form of a solution.
- The aluminum compound is generally an alumina precursor, that is to say a compound which, after calcination, can result in alumina. This compound can thus be an aluminum hydroxide, such as bayerite, hydrargillite or gibbsite, or nordstrandite, or an aluminum oxyhydroxide, such as boehmite, pseudoboehmite and diaspore. The aluminum compound can be provided in the form of an aqueous suspension, in particular of an acidic suspension, for example comprising nitric acid. This suspension is then mixed with the dispersion of the supported oxide and the stabilizing element, the latter in the form of a solution, for example.
- The second stage of the process consists in bringing together the mixture obtained in stage (a) and a base.
- Use may be made, as base, of products of the hydroxide, carbonate or basic carbonate type, for example. Mention may be made of alkali metal or alkaline earth metal hydroxides, or secondary, tertiary or quaternary amines. However, amines and aqueous ammonia may be preferred insofar as they reduce the risks of pollution by alkali metal or alkaline earth metal cations. Urea may also be mentioned.
- The contacting operation can be carried out in any order in a liquid medium.
- The operation of bringing into contact with the base results in the formation of a precipitate in suspension in the liquid reaction medium.
- The third stage is just an optional stage. This stage (c) consists in subjecting the suspension to a maturing. The maturing is carried out by heating the suspension at a temperature of at least 60° C., more particularly of at least 80° C. Generally, this temperature is at most 200° C., more particularly at most 150° C. The medium is thus maintained at a constant temperature for a time which is usually at least 30 minutes and more particularly at least 1 hour. The maturing can be carried out at atmospheric pressure or optionally at a higher pressure.
- On conclusion of stage (b) or optionally of the maturing stage, when the latter is carried out, the abovementioned stages (d) and (e) are carried out. These two stages are similar to the final two stages of the first process of the invention and everything which was described above likewise applies to these stages (d) and (e). However, it should be noted that the drying can be carried out by a means other than atomization, for example in an oven.
- An alternative form can be used in the context of this third process. This alternative form consists, on conclusion of stage (b) or optionally of the maturing stage, when the latter is carried out, in separating the precipitate from the suspension, in washing it and in redispersing it in water to form a second suspension. It is the latter suspension which is subsequently dried in stage (d).
- The final calcination stage of this third process can be carried out in the same way as for the preceding processes and thus that which was described above for this calcination likewise applies here.
- E Fourth Process for the Preparation of the Compositions of the Invention
- The fourth process of the invention is now described below.
- This process comprises the following stages:
-
- (a) a liquid mixture comprising a colloidal dispersion of the supported oxide and, if appropriate, of the oxide of the element M and an aluminum compound is formed;
- (b) the preceding mixture and a base are brought together, whereby a suspension comprising a precipitate is obtained;
- (c) the suspension is optionally subjected to a maturing;
- (d) a compound of the stabilizing element is added to the suspension thus obtained;
- (e) the suspension resulting from the preceding stage is dried;
- (f) the dried product thus obtained is calcined.
- This process differs from the third process in that the compound of the stabilizing element is introduced in a different stage, on conclusion of stage (b) or optionally on the maturing stage, if the latter exists. Consequently, everything which was described for the third process likewise applies here. The compound of the stabilizing element is in particular of the same type as described above. Furthermore, it is also possible to employ the alternative form described above for the third process in which, on conclusion of stage (b) or optionally of the maturing stage, when the latter is carried out, the precipitate is separated from the suspension, washed and redispersed in water to form a second suspension. In this case, the compound of the stabilizing element is added to this second suspension.
- The fourth process described here applies very particularly to the case where the stabilizing element is barium or strontium.
- The compositions of the invention as described above or as obtained by the processes described above are provided in the form of powders but they can optionally be shaped in order to be provided in the form of granules, bulbs, cylinders or honeycombs of variable sizes.
- The compositions of the invention can be used as catalysts or catalyst supports. Thus, the invention also relates to catalytic systems comprising the compositions of the invention. These systems comprise a coating (wash coat), with catalytic properties, based on these compositions and on a binder of known type, on a substrate of the metal or ceramic monolith type, for example. The coating can itself also comprise a support of the type of those mentioned above. This coating is obtained by mixing the composition with the binder, such as to form a suspension which can subsequently be deposited on the substrate.
- These catalytic systems and more particularly the compositions of the invention can have a great many applications. They are therefore particularly well suited to, and thus useable in, the catalysis of various reactions, such as, for example, dehydration, hydrosulfurization, hydrodenitrification, desulfurization, hydrodesulfurization, dehydrohalogenat ion, reforming, steam reforming, cracking, hydrocracking, hydrogenation, dehydrogenation, isomerization, dismutation, oxychlorination, dehydrocyclization of hydrocarbons or other organic compounds, oxidation and/or reduction reactions, the Claus reaction, treatment of exhaust gases from internal combustion engines, in particular for automobile afterburning and in particular three-way catalysis, demetallation, methanation, the shift conversion or catalytic oxidation of the soot emitted by internal combustion engines, such as diesel engines or gasoline engines operating under lean burn conditions. Finally, the catalytic systems and the compositions of the invention can be used for the removal of NOx compounds by trapping the latter or as catalyst for the selective reduction of NOx compounds with urea/ammonia.
- In the case of the uses in catalysis, the compositions of the invention can be employed in combination with precious metals or also transition metals in the oxide, sulfide or other form and they thus act as support for these metals. The nature of these metals and the techniques for the incorporation of the latter in the support compositions are well known to a person skilled in the art. For example, the metals can be gold, silver, platinum, rhodium, palladium, iridium, molybdenum, tungsten, nickel, cobalt, manganese or vanadium; they can in particular be incorporated in the compositions by impregnation.
- Among the uses mentioned, the treatment of exhaust gases from internal combustion engines (automobile afterburning catalysis) is a particularly advantageous application. For this reason, the invention also relates to a process for the treatment of exhaust gases from internal combustion engines which is characterized in that use is made, as catalyst, of a catalytic system as described above or of a composition according to the invention and as described above.
- It should be noted that the compositions of the invention in which the support is based on stabilized alumina are particularly advantageous as NOx trap. The invention thus also relates to a process for the treatment of exhaust gases from internal combustion engines which is characterized in that use is made, as NOx trap, of a composition according to the invention in which the support is based on stabilized alumina or a catalytic system comprising such a composition. This composition can more particularly be that corresponding to one of the two embodiments described above in which the support is based on alumina stabilized by barium, strontium or lanthanum and the supported oxide mixtures of cerium oxide, of zirconium oxide and of oxide of a rare earth metal other than cerium or of cerium oxide, of praseodymium oxide and of oxide of a rare earth metal other than cerium and praseodymium.
- The abovementioned systems are, for the treatment of exhaust gases, fitted in a known way in the exhaust mufflers of motor vehicles.
- Examples will now be given.
- This example relates to a composition based on cerium oxide on a silica support which is prepared by the second process described above.
- A mixture comprising 70% of SiO2 and 30% of CeO2 is prepared by mixing, in a beaker with stirring, 35 g of SiO2 powder (170 m2/g), dispersed in 500 ml of H2O at pH 0.5, with an acidic (pH 0.5) Ce(NO3)4 solution comprising 15 g of CeO2 (CeO2 80 g/l). The combined mixture is transferred into an autoclave and brought to 150° C. for 2 hours while stirring at 300 revolutions/min.
- The cooled mixture is separated by filtration and washed with 2 l of water at pH 9. The cake obtained is dispersed in water at a concentration of oxide of 50 g/l (oxide) and then matured at 100° C. for 2 hours with stirring. After cooling, the suspension is separated by centrifuging. The cake is subsequently calcined under air at 800° C. for 6 h.
- This example relates to a composition based on a mixed oxide of cerium and of zirconium on a silica support which is prepared by the first process described above.
- A colloidal dispersion of particles of a mixed oxide of formula Ce0.5Zr0.5O2 is prepared beforehand.
- For this, 95.7 ml of a first solution, comprising 1.5 M/l of Ce(NO3)4 and 0.5 M of HNO3, are mixed with 43.7 ml of a second solution comprising 3.3 M/l of ZrO(NO3)2. The volume of the solution obtained is brought to 2300 ml by addition of water. The final pH is 1.9.
- 186 ml of 28% NH3 solution are added instantaneously. The pH increases to 10 and the formation of a precipitate is observed.
- The precipitate is filtered off and then washed with 2400 ml of deionized water. Washing is repeated 3 times in succession with an identical volume of washing solution. The pH of the final suspension is 7.5.
- The cake is resuspended in a solution comprising 20.2 g of a 68% nitric acid HNO3 solution (H+/(Ce+Zr)=0.75 in moles) and the volume is made up to 500 ml by addition of deionized water. The Ce+Zr concentration is equal to 0.29 mol/l. After stirring overnight, a colloidal dispersion with a size of 4 nm is obtained which is clear to the eye.
- Aminocaproic acid is added to this dispersion so as to obtain a final pH of 4.5 (98% 6-aminocaproic acid, Aldrich).
- 100 g of SiO2 powder (170 m2/g) are added to 550 ml of the colloidal dispersion of mixed Ce/Zr oxide in a beaker with stirring. The mixture is kept stirred for 15 minutes.
- This suspension is atomized at 110° C. (outlet temperature 110° C., inlet temperature 220° C.) with a flow rate of 1 l/h.
- The powder is calcined under air at 800° C. for 6 h.
- This example relates to a composition based on a mixed oxide of cerium and of zirconium on an alumina support which is prepared by the first process described above.
- A boehmite sol is prepared in a beaker equipped with a magnetic bar by dispersing, with stirring, 78.6 g of an AlOOH powder (Pural B21 alumina comprising 71.25% of Al2O3) in 700 ml of H2O brought to pH 2 using a 68% concentrated HNO3 solution. After a few hours, a gel is obtained at pH 4.
- At the same time, a colloidal dispersion of particles of mixed oxide of formula Ce0.5Zr0.5O2 is prepared as described in example 2. Aminocaproic acid is likewise added thereto, so as to obtain a final pH of 4.5.
- 2 liters of the dispersion of mixed oxide CeO2/ZrO2 are introduced with stirring at the rate of 50 ml/min into the 700 ml of the boehmite dispersion prepared above. The mixture is kept stirred for 15 minutes and then atomized (inlet temperature 245° C., outlet temperature 110° C.) at a flow rate of 1 liter/hour.
- The powder is calcined under air at 800° C. for 6 h.
- The characteristics of size of the supported oxide and of specific surface of the composition for the compositions prepared in examples 1 to 3 are given in the following table 1.
-
TABLE 1 Sizes of the supported particles and specific surfaces Calcination 800° C./6 h Example X-ray size (nm) BETS (m2/g) 1 6 161 2 6 95 3 6 113 - In this example, the values for reducibility of the cerium, measured for the compositions described in the preceding examples, are given.
- The reducibility of the cerium is measured by temperature-programmed reduction in the following way. Use is made of a Micromeritics Autochem 2920 device with a quartz reactor and a 200 mg sample which has been calcined beforehand at 800° C. for 6 hours under air. The gas is hydrogen at 10% by volume in argon and with a flow rate of 25 ml/min. The temperature rise takes place from ambient temperature to 900° C. at the rate of 20° C./min. The signal is detected with a thermal conductivity detector. The temperature is measured in the sample using a thermocouple.
- The reducibility of the cerium is calculated from the hydrogen consumption, it being understood that ½ mol of H2 consumed and measured by the method described above corresponds to 1 mol of reduced Ce(IV). The hydrogen consumption is calculated from the missing area of the hydrogen signal from the base line at 30° C. to the base line at 900° C. (respectively 600° C.) when the reducibility is measured between 30° C. and 900° C. (respectively 600° C.)
- The reducibility values are collated in table 2.
-
TABLE 2 Reducibility of the cerium (%) Example 30° C.-600° C. 30° C.-900° C. 1 41 100 2 44 87 3 41 82
The examples which follow relate to compositions for which the support is based on stabilized alumina. - The starting materials used in these examples are as follows:
- Sasol SB1 boehmite comprising 78% by weight of oxide
- Barium nitrate comprising 99% by weight of oxide
- Lanthanum nitrate solution comprising 454 g/l of oxide
- Ceric nitrate solution comprising 256 g/l of oxide with a cerium(III) content of 0.11 mol/l and a Ce(III)/total cerium atomic ratio of 0.06
- Zirconyl nitrate solution comprising 18.7% by weight of oxide
- 68 vol % nitric acid
- 28 vol % aqueous ammonia
- This example relates to a composition based on cerium oxide on a support made of alumina stabilized by lanthanum, the proportions by weight of which, expressed as oxide, are 75%, 20% and 5% respectively for the aluminum, the lanthanum and the cerium.
- 96 g of boehmite are added to an acidic solution, comprising 19 g of 5 mol/l nitric acid and 300 ml of demineralized water, in a beaker equipped with a magnetic bar and a pH electrode. The pH of the solution is 1.9. 35 g of the cerium oxide sol described in example 4 of European patent No. 208 581 B1 and then a mixture of 74 g of lanthanum nitrate in 50 ml of demineralized water are added to this mixture with stirring. This mixture is then gradually introduced with stirring into a vessel heel comprising 25 g of aqueous ammonia and 500 ml of demineralized water. The reaction mixture is subsequently subjected to maturing at 100° C. for one hour. The solid phase is separated from the supernatant by centrifugation. The solid phase is redispersed in demineralized water so that the total volume is 600 ml. The suspension is subsequently atomized on a device of Büchi Mini-Spray Dryer 190 type, inlet temperature=230° C., outlet temperature=115° C.
- The powder obtained is calcined under air at 600° C. for 2 h.
- The specific surfaces obtained after subsequent calcinations at different temperatures are shown below.
- 2 h 600° C.=166 m2/g
- 6 h 800° C.=120 m2/g
- 2 h 900° C.=112 m2/g
- 2 h 1000° C.=70 m2/g
- This example relates to a composition based on mixed oxide of cerium, of zirconium and of praseodymium comprising 25% by weight of oxides on a support formed of alumina stabilized by lanthanum in the overall proportions by weight, expressed as oxide, of 14%/6%/5%/15%/60% respectively for CeO2/ZrO2/Pr6O11/La2O3/Al2O3.
- 1) Preparation of a Colloidal Dispersion of CeO2—ZrO2—Pr6O11 Mixed Oxide
- A colloidal dispersion of particles of a CeO2—ZrO2—Pr6O11 mixed oxide is prepared beforehand according to the specific process described above.
- 320 g of cerium nitrate solution, 121.5 g of zirconyl nitrate solution and 70 g of praseodymium nitrate solution are introduced with stirring into a beaker comprising 151 ml of demineralized water. The solution thus obtained is gradually introduced with stirring into a vessel heel comprising 160 g of aqueous ammonia and 321 g of demineralized water. The solid phase is separated from the supernatant by filtration. The solid phase is washed with demineralized water or in a sintered glass filter. The solid phase is redispersed in a mixture of 45 g of nitric acid and 250 g of demineralized water. The solution obtained is then made up with demineralized water in order to achieve a total volume of 950 ml. The concentration of the solution is then 112 g/l of oxides and the pH is 1.0. This dispersion is heated at 80° C. for 1 h and a colloidal dispersion is obtained.
- 2) Deposition of the Colloidal Dispersion of CeO2—ZrO2—Pr6O11 Mixed Oxide on the Support Formed of Alumina Stabilized with Lanthanum
- A suspension of 38.5 g of boehmite and 8 ml of nitric acid (5M) is added to 125 g of the colloidal dispersion of CeO2—ZrO2—Pr6O11 mixed oxide prepared in 1). 28 g of lanthanum nitrate solution are subsequently added with stirring and the mixture is made up with demineralized water in order to obtain a total volume of 500 ml. This mixture is gradually introduced with stirring into a vessel heel comprising 22.5 g of aqueous ammonia and 200 ml of demineralized water. The final pH of the suspension is 9. The medium is subsequently heated at 95° C. for 1 h and is then cooled before being filtered in order to recover the solid phase, which is then washed with demineralized water on a sintered glass filter and redispersed in demineralized water (total volume of 500 ml) at a concentration of oxides of 100 g/l.
- The suspension is then atomized on a device of Büchi Mini-Spray Dryer 190 type, inlet temperature=225° C., outlet temperature=115° C.
- The powder obtained is calcined under air at 800° C. for 6 h.
- The specific surfaces obtained after subsequent calcinations at different temperatures are shown below.
- 6 h 800° C.=120 m2/g
- 2 h 900° C.=94 m2/g
- 2 h 1000° C.=71 m2/g
- This example relates to a composition based on mixed oxide of cerium, of zirconium and of praseodymium charged with 25% by weight of oxides on support made of alumina stabilized with barium in overall proportions by weight, expressed as oxide, of 14%/6%/5%/15%/60% respectively for CeO2/ZrO2/Pr6O11/BaO/Al2O3.
- A dispersion of 38.5 g of boehmite and 1.5 g of 15.2 mol/l concentrated nitric acid is added, with stirring, to 125 g of the colloidal dispersion of CeO2—ZrO2—Pr6O11 mixed oxide prepared in 1) of example 6. 515 ml of demineralized water are subsequently added with stirring in order to obtain a suspension comprising 50 g/l of oxides. This suspension is gradually introduced with stirring into a vessel heel comprising 21 g of aqueous ammonia and 176 ml of demineralized water. The final pH of the suspension is 9.3 at the end of the introduction. The medium is subsequently heated at 100° C. for 1 h and then it is cooled before being filtered in order to recover the solid phase, which is then washed with demineralized water on a sintered glass filter. The solid is subsequently redispersed in order to obtain a total volume of 500 ml in a solution of 160 ml of demineralized water and 13 g of barium nitrate.
- The suspension is then atomized on a device of Büchi Mini-Spray Dryer 190 type, inlet temperature=235° C., outlet temperature=110° C.
- The powder obtained is calcined under air at 600° C. for 2 h.
- The specific surfaces obtained after subsequent calcinations at different temperatures are shown below.
- 2 h 600° C.=142 m2/g
- 6 h 800° C.=112 m2/g
- 2 h 900° C.=93 m2/g
- 2 h 1000° C.=76 m2/g
- This example relates to a composition based on mixed oxide of cerium, of zirconium and of lanthanum comprising 25% by weight of oxides on a support formed of alumina stabilized with barium in overall proportions by weight, expressed as oxide, of 20.4/2.4/2.2/15/60% respectively for CeO2/ZrO2/La2O3/BaO/Al2O3.
- 1) Preparation of a Colloidal Dispersion of CeO2—ZrO2—La2O3 Mixed Oxide
- A colloidal dispersion of particles of a CeO2—ZrO2—La2O3 mixed oxide is first prepared according to the process described in example 6.
- 457 g of cerium nitrate solution, 51 g of zirconyl nitrate solution and 33.5 g of lanthanum nitrate solution are introduced with stirring into a beaker comprising 126 ml of demineralized water. The solution thus obtained is gradually introduced with stirring into a vessel heel comprising 165 g of aqueous ammonia and 316 g of demineralized water. At the end of the introduction, there is a pH of 9.2. The solid phase is separated from the supernatant by filtration. The solid phase is washed with demineralized water on a sintered glass filter. The solid phase is redispersed in a mixture of 50 g of nitric acid and 200 g of demineralized water. The solution obtained is then made up with demineralized water in order to achieve a total volume of 950 ml. The concentration of the solution is then 111.5 g/l of oxides and the pH is 0.9. This dispersion is heated at 80° C. for 1 h and a colloidal dispersion is obtained.
- 2) Deposition of the Colloidal Dispersion of CeO2—ZrO2—La2O3 Mixed Oxide on the Support Formed of Alumina Stabilized with Barium
- A suspension of 38.5 g of boehmite and 8.5 ml of nitric acid (5M) is added to 126 g of the colloidal dispersion of CeO2—ZrO2—La2O3 mixed oxide prepared in 1), followed by 535 ml of demineralized water. This mixture is gradually introduced with stirring into a vessel heel comprising 25 g of aqueous ammonia and 200 ml of demineralized water. The final pH of the suspension is 9.2. The medium is subsequently heated at 95° C. for 1 h and is then cooled before being filtered in order to recover the solid phase, which is then washed with demineralized water on a sintered glass filter. The solid is subsequently redispersed in a mixture of 13 g of barium nitrate and 160 ml of demineralized water. The mixture is subsequently made up with demineralized water in order to obtain a total volume of 500 ml for the suspension.
- The suspension is then atomized on a device of Büchi Mini-Spray Dryer 190 type, inlet temperature=225° C., outlet temperature=110° C.
- The powder obtained is calcined under air at 600° C. for 2 h.
- The specific surfaces obtained after subsequent calcinations at different temperatures are shown below.
- 2 h 600° C.=136 m2/g
- 6 h 800° C.=105 m2/g
- 2 h 900° C.=92 m2/g
- 2 h 1000° C.=76 m2/g
- This example relates to a composition based on mixed oxide of cerium, of lanthanum and of praseodymium comprising 25% by weight of oxides on a support made of alumina stabilized with lanthanum in the overall proportions by weight, expressed as oxide, of 19/18/3/60% respectively for CeO2/La2O3/Pr6O11/Al2O3.
- 1) Preparation of a Colloidal Dispersion of CeO2—La2O3—Pr6O11 Mixed Oxide
- A colloidal dispersion of particles of a mixed oxide of CeO2—La2O3—Pr6O11 mixed oxide is prepared beforehand.
- 426 g of cerium nitrate solution, 48 g of lanthanum nitrate solution and 38 g of praseodymium nitrate solution are introduced with stirring into a beaker comprising 147 ml of demineralized water. The solution thus obtained is gradually introduced with stirring into a vessel heel comprising 167 g of aqueous ammonia and 314 g of demineralized water. The solid phase is separated from the supernatant by filtration. The solid phase is washed with demineralized water on a sintered glass filter. The solid phase is redispersed in a mixture of 45 g of 68 vol % nitric acid and 300 g of demineralized water. The solution obtained is then made up with demineralized water in order to achieve a total volume of 1 l. The concentration of the solution is then 102 g/l of oxides and the pH is 1.0. This dispersion is heated at 80° C. for 1 h and a colloidal dispersion is obtained.
- 2) Deposition of the Colloidal Dispersion of CeO2—La2O3—Pr6O11 Mixed Oxide on the Support Made of Alumina Stabilized with Lanthanum
- A suspension of 38.5 g of boehmite and 1.7 ml of nitric acid (15.2M) is added to 137 g of the colloidal dispersion of CeO2—La2O3—Pr6O11 mixed oxide prepared in 1). The mixture is made up with demineralized water in order to obtain a total volume of 650 ml. The pH of the medium is 2.1. 28 g of lanthanum nitrate solution are then gradually introduced with stirring. The resulting mixture is gradually introduced with stirring into a vessel heel comprising 23 g of aqueous ammonia and 200 ml of demineralized water. The final pH of the suspension is 9.2. The medium is subsequently heated at 96° C. for 1 h and is then cooled to 50° C. before being filtered in order to recover the solid phase, which is then washed with demineralized water on a sintered glass filter and redispersed in 170 ml of demineralized water in order to obtain a concentration of oxides of 100 g/l.
- The suspension is then atomized on a device of Büchi Mini-Spray Dryer 190 type, inlet temperature=240° C., outlet temperature=115° C.
- The powder obtained is calcined under air at 800° C. for 6 h.
- The specific surfaces obtained after subsequent calcinations at different temperatures are shown below.
- 6 h 800° C.=102 m2/g
- 2 h 900° C.=83 m2/g
- 2 h 1000° C.=61 m2/g
- In this example, the values for reducibility of the compositions described in examples 5 to 9 are given.
- The reducibility of the compositions is measured by temperature-programmed reduction in the following way. Use is made of a Micromeritics Autochem 2920 device with a quartz reactor and a 200 mg sample which has been calcined beforehand at 800° C. for 6 hours under air. The gas is hydrogen at 10% by volume in argon and with a flow rate of 25 ml/min. The temperature rise takes place with ambient temperature to 900° C. at the rate of 20° C./min. The signal is detected with a thermal conductivity detector. The temperature is measured in the sample using a thermocouple.
- The reducibility of the cerium is calculated from the hydrogen consumption, it being understood that ½ mol of H2 consumed and measured by the method described above corresponds to 1 mol of reduced Ce(IV). The hydrogen consumption is calculated from the missing area of the hydrogen signal from the base line at 30° C. to the base line at 900° C. when the reducibility is measured between 30° C. and 900° C.
- The reducibility values are collated in table 3.
-
TABLE 3 Reducibility of the Reducibility of the cerium Example cerium (%) and praseodymium (%) 5 100 — 6 — 81 7 — 84 8 96 — 9 — 81 - Measurement of catalytic performance as storage capacity for NOx compounds in an oxidizing medium.
- This example illustrates the effectiveness of these materials used as precious metal support with regard to their storage capacity for nitrogen oxides NOx for catalytic compositions comprising 1% by weight of platinum prepared from the compositions of the preceding examples and in the following way.
- 5 g of compound according to one of the above examples are introduced into a beaker and then covered with water (50 ml) before the addition of a solution of tetraamine platinum hydroxide salt (3.125 ml at 16 g/l). After evaporation on a rotary evaporator, the catalytic composition thus obtained is dried in an oven at 120° C. for 2 h, then calcined at 500° C. under air for 2 h and aged at 700° C. under a 90% air/10% H2O mixture for 4 hours.
- The NOx storage capacity is measured under the following conditions:
- The catalytic composition as prepared above is introduced into a reactor and then pretreated at 300° C. for 12 hours under a gas stream with the following composition:
-
9% O2+10% H2O+2% SO2+79% N2 (corresponding to 1000 ppm of SO2). - The reactor is isolated and then cooled to ambient temperature under an N2 stream. This catalytic composition, thus sulfated, is introduced into a fresh reactor and heated from a temperature of 150° C. to a temperature of 600° C. under a reducing gas stream with the following composition:
-
4.9% O2+10% CO+5% CO2+10% HC (2500 ppm of C3H6+2500 ppm of C3H8 in N2)+5% H2O+65.1% N2. - The catalytic composition as prepared above was subsequently maintained under this reducing stream for 20 minutes at a temperature of 600° C. The purpose of this treatment is to simulate a sulfation/desulfation cycle.
- The reactor is subsequently isolated and then cooled under static conditions to ambient temperature. The reaction stream, with the composition: 10% O2+5% H2O+10% CO2+300 ppm NO in nitrogen, analyzed continuously by a Nicolet Magna 560 Fourier transform infrared (FT-IR) spectrometer, is introduced into the catalytic reactor, placed beforehand at the desired reaction temperature. After stabilization of the stream monitored by NO+NO2 analysis, the respective concentrations of NO and NO2 at the reactor outlet are continuously determined by the FTIR spectrometer.
- The integration of the NO and NO2 concentrations during the minute following the arrival of the reaction stream over the catalytic composition makes it possible to calculate the amount of trapped NOx compounds. The results are expressed by the amount by weight of trapped NOx compounds (%) at 1 minute, with respect to the total amount of NOx compounds fed during this minute.
- The measurements are subsequently carried out on other samples of catalytic compositions at the desired temperatures.
- The amounts of NOx compounds trapped at the temperatures of 200° C., 300° C., 350° C. and 400° C. are listed in table 4. The catalytic compositions of tests 1, 2 and 3 of this table correspond respectively to the products obtained after impregnation with platinum, according to the process described above, of the composition of example 5 (test 1), example 7 (test 2) and example 9 (test 3).
-
TABLE 4 Trapped NOx compounds as % by weight Test 200° C. 250° C. 300° C. 400° C. Test 1 87 89 73 59 (composition example 5) Test 2 97 Not Not 92 (composition determined determined example 7) Test 3 75 Not Not 75 (composition determined determined example 9)
It is seen, from the results of table 4, that the compositions of the invention exhibit a high NOx storage efficiency in the temperature region between 200° C. and 400° C. They are very particularly effective in the region of low temperatures, at 300° C. or below, in particular at temperatures as low as 200° C. The catalytic compositions of the invention are therefore particularly effective over the entire temperature range and in particular at low temperatures, from 200° C. to 300° C. and more particularly still at 200° C. and 250° C.
Claims (24)
1.-23. (canceled)
24. A catalyst/catalyst support composition comprising a supported oxide, based on a cerium oxide, deposited onto a support based on silica, alumina, titanium oxide or zirconium oxide, which comprises particles of said supported oxide deposited onto said support, said particles being separate or in the form of aggregates, having a size of at most 500 nm, and which exhibits, after calcination at a temperature of at least 800° C. for 6 hours, a reducibility measured from 30° C. to 900° C. of at least 80%.
25. A catalyst/catalyst support composition comprising a supported oxide, based on a cerium oxide, deposited onto an alumina-based support, which comprises particles of said supported oxide deposited onto said support, said particles being separate or in the form of aggregates, having a size of at most 500 nm, and which exhibits, after calcination at a temperature of at least 800° C. for 6 hours, a reducibility measured from 30° C. to 900° C. of at least 80%, the alumina support of which additionally being devoid of the elements barium and strontium.
26. A catalyst/catalyst support composition as defined by claim 24 , wherein the supported oxide comprises a mixture of a cerium oxide and at least one oxide of another element M selected from among zirconium and the rare earth metals other than cerium.
27. The catalyst/catalyst support composition as defined by claim 24 , wherein said particles, separate or in the form of aggregates thereof, have a size of at most 50 nm.
28. The catalyst/catalyst support composition as defined by claim 24 , wherein said particles, separate or in the form of aggregates thereof, have a size of at most 10 nm.
29. The catalyst/catalyst support composition as defined by claim 24 , exhibiting a reducibility of at least 85%.
30. The catalyst/catalyst support composition as defined by claim 24 , wherein the supported oxide comprises cerium oxide or a mixture of a cerium oxide and of a zirconium oxide, and, optionally, an oxide of a rare earth metal other than cerium, and having a zirconium content such that the Ce/Zr atomic ratio is at least 1, and in that it exhibits, after calcination at a temperature of at least 800° C. for 6 hours, a reducibility, measured from 30° C. to 600° C., of at least 35%.
31. The catalyst/catalyst support composition as defined by claim 24 , wherein the support essentially consists of alumina or alumina stabilized by at least one element selected from among the rare earth metals, silicon and zirconium.
32. The catalyst/catalyst support composition as defined by claim 24 , wherein the supported oxide comprises a mixture of a cerium oxide, of a zirconium oxide and of an oxide of a rare earth metal other than cerium and wherein the support is based on alumina stabilized by an element selected from the group consisting of barium, strontium and lanthanum.
33. The catalyst/catalyst support composition as defined by claim 24 , wherein the supported oxide comprises a mixture of a cerium oxide, of a praseodymium oxide and of an oxide of a rare earth metal other than cerium and praseodymium and wherein the support is based on alumina stabilized by an element selected from the group consisting of barium, strontium and lanthanum.
34. The catalyst/catalyst support composition as defined by claim 24 , wherein it exhibits a proportion of supported oxide of at most 75% by weight.
35. A process for the preparation of a catalyst/catalyst support composition as defined by claim 24 , which comprises the following stages:
(a) admixing a colloidal dispersion of the supported oxide and, if appropriate, of the oxide of the element M and a suspension of the support;
(b) drying the mixture thus formed by atomization; and
(c) calcining the dried product thus obtained.
36. The process as defined by claim 35 , wherein the colloidal dispersion of the supported oxide additionally comprises an amino acid.
37. A process for the preparation of a catalyst/catalyst support composition as defined by claim 24 , which comprises the following stages:
(a) providing a liquid mixture comprising a salt of cerium and, if appropriate, of the element M and a suspension of the support;
(b) heating the mixture thus formed at a temperature of at least 100° C.;
(c) recovering the precipitate thus obtained; and
(d) calcining said precipitate.
38. A process for the preparation of a catalyst/catalyst support composition as defined by claim 24 , wherein the support comprises alumina stabilized by a stabilizing element selected from among the rare earth metals, barium and strontium, which comprises the following stages:
(a) providing a liquid mixture comprising a colloidal dispersion of the supported oxide and, if appropriate, of the oxide of the element M, an aluminum compound and a compound of the stabilizing element;
(b) mixing the mixture thus provided and a base, whereby a suspension comprising a precipitate is obtained;
(c) drying the suspension thus obtained; and
(d) calcining the dried product thus obtained.
39. A process for the preparation of a catalyst/catalyst support composition as defined by claim 24 , wherein the support comprises alumina stabilized by a stabilizing element selected from among the rare earth metals, barium and strontium, which comprises the following stages:
(a) providing a liquid mixture comprising a colloidal dispersion of the supported oxide and, if appropriate, of the oxide of the element M and an aluminum compound;
(b) mixing the mixture thus provided and a base, whereby a suspension comprising a precipitate is obtained;
(c) adding a compound of a stabilizing element to the suspension thus obtained;
(d) drying the suspension resulting from the preceding stage (c); and
(e) calcining the dried product thus obtained.
40. The process as defined by claim 38 , wherein the suspension resulting from stage (b) is subjected to a maturing before stage (c).
41. The process as defined by claim 38 , wherein the suspension is dried by atomization.
42. The process as defined by claim 38 , wherein before the drying stage, the precipitate is separated from the suspension, washed and redispersed in water to form another suspension.
43. The process as defined by claim 38 , wherein the compound of the stabilizing element is a salt thereof.
44. A catalytic system which comprises a catalyst/catalyst support composition as defined by claim 24 .
45. In a process for the catalytic treatment of exhaust gases emanating from an internal combustion engine, the improvement which comprises, as the catalyst/catalyst support therefor, the composition as defined by claim 24 .
46. The process as defined by claim 45 , said treatment including a NOx trap.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR0607658A FR2905371B1 (en) | 2006-08-31 | 2006-08-31 | HIGH REDUCIBILITY COMPOSITION BASED ON NANOMETRY CERIUM OXIDE ON A CARRIER, PREPARATION METHOD AND USE AS CATALYST |
FR0607658 | 2006-08-31 | ||
PCT/EP2007/058901 WO2008025753A2 (en) | 2006-08-31 | 2007-08-28 | Composition with high reducibility made of a nanometric cerium oxide on a support, method of preparation and use as catalyst |
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US15/883,766 Continuation US10882025B2 (en) | 2006-08-31 | 2018-01-30 | Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate |
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US20100111789A1 true US20100111789A1 (en) | 2010-05-06 |
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US12/439,448 Abandoned US20100111789A1 (en) | 2006-08-31 | 2007-08-28 | Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate |
US15/883,766 Active 2027-11-29 US10882025B2 (en) | 2006-08-31 | 2018-01-30 | Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate |
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US (2) | US20100111789A1 (en) |
EP (1) | EP2059339B1 (en) |
JP (1) | JP5541920B2 (en) |
KR (1) | KR101130908B1 (en) |
CN (1) | CN101516501B (en) |
CA (1) | CA2660002C (en) |
DK (1) | DK2059339T3 (en) |
FR (1) | FR2905371B1 (en) |
PL (1) | PL2059339T3 (en) |
RU (1) | RU2411995C2 (en) |
WO (1) | WO2008025753A2 (en) |
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Also Published As
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RU2411995C2 (en) | 2011-02-20 |
EP2059339A2 (en) | 2009-05-20 |
CN101516501A (en) | 2009-08-26 |
FR2905371A1 (en) | 2008-03-07 |
CA2660002C (en) | 2015-06-02 |
FR2905371B1 (en) | 2010-11-05 |
EP2059339B1 (en) | 2021-11-24 |
DK2059339T3 (en) | 2022-03-07 |
KR101130908B1 (en) | 2012-03-28 |
CA2660002A1 (en) | 2008-03-06 |
RU2009111589A (en) | 2010-10-10 |
CN101516501B (en) | 2013-09-25 |
US10882025B2 (en) | 2021-01-05 |
WO2008025753A3 (en) | 2008-10-30 |
JP5541920B2 (en) | 2014-07-09 |
PL2059339T3 (en) | 2022-05-09 |
KR20090047497A (en) | 2009-05-12 |
US20180345252A1 (en) | 2018-12-06 |
WO2008025753A2 (en) | 2008-03-06 |
JP2010501346A (en) | 2010-01-21 |
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