US20020187894A1 - Catalyst material and a process for its preparation - Google Patents
Catalyst material and a process for its preparation Download PDFInfo
- Publication number
- US20020187894A1 US20020187894A1 US10/177,074 US17707402A US2002187894A1 US 20020187894 A1 US20020187894 A1 US 20020187894A1 US 17707402 A US17707402 A US 17707402A US 2002187894 A1 US2002187894 A1 US 2002187894A1
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- United States
- Prior art keywords
- support material
- oxide
- basic
- catalyst material
- aluminum oxide
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- Abandoned
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- 239000000463 material Substances 0.000 title claims abstract description 163
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 40
- 230000008569 process Effects 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000005470 impregnation Methods 0.000 claims abstract description 30
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 29
- 229910001038 basic metal oxide Inorganic materials 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 12
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- -1 platinum group metals Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000011148 porous material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 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 description 4
- 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 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 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 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003032 molecular docking Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NYWGIWKOAHIKGZ-UHFFFAOYSA-N [La].C=C Chemical group [La].C=C NYWGIWKOAHIKGZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0248—Coatings comprising impregnated particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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 invention provides a powdered catalyst material based on aluminum oxide, which contains at least one basic metal oxide and at least one noble metal from the platinum group of the Periodic System of Elements, as well as aluminum oxide.
- the catalyst according to the invention has outstanding thermal stability with a high surface area and a high, aging-stable dispersion of the catalytically active components. It is particularly suitable for the production of catalysts for the treatment of exhaust gases from internal combustion engines.
- Aluminum oxide is frequently used as a support material for the catalytically active elements from the platinum group. It is obtainable in so-called high surface area modifications on whose surface the noble metals from the platinum group can be deposited in a high dispersion.
- High surface area materials in the context of this invention are materials with a specific surface area of more than 10 m 2 /g, determined by evaluating nitrogen adsorption isotherms in accordance with DIN 66132.
- Aluminum oxides which satisfy this condition are called active aluminum oxides. These include chi, kappa, gamma, delta, theta and eta aluminum oxide (see Ullmann's Encyclopedia of Industrial Chemistry, vol. Al, 561-562, 1985, which is incorporated herein by reference in its entirety).
- the catalytic activity of the expensive platinum group metals have to be deposited in a very high dispersion on the support material. Efforts are made to produce crystallite sizes for the noble metals of between 1 and 10 nm on the surface of the support material.
- the noble metals are deposited, for example, by impregnating the support material with aqueous solutions of precursor compounds of the noble metals. Then the impregnated material is dried and calcined to decompose the noble metal compounds, optionally under reducing conditions.
- U.S. Pat. No. 3,867,312 describes the preparation of a support material based on aluminum oxide which contains oxides of the lanthanides uniformly distributed in the support material. This slows down phase conversion of the aluminum oxide.
- the lanthanide oxides may be present in the support material in concentrations of 1 to 45 wt. %, with respect to the aluminum oxide.
- the support material is obtained, for example, by melting lanthanum acetate and aluminum nitrate together by heating and by converting these into the oxides by increasing the temperature further to 600° C. This patent is incorporated herein by reference in its entirety.
- U.S. Pat. No. 4,170,573 describes a catalyst material in the form of a support material consisting of cerium oxide, lanthanum oxide and aluminum oxide, onto which platinum group metals are deposited.
- active aluminum oxide is impregnated with a solution of lanthanum nitrate, dried and calcined for one hour at a bed temperature between 1223 and 1253° C. Then the material is impregnated with an aqueous solution of cerium nitrate in a similar way, dried and calcined.
- the catalytically active noble metals are deposited onto this support material using ammonium/sulfito complexes of these metals.
- the surface area of the materials prepared in this way is less than 50 m 2 /g.
- EP 0 170 841 ⁇ l describes a catalyst which has 1 to 10 wt. % of lanthanum oxide as stabilizer, 1 to 20 wt. % of cerium oxide as promoter, at least 0.5 to 5 wt. % of an alkali metal oxide as promoter, and one or more platinum group metals on an aluminum oxide support material.
- Lanthanum oxide and the promoters are incorporated in the support material which is present in the form of pellets by impregnation. After impregnating the pellets with a salt of lanthanum, the support is calcined at temperatures between 800 and 1100° C. in order to convert the salt into lanthanum oxide and for thermal stabilization purposes.
- This patent is incorporated herein by reference in its entirety.
- EP 0 171 640 A2 describes a catalyst which contains a composite material consisting of aluminum oxide, lanthanum oxide, cerium oxide and at least one platinum group metal. Lanthanum and cerium are introduced into the aluminum oxide in sequence by impregnating with lanthanum nitrate and cerium nitrate, and are then converted into the oxides by calcining at a temperature of at least 983° C. The resulting material has a surface area of less than 50 m 2 /g. This patent is incorporated herein by reference in its entirety.
- Another process for preparing a thermally stable support material based on aluminum oxide is the solgel process.
- This process provides a homogeneous distribution of aluminum and rare earths, at the atomic level, by the co-precipitation of oxidic aerogels of aluminum and rare earths. These materials have a constant ratio by weight of aluminum oxide to rare earth oxide over the entire volume of the solid material.
- the highly dispersed composite material obtained is then stabilized by calcination.
- the surface areas which can be produced using this process, with good thermal stability, are substantially higher than those achieved by the previously described impregnation method. Typical values are 100 to 300 m 2 /g.
- the impregnated material In order to stabilize aluminum oxide by impregnation with, for example, lanthanum oxide, the impregnated material has to be calcined at temperatures of more than 800° C. in order to enable diffusion of lanthanum into the inner depths of the particles of aluminum oxide, and incorporation into the crystal lattice of aluminum oxide.
- the resulting material generally has a surface area of less than 50 m 2 /g and a substantially homogeneous distribution of doping element over the cross section of the aluminum oxide particles.
- Preparing a stabilized support material based on aluminum oxide by co-precipitation provides a support material with a substantially higher surface area than when using the impregnation methods.
- the doping element is distributed very homogeneously over the cross section of the support particles.
- the catalytically active components are mostly applied to these stabilized support materials by impregnation. It is important here to produce a high dispersion of the catalytically active components, which are very stable even under high thermal stresses. This is not always guaranteed with known support materials. In particular, grain enlargement due to diffusion of the particles to the surface, and aggregation of these, is frequently observed, so the catalytic activity of these materials is reduced by high temperatures.
- the object of the present invention is to provide a catalyst material based on aluminum oxide which has a high surface area and a high dispersion of catalytically active components.
- the thermal stability of the surface area of the support material and of the dispersion of catalytically active components is intended to be better than those of traditional materials.
- Another object of the invention is the method of preparing the catalyst material according to the invention.
- a powdered catalyst material based on aluminum oxide which contains aluminum oxide, at least one basic metal oxide and, as catalytically active components, at least one noble metal from the platinum group of the Periodic System of Elements, wherein aluminum oxide and the basic metal oxides form a composite material which acts as support material for the catalytically active components.
- the catalyst material is obtainable by the following process steps:
- the catalyst material according to the invention is thus obtained by subsequent re-impregnation of a support material already stabilized by basic oxides with precursor compounds of basic oxides.
- stabilized aluminum oxide in the context of this invention is understood to be a material disclosed in the prior art, the crystallographic structure and specific surface area of which have been stabilized against high temperatures by doping with basic oxides.
- This is preferably an active aluminum oxide doped with 1 to 10 wt. % of lanthanum oxide.
- such a material can be obtained by impregnating with precursors of basic oxides followed by calcining at temperatures above 800° C.
- the material obtained in this way is characterized by a substantially homogeneous distribution of doping elements over the cross section of the powder particles.
- these materials may also be obtained by a co-precipitation process.
- These materials are also characterized by a homogeneous distribution of doping elements over the cross section of the powder particles. Due to the requirement that the surface area be at least 80 m 2 /g, the stabilized aluminum oxides obtained by co-precipitation are most suitable as starting materials for the catalyst material according to the invention.
- aqueous impregnation solutions are preferably used, but organic solutions may also be used.
- the material is dried at an elevated temperature of, for example, 100 to 200° C., and calcined at below 800° C. in order to convert the precursor compounds into basic oxides.
- the objective of this calcination step is to convert the precursor compounds into the corresponding oxides, and not forced thermal diffusion of the doping elements into the aluminum oxide lattice. Therefore, temperatures of less than 700° C. are preferably used.
- the appropriate calcination temperature depends on the precursor compounds used and may be lowered to, for example, 600 to 500° C. when using nitrates.
- an elevated concentration of basic oxides is produced at the surface of the support material by means of this action.
- These basic oxides lead to an elevated concentration of hydroxyl groups at the surface which are used as docking points for the precursor compounds of catalytically active noble metals subsequently applied in process step d), and lead to stable anchorage of the noble metal particles on the surface after subsequent calcination in process step e).
- the result of this step is a catalyst material with high thermal stability of the support and a high dispersion of catalytically active noble metals and very good aging and thermal stability of this dispersion, due to reduced mobility of the noble metal particles on the surface of the support.
- the catalyst material according to the invention has a specific BET surface area, measured in accordance with DIN 66132, of more than 80 m 2 /g.
- the total pore volume is preferably between 0.3 and 0.9 ml/g.
- the stabilized aluminum oxide provided in step a) may have the various crystal structures of the transition oxides of aluminum oxide.
- the aluminum oxide contains basic oxides, preferably in concentrations between 0.5 and 20 wt. %, with respect to the total weight of stabilized aluminum oxide or support material.
- additional basic oxides are deposited, preferably at a concentration of 5 to 15 wt. %, with respect to the total weight of support material, so that the total concentration of basic oxides in the support material is 1 to 35 wt. %.
- the catalyst material according to the invention is preferably stabilized and doped with basic oxides from the alkaline earth and rare earth oxides, in particular with oxides of the elements magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, terbium and ytterbium. These oxides may be present individually or as a mixture. Stabilization and doping of the aluminum oxide with oxides of lanthanum, cerium, or mixtures thereof, is especially advantageous.
- Suitable precursors of the basic oxides are any soluble compounds of the alkaline earth and rare earth metals. These include soluble organic complex compounds, acetates, nitrates and chlorides. Organic complex compounds, acetates and nitrates, which are deposited onto the treated support material using a known impregnation process, are preferably used.
- the pore volume impregnation method in which the precursor compounds are dissolved in a volume of solvent which corresponds to about 60 to 110% of the absorption capacity of the initially introduced support material, is preferably used. If the solubility of the precursor compound is not sufficiently high to apply the desired amount in one step, then the impregnation procedure may be repeated several times, until the desired amount has been deposited on the support material.
- noble metals from the platinum group are used as noble metals, in particular platinum, palladium, rhodium and iridium, which may be deposited individually or in various combinations and mixing ratios at concentrations of 0.01 to 5 wt. %, with respect to the total weight of catalyst material.
- the catalyst material according to the invention has an elevated concentration of basic oxides at the surface.
- Tests using secondary ion mass spectrometry (SIMS) have shown that, in particular in an outer edge zone with a thickness of less than 100 atomic layers, the concentration of the metals forming the basic oxides, relative to aluminum, is at least 20% greater than at a depth with a thickness of more than 100 atom layers.
- the invention also provides a powdered catalyst material based on aluminum oxide which contains at least one basic metal oxide and, as catalytically active components, at least one noble metal from the platinum group in the Periodic System of Elements in addition to aluminum oxide, wherein aluminum oxide and the basic metal oxides form a composite material which acts as a support material for the catalytically active components, characterized in that the catalyst material has a specific surface area of more than 80 m 2 /g, and the ratio of the SIMS intensities of the metals forming the basic metal oxides to aluminum at the surface of the powder particles is at least 20% greater than at a depth of more than 100 atomic layers from the surface of the particles.
- the catalyst material has a total concentration of basic oxides of between 1 and 35 wt. %, with respect to the total weight of catalyst material.
- Enrichment of the basic oxides at the surface of the support material increases the concentration of hydroxyl groups at the surface of the particles and these are used as docking points for the precursor compounds of platinum group metals when depositing the catalytically active platinum group metals.
- the increased functionalization of the surface leads to a very high dispersion of deposited noble metals, and also improves anchorage of the deposited noble metal crystallites on the surface, so that the risk of neighboring crystallites aggregating due to increased mobility at high temperatures is reduced.
- the measurements are performed as follows: the loose powder is introduced, in a sample holder, into the measurement chamber of a mass spectrometer, and this is evacuated down to a pressure of 10 ⁇ 8 to 10 ⁇ 9 mbar. Then the powder surface is bombarded with 5 keV argon ions, with simultaneous charge compensation, so that the outer atoms are stripped off, layer by layer. The secondary ions emitted during this process are analyzed. Their distribution with respect to each other corresponds to the distribution of the corresponding elements in the surface of the sample. To normalize the experimental values, the ratios of the measured intensities of secondary ions to the intensity of aluminum ions are calculated. This procedure provides a picture of the distribution of elements as a function of the depth of abrasion relative to the main element in the support material.
- the area measured that is, the surface of powder bombarded with argon ions is 4 ⁇ 4 mm 2 , and is thus many times greater than the cross-sectional area of the individual powder particles, which have a diameter of only between 0.1 and 50 ⁇ m.
- the measurement thus provides the average distribution of elements over many powder particles. This means that random results are largely excluded.
- FIG. 1 SIMS depth profile of lanthanum for support material 1;
- FIG. 2 SIMS depth profile of lanthanum for support material 2;
- FIG. 3 SIMS depth profile of lanthanum for support material 3
- FIG. 4 Temperature at which a 50% conversion of hydrocarbons (HC) and carbon monoxide (CO) is achieved for catalysts in examples 1 to 3 with a normalized air to fuel ratio of 0.999 and periodic modulation of the air/fuel ratio A/F by ⁇ 0.5 at a frequency of 1 Hz (1 Hz; ⁇ 0.5 A/F);
- FIG. 5 Temperature at which a 50% conversion of hydrocarbons (HC) and carbon monoxide (CO) is achieved for catalysts in examples 1 to 3 with a normalized air to fuel ratio of 1.05 (static, with no modulation of A/F);
- FIG. 6 Temperature at which a 50% conversion of hydrocarbons (HC) and carbon monoxide (CO) is achieved for catalysts in examples 1 to 3 with a normalized air to fuel ratio of 1.1 (static, with no modulation of A/F).
- Support Material 1 is
- a commercially available aluminum oxide stabilized with 3 wt. % of lanthanum oxide with a BET surface area in the freshly calcined state of 143 ml/g is used as support material 1.
- Support Material 2 is
- support material 2 2000 g of support material 1 were impregnated with 856 g of a lanthanum ethylene diamine tetra acetate solution with a lanthanum content of 2.4 wt. %, using the pore volume impregnation method.
- the impregnation solution had a pH of 5.
- the powder obtained in this way was then dried for 12 hours at 120° C. and then calcined for 1 hour at 750° C. in air. Due to this subsequent impregnation, an additional 1 wt. % of lanthanum oxide was deposited on the support material, so that the total concentration of lanthanum oxide in the support material was 4 wt. %.
- the specific surface area of the material decreased from 143 m 2 /g to 131 m 2 /g due to the subsequent impregnation procedure.
- Support Material 3 is
- support material 3 2000 g of support material 1 were impregnated with 856 g of a lanthanum nitrate solution with a lanthanum oxide content of 16 wt. %, using the pore volume impregnation method.
- the impregnation solution had a pH of 4.
- the powder obtained in this way was then dried for 12 hours at 120° C. and then calcined for 1 hour at 500° C. in air.
- FIGS. 1 to 3 show the SIMS spectra for lanthanum as a function of the time of bombardment of the sample surface with argon ions, in three-dimensional images. Each spectrum corresponds to a specific abraded depth. The last spectrum in these images corresponds to an abraded depth of about 100 atomic layers.
- the depth profile for support material 1 shows a reduced lanthanum concentration at the surface, but this changes to a constant concentration, with increasing depth of abrasion.
- the depth profiles for the support materials prepared according to the invention show a clearly increased lanthanum concentration in an edge zone of a few atomic layers, which falls away to a constant value with increasing depth of abrasion.
- Table 1 gives the ratio of SIMS intensities determined for aluminum to the intensities determined for lanthanum for three different depths of abrasion, initially (at the surface), in the middle, and at the end of the test. TABLE 1 Quotients of SIMS intensities for Al/La.
- Site of Support measurement material 1
- Support material 2 Support material 3 Start 70.8 63.8 17.9
- Middle 69.7
- the Al/La ratio changes, in support materials 2 and 3 prepared according to the invention, by a factor of 2 from the surface to a depth of about 100 atomic layers. Accordingly, the concentration of lanthanum is enriched at the surface of the particles of support material.
- Car exhaust gas catalysts were prepared using support materials 1 to 3, and their light off temperatures for the conversion of hydrocarbons and carbon monoxide were determined.
- the catalysts were intended for use as start catalysts located close to the engine and which are subjected to very high temperatures during operation.
- the support structures for all the catalysts were honeycomb structures made of cordierite with a volume of 0.3 l and a cell density of 46.5 cm ⁇ 2 .
- 120 g of support material 1 were mixed with 20 g of a cerium/zirconium mixed oxide (70 wt. % cerium oxide and 30 wt. % zirconium oxide with a BET surface area in the freshly calcined state of 87 m 2 /g) impregnated with 0.7 g of platinum and 3.2 g of palladium using the pore volume impregnation method. The impregnated mixture was then dried and calcined at 500° C. in air.
- a cerium/zirconium mixed oxide 70 wt. % cerium oxide and 30 wt. % zirconium oxide with a BET surface area in the freshly calcined state of 87 m 2 /g
- the impregnated mixture was then dried and calcined at 500° C. in air.
- This powder was stirred with water to give an aqueous suspension and milled to a particle size of 3 to 5 ⁇ m (d 50 ).
- the oxidic solids in the dispersion were applied to one of the support structures provided, using an immersion method.
- the loading concentration was 160 g of catalyst material per liter of honeycomb structure volume.
- a catalyst was prepared using the same method as described in example 1, but using support material 2.
- a catalyst was prepared using the same method as described in example 1, but using support material 3.
- All the catalysts were aged for 4 hours at 1100° C. in an atmosphere consisting of 88 vol.% nitrogen, 10 vol.% water and 2 vol.% oxygen before measuring the light off temperatures in the engine.
- the light off temperatures were measured in a 2 l petrol engine.
- the catalysts were increasingly heated with normalized air to fuel ratios of 0.999 (1 Hz 0. 5 A/F) and 1.05 (static) or 1.1 (static) and subjected to a space velocity of 206000 h ⁇ 1 .
- the conversions of hydrocarbons and carbon monoxide were determined as a function of the temperature.
- the temperatures for a conversion of 50% for each of the harmful substances were determined from these measurements for the individual catalysts.
- German priority application 199 08 394.0 is relied on and incorporated herein by reference.
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Abstract
A powdered catalyst material based on aluminum oxide, which contains at least one basic metal oxide and at least one noble metal from the platinum group of the Periodic System of Elements in addition to aluminum oxide. The catalyst material is obtainable by loading a support material already stabilized by basic oxides by renewed impregnation with further basic oxides. After drying and calcining this post-impregnated material at temperatures below 800° C., the catalytically active noble metals are also incorporated into the support material by impregnation.
Description
- The invention provides a powdered catalyst material based on aluminum oxide, which contains at least one basic metal oxide and at least one noble metal from the platinum group of the Periodic System of Elements, as well as aluminum oxide. The catalyst according to the invention has outstanding thermal stability with a high surface area and a high, aging-stable dispersion of the catalytically active components. It is particularly suitable for the production of catalysts for the treatment of exhaust gases from internal combustion engines.
- Aluminum oxide is frequently used as a support material for the catalytically active elements from the platinum group. It is obtainable in so-called high surface area modifications on whose surface the noble metals from the platinum group can be deposited in a high dispersion.
- High surface area materials in the context of this invention are materials with a specific surface area of more than 10 m 2/g, determined by evaluating nitrogen adsorption isotherms in accordance with DIN 66132. Aluminum oxides which satisfy this condition are called active aluminum oxides. These include chi, kappa, gamma, delta, theta and eta aluminum oxide (see Ullmann's Encyclopedia of Industrial Chemistry, vol. Al, 561-562, 1985, which is incorporated herein by reference in its entirety).
- For optimum use of the catalytic activity of the expensive platinum group metals, they have to be deposited in a very high dispersion on the support material. Efforts are made to produce crystallite sizes for the noble metals of between 1 and 10 nm on the surface of the support material. The noble metals are deposited, for example, by impregnating the support material with aqueous solutions of precursor compounds of the noble metals. Then the impregnated material is dried and calcined to decompose the noble metal compounds, optionally under reducing conditions.
- Four properties of the catalyst material obtained in this way are important for later use in catalytic processes:
- a) the surface area of the material, measured as the specific BET surface area according to DIN 66132;
- b) the resistance of the crystallographic structure and surface area of the support material to stresses which occur during the catalytic process, in particular to high temperatures;
- c) the dispersion of the catalytically active components on the surface area of the support material;
- d) the resistance of the dispersion of catalytically active components to stresses which occur during the catalytic process, in particular to high temperatures.
- In order to stabilize the crystallographic structure and the surface area of the aluminum oxide used as support material, this is frequently doped with basic metal oxides such as, for example, barium oxide and lanthanum oxide, cerium oxide, or other rare earth oxides or mixtures of these oxides. This results in a slowing of the conversion into thermally stable, but low surface area, alpha aluminum oxide. The amount of doping components required for this purpose is 1 to 10 wt. %, with respect to the total weight of doped aluminum oxide.
- U.S. Pat. No. 3,867,312 describes the preparation of a support material based on aluminum oxide which contains oxides of the lanthanides uniformly distributed in the support material. This slows down phase conversion of the aluminum oxide. The lanthanide oxides may be present in the support material in concentrations of 1 to 45 wt. %, with respect to the aluminum oxide. The support material is obtained, for example, by melting lanthanum acetate and aluminum nitrate together by heating and by converting these into the oxides by increasing the temperature further to 600° C. This patent is incorporated herein by reference in its entirety.
- U.S. Pat. No. 4,170,573 describes a catalyst material in the form of a support material consisting of cerium oxide, lanthanum oxide and aluminum oxide, onto which platinum group metals are deposited. To prepare the support material, active aluminum oxide is impregnated with a solution of lanthanum nitrate, dried and calcined for one hour at a bed temperature between 1223 and 1253° C. Then the material is impregnated with an aqueous solution of cerium nitrate in a similar way, dried and calcined. The catalytically active noble metals are deposited onto this support material using ammonium/sulfito complexes of these metals. The surface area of the materials prepared in this way is less than 50 m 2/g. This patent is incorporated herein by reference in its entirety.
- EP 0 170 841 μl describes a catalyst which has 1 to 10 wt. % of lanthanum oxide as stabilizer, 1 to 20 wt. % of cerium oxide as promoter, at least 0.5 to 5 wt. % of an alkali metal oxide as promoter, and one or more platinum group metals on an aluminum oxide support material. Lanthanum oxide and the promoters are incorporated in the support material which is present in the form of pellets by impregnation. After impregnating the pellets with a salt of lanthanum, the support is calcined at temperatures between 800 and 1100° C. in order to convert the salt into lanthanum oxide and for thermal stabilization purposes. This patent is incorporated herein by reference in its entirety.
- EP 0 171 640 A2 describes a catalyst which contains a composite material consisting of aluminum oxide, lanthanum oxide, cerium oxide and at least one platinum group metal. Lanthanum and cerium are introduced into the aluminum oxide in sequence by impregnating with lanthanum nitrate and cerium nitrate, and are then converted into the oxides by calcining at a temperature of at least 983° C. The resulting material has a surface area of less than 50 m 2/g. This patent is incorporated herein by reference in its entirety.
- Another process for preparing a thermally stable support material based on aluminum oxide is the solgel process. This process provides a homogeneous distribution of aluminum and rare earths, at the atomic level, by the co-precipitation of oxidic aerogels of aluminum and rare earths. These materials have a constant ratio by weight of aluminum oxide to rare earth oxide over the entire volume of the solid material. The highly dispersed composite material obtained is then stabilized by calcination. The surface areas which can be produced using this process, with good thermal stability, are substantially higher than those achieved by the previously described impregnation method. Typical values are 100 to 300 m 2/g.
- The properties of the known processes for preparing a stabilized support material based on aluminum oxide are thus characterized as follows:
- In order to stabilize aluminum oxide by impregnation with, for example, lanthanum oxide, the impregnated material has to be calcined at temperatures of more than 800° C. in order to enable diffusion of lanthanum into the inner depths of the particles of aluminum oxide, and incorporation into the crystal lattice of aluminum oxide. The resulting material generally has a surface area of less than 50 m 2/g and a substantially homogeneous distribution of doping element over the cross section of the aluminum oxide particles.
- Preparing a stabilized support material based on aluminum oxide by co-precipitation provides a support material with a substantially higher surface area than when using the impregnation methods. The doping element is distributed very homogeneously over the cross section of the support particles.
- The catalytically active components are mostly applied to these stabilized support materials by impregnation. It is important here to produce a high dispersion of the catalytically active components, which are very stable even under high thermal stresses. This is not always guaranteed with known support materials. In particular, grain enlargement due to diffusion of the particles to the surface, and aggregation of these, is frequently observed, so the catalytic activity of these materials is reduced by high temperatures.
- Thus, the object of the present invention is to provide a catalyst material based on aluminum oxide which has a high surface area and a high dispersion of catalytically active components. The thermal stability of the surface area of the support material and of the dispersion of catalytically active components is intended to be better than those of traditional materials. Another object of the invention is the method of preparing the catalyst material according to the invention.
- These objects are achieved by a powdered catalyst material based on aluminum oxide which contains aluminum oxide, at least one basic metal oxide and, as catalytically active components, at least one noble metal from the platinum group of the Periodic System of Elements, wherein aluminum oxide and the basic metal oxides form a composite material which acts as support material for the catalytically active components. The catalyst material is obtainable by the following process steps:
- a) provision of a powdered aluminum oxide stabilized with basic oxides as support material, which has a specific surface area of more than 80 m 2/g,
- b) impregnation of the support material with a solution of at least one precursor compound of alkaline earth and rare earth metals,
- c) drying of the impregnated support material and calcination at temperatures below 800° C.,
- d) repetition of process steps b) and c) until the desired loading with basic oxides is achieved,
- e) renewed impregnation of the material obtained with a solution of precursor compounds of the catalytically active noble metals, and
- f) finally drying and calcining.
- The catalyst material according to the invention is thus obtained by subsequent re-impregnation of a support material already stabilized by basic oxides with precursor compounds of basic oxides.
- The expression “stabilized aluminum oxide” in the context of this invention is understood to be a material disclosed in the prior art, the crystallographic structure and specific surface area of which have been stabilized against high temperatures by doping with basic oxides. This is preferably an active aluminum oxide doped with 1 to 10 wt. % of lanthanum oxide. As explained at the beginning, such a material can be obtained by impregnating with precursors of basic oxides followed by calcining at temperatures above 800° C. The material obtained in this way is characterized by a substantially homogeneous distribution of doping elements over the cross section of the powder particles. Alternatively, these materials may also be obtained by a co-precipitation process. These materials are also characterized by a homogeneous distribution of doping elements over the cross section of the powder particles. Due to the requirement that the surface area be at least 80 m 2/g, the stabilized aluminum oxides obtained by co-precipitation are most suitable as starting materials for the catalyst material according to the invention.
- For the post-impregnation procedure in process step b), aqueous impregnation solutions are preferably used, but organic solutions may also be used. After impregnation in step b), the material is dried at an elevated temperature of, for example, 100 to 200° C., and calcined at below 800° C. in order to convert the precursor compounds into basic oxides. The objective of this calcination step is to convert the precursor compounds into the corresponding oxides, and not forced thermal diffusion of the doping elements into the aluminum oxide lattice. Therefore, temperatures of less than 700° C. are preferably used. The appropriate calcination temperature depends on the precursor compounds used and may be lowered to, for example, 600 to 500° C. when using nitrates.
- According to current understanding of the invention, an elevated concentration of basic oxides is produced at the surface of the support material by means of this action. These basic oxides lead to an elevated concentration of hydroxyl groups at the surface which are used as docking points for the precursor compounds of catalytically active noble metals subsequently applied in process step d), and lead to stable anchorage of the noble metal particles on the surface after subsequent calcination in process step e). The result of this step is a catalyst material with high thermal stability of the support and a high dispersion of catalytically active noble metals and very good aging and thermal stability of this dispersion, due to reduced mobility of the noble metal particles on the surface of the support.
- The catalyst material according to the invention has a specific BET surface area, measured in accordance with DIN 66132, of more than 80 m 2/g. The total pore volume is preferably between 0.3 and 0.9 ml/g.
- The stabilized aluminum oxide provided in step a) may have the various crystal structures of the transition oxides of aluminum oxide. In order to stabilize these characteristics, the aluminum oxide contains basic oxides, preferably in concentrations between 0.5 and 20 wt. %, with respect to the total weight of stabilized aluminum oxide or support material.
- Due to subsequent impregnation, additional basic oxides are deposited, preferably at a concentration of 5 to 15 wt. %, with respect to the total weight of support material, so that the total concentration of basic oxides in the support material is 1 to 35 wt. %.
- Different basic oxides may be combined in the catalyst material according to the invention, that is, the basic oxides used to stabilize the starting material do not have to be identical to the oxides deposited on the support material in process steps b) and c).
- The catalyst material according to the invention is preferably stabilized and doped with basic oxides from the alkaline earth and rare earth oxides, in particular with oxides of the elements magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, terbium and ytterbium. These oxides may be present individually or as a mixture. Stabilization and doping of the aluminum oxide with oxides of lanthanum, cerium, or mixtures thereof, is especially advantageous.
- Suitable precursors of the basic oxides are any soluble compounds of the alkaline earth and rare earth metals. These include soluble organic complex compounds, acetates, nitrates and chlorides. Organic complex compounds, acetates and nitrates, which are deposited onto the treated support material using a known impregnation process, are preferably used. The pore volume impregnation method, in which the precursor compounds are dissolved in a volume of solvent which corresponds to about 60 to 110% of the absorption capacity of the initially introduced support material, is preferably used. If the solubility of the precursor compound is not sufficiently high to apply the desired amount in one step, then the impregnation procedure may be repeated several times, until the desired amount has been deposited on the support material.
- To apply the catalytically active noble metals, known impregnation techniques may also be used, wherein the pore volume impregnation method is also preferred for the noble metals. According to the invention, metals from the platinum group are used as noble metals, in particular platinum, palladium, rhodium and iridium, which may be deposited individually or in various combinations and mixing ratios at concentrations of 0.01 to 5 wt. %, with respect to the total weight of catalyst material.
- As explained above, the catalyst material according to the invention has an elevated concentration of basic oxides at the surface. Tests using secondary ion mass spectrometry (SIMS) have shown that, in particular in an outer edge zone with a thickness of less than 100 atomic layers, the concentration of the metals forming the basic oxides, relative to aluminum, is at least 20% greater than at a depth with a thickness of more than 100 atom layers.
- Accordingly, the invention also provides a powdered catalyst material based on aluminum oxide which contains at least one basic metal oxide and, as catalytically active components, at least one noble metal from the platinum group in the Periodic System of Elements in addition to aluminum oxide, wherein aluminum oxide and the basic metal oxides form a composite material which acts as a support material for the catalytically active components, characterized in that the catalyst material has a specific surface area of more than 80 m 2/g, and the ratio of the SIMS intensities of the metals forming the basic metal oxides to aluminum at the surface of the powder particles is at least 20% greater than at a depth of more than 100 atomic layers from the surface of the particles.
- Considerations governing the choice of basic oxides, catalytically active noble metals, and concentrations, are the same as those mentioned above. In particular, the catalyst material has a total concentration of basic oxides of between 1 and 35 wt. %, with respect to the total weight of catalyst material.
- Enrichment of the basic oxides at the surface of the support material increases the concentration of hydroxyl groups at the surface of the particles and these are used as docking points for the precursor compounds of platinum group metals when depositing the catalytically active platinum group metals. The increased functionalization of the surface leads to a very high dispersion of deposited noble metals, and also improves anchorage of the deposited noble metal crystallites on the surface, so that the risk of neighboring crystallites aggregating due to increased mobility at high temperatures is reduced.
- Surface enrichment of the basic oxides in accordance with the invention is substantially restricted to a very thin edge zone with a thickness of a few atomic diameters. The variation in concentration of elements in the edge zone can be measured using secondary ion mass spectrometry (SIMS). The application of secondary ion mass spectrometry to investigating the surfaces of powders is described in “SIMS/XPS Study on the Deactivation and Reactivation of BMFI Catalysts Used in the Vapor Phase Beckmann Rearrangement” by P. Albers et al. Journal of Catalysis, vol. 176, 1998, 561-568, which is incorporated herein by reference in its entirety.
- The measurements are performed as follows: the loose powder is introduced, in a sample holder, into the measurement chamber of a mass spectrometer, and this is evacuated down to a pressure of 10 −8 to 10−9 mbar. Then the powder surface is bombarded with 5 keV argon ions, with simultaneous charge compensation, so that the outer atoms are stripped off, layer by layer. The secondary ions emitted during this process are analyzed. Their distribution with respect to each other corresponds to the distribution of the corresponding elements in the surface of the sample. To normalize the experimental values, the ratios of the measured intensities of secondary ions to the intensity of aluminum ions are calculated. This procedure provides a picture of the distribution of elements as a function of the depth of abrasion relative to the main element in the support material.
- The area measured, that is, the surface of powder bombarded with argon ions is 4×4 mm 2, and is thus many times greater than the cross-sectional area of the individual powder particles, which have a diameter of only between 0.1 and 50 μm. The measurement thus provides the average distribution of elements over many powder particles. This means that random results are largely excluded.
- The invention is now explained in more detail using a few examples. The following figures are provided:
- FIG. 1: SIMS depth profile of lanthanum for
support material 1; - FIG. 2: SIMS depth profile of lanthanum for
support material 2; - FIG. 3: SIMS depth profile of lanthanum for
support material 3 - FIG. 4: Temperature at which a 50% conversion of hydrocarbons (HC) and carbon monoxide (CO) is achieved for catalysts in examples 1 to 3 with a normalized air to fuel ratio of 0.999 and periodic modulation of the air/fuel ratio A/F by ±0.5 at a frequency of 1 Hz (1 Hz; ±0.5 A/F);
- FIG. 5: Temperature at which a 50% conversion of hydrocarbons (HC) and carbon monoxide (CO) is achieved for catalysts in examples 1 to 3 with a normalized air to fuel ratio of 1.05 (static, with no modulation of A/F);
- FIG. 6: Temperature at which a 50% conversion of hydrocarbons (HC) and carbon monoxide (CO) is achieved for catalysts in examples 1 to 3 with a normalized air to fuel ratio of 1.1 (static, with no modulation of A/F).
- The following support materials were used or prepared to produce car exhaust gas catalysts using catalyst materials according to the invention:
- Support Material 1:
- A commercially available aluminum oxide stabilized with 3 wt. % of lanthanum oxide with a BET surface area in the freshly calcined state of 143 ml/g is used as
support material 1. - Support Material 2:
- To prepare
support material 2, 2000 g ofsupport material 1 were impregnated with 856 g of a lanthanum ethylene diamine tetra acetate solution with a lanthanum content of 2.4 wt. %, using the pore volume impregnation method. The impregnation solution had a pH of 5. The powder obtained in this way was then dried for 12 hours at 120° C. and then calcined for 1 hour at 750° C. in air. Due to this subsequent impregnation, an additional 1 wt. % of lanthanum oxide was deposited on the support material, so that the total concentration of lanthanum oxide in the support material was 4 wt. %. - The specific surface area of the material decreased from 143 m 2/g to 131 m2/g due to the subsequent impregnation procedure.
- Support Material 3:
- To prepare
support material 3, 2000 g ofsupport material 1 were impregnated with 856 g of a lanthanum nitrate solution with a lanthanum oxide content of 16 wt. %, using the pore volume impregnation method. The impregnation solution had a pH of 4. The powder obtained in this way was then dried for 12 hours at 120° C. and then calcined for 1 hour at 500° C. in air. - Due to this subsequent impregnation, an additional 7 wt. % of lanthanum oxide was deposited on the support material, so that the total concentration of lanthanum oxide in the support material was 10 wt. %. The specific surface area of the material decreased from 143 m 2/g to 123 m2/g.
- SIMS depth profiles were determined for lanthanum and aluminum in the three support materials, using the method described above. FIGS. 1 to 3 show the SIMS spectra for lanthanum as a function of the time of bombardment of the sample surface with argon ions, in three-dimensional images. Each spectrum corresponds to a specific abraded depth. The last spectrum in these images corresponds to an abraded depth of about 100 atomic layers.
- The depth profile for
support material 1 shows a reduced lanthanum concentration at the surface, but this changes to a constant concentration, with increasing depth of abrasion. The depth profiles for the support materials prepared according to the invention, on the other hand, show a clearly increased lanthanum concentration in an edge zone of a few atomic layers, which falls away to a constant value with increasing depth of abrasion. - Table 1 gives the ratio of SIMS intensities determined for aluminum to the intensities determined for lanthanum for three different depths of abrasion, initially (at the surface), in the middle, and at the end of the test.
TABLE 1 Quotients of SIMS intensities for Al/La. Site of Support measurement material 1 Support material 2Support material 3Start 70.8 63.8 17.9 Middle 69.7 101 19.4 End 75.1 113 24.0 - As shown by these results, the Al/La ratio changes, in
2 and 3 prepared according to the invention, by a factor of 2 from the surface to a depth of about 100 atomic layers. Accordingly, the concentration of lanthanum is enriched at the surface of the particles of support material.support materials - Car exhaust gas catalysts were prepared using
support materials 1 to 3, and their light off temperatures for the conversion of hydrocarbons and carbon monoxide were determined. The catalysts were intended for use as start catalysts located close to the engine and which are subjected to very high temperatures during operation. The support structures for all the catalysts were honeycomb structures made of cordierite with a volume of 0.3 l and a cell density of 46.5 cm−2. - 120 g of
support material 1 were mixed with 20 g of a cerium/zirconium mixed oxide (70 wt. % cerium oxide and 30 wt. % zirconium oxide with a BET surface area in the freshly calcined state of 87 m2/g) impregnated with 0.7 g of platinum and 3.2 g of palladium using the pore volume impregnation method. The impregnated mixture was then dried and calcined at 500° C. in air. - This powder was stirred with water to give an aqueous suspension and milled to a particle size of 3 to 5 μm (d 50). The oxidic solids in the dispersion were applied to one of the support structures provided, using an immersion method. The loading concentration was 160 g of catalyst material per liter of honeycomb structure volume.
- A catalyst was prepared using the same method as described in example 1, but using
support material 2. - A catalyst was prepared using the same method as described in example 1, but using
support material 3. - All the catalysts were aged for 4 hours at 1100° C. in an atmosphere consisting of 88 vol.% nitrogen, 10 vol.% water and 2 vol.% oxygen before measuring the light off temperatures in the engine.
- The light off temperatures were measured in a 2 l petrol engine. For this purpose, the catalysts were increasingly heated with normalized air to fuel ratios of 0.999 (1 Hz 0. 5 A/F) and 1.05 (static) or 1.1 (static) and subjected to a space velocity of 206000 h −1. During the heating process, the conversions of hydrocarbons and carbon monoxide were determined as a function of the temperature. The temperatures for a conversion of 50% for each of the harmful substances were determined from these measurements for the individual catalysts.
- The results determined are shown graphically in FIGS. 4 to 6. As can be seen from these results, the catalysts in examples 2 and 3 which were prepared using support materials according to the invention are characterized by a substantially reduced light off temperature, although, due to the subsequent impregnation procedure, the specific surface area of the support materials was less than the specific surface area of the support material used in example 1.
- Further variations and modifications of the foregoing will be apparent to those skilled in the art and are intended to be encompassed by the claims appended hereto.
- German priority application 199 08 394.0 is relied on and incorporated herein by reference.
Claims (15)
1. A powdered catalyst material of aluminum oxide, at least one basic metal oxide, and at least one catalytically active noble metal, wherein aluminum oxide and the at least one basic metal oxide form a support material for the at least one catalytically active component, the powdered catalyst material obtained by a process comprising:
a) providing as a support material a powdered aluminum oxide stabilized with at least one basic oxide, and having a specific surface area greater than 80 m2/g;
b) impregnating the support material with a solution of at least one precursor compound of a member selected from the group consisting of at least one alkaline earth metal and at least one rare earth metal;
c) drying the resulting impregnated support material; and
d) calcining the resulting dried impregnated support material at a temperature below 800° C.;
e) repeating process steps b) through d) until a desired loading with basic oxides is achieved; and
f) impregnating the resulting calcined impregnated support material with a solution of at least one precursor compound of at least one catalytically active noble metal;
g) drying the resulting further impregnated support material; and
h) calcining the resulting dried impregnated support material to obtain the powdered catalyst material product.
2. The catalyst material according to claim 1 , wherein the powdered aluminum oxide support material provided has a concentration of basic oxides in step a) of from 0.5 to 20 wt %, with respect to the total weight of support material.
3. The catalyst material according to claim 2 , wherein the concentration of the member selected from the group consisting of at least one alkaline earth metal and at least one rare earth metal incorporated into the support material by impregnation in step b) is from 0.5 to 15 wt. %, with respect to the total weight of support material.
4. The catalyst material according to claim 1 , wherein the at least one basic oxide of step a) is selected from the group consisting of alkaline earth oxides and rare earth oxides.
5. The catalyst material according to claim 4 , wherein the at least one basic oxide is at least one member selected from the group consisting of lanthanum oxide and cerium oxide.
6. The catalyst material according to claim 1 , wherein the at least one catalytically active noble metal is at least one member selected from the group consisting of platinum, palladium, rhodium, iridium, and mixtures thereof, which are present in a concentration of from 0.01 to 5 wt. %, with respect to the total weight of catalyst material.
7. A powdered catalyst material comprising aluminum oxide, at least one basic metal oxide, and at least one catalytically active noble metal,
wherein the aluminum oxide and the at least one basic metal oxide form a composite support material for catalytically active components,
wherein the catalyst material has a specific surface area of more than 80 m2/g,
wherein a ratio of SIMS intensities of the basic metal oxides to SIMS intensities of the aluminum, at the surface of the powder particles, is at least 20% greater than that at a depth of more than 100 atomic layers from the surface of the particles.
8. The catalyst material according to claim 7 , wherein the at least one basic metal oxide is at least one member selected from the group consisting of alkaline earth oxides and rare earth oxides.
9. The catalyst material according to claim 8 , wherein the at least one basic metal oxide is at least one member selected from the group consisting of lanthanum oxide and cerium oxide.
10. The catalyst material according to claim 9 , wherein the at least one basic metal oxide is present in a concentration, with respect to the total weight of the catalyst material, of between 1 and 35 wt. %.
11. The catalyst material according to claim 10 , wherein the at least one noble metal is at least one member selected from the group consisting of platinum, palladium, rhodium, iridium, and mixtures thereof and is present in a concentration of 0 01 to 5 wt %, with respect to the total weight of the catalyst material.
12. A process for preparing a powdered catalyst material, comprising:
a) providing as support material a powdered aluminum oxide stabilized with at least one basic oxide, and having a specific surface area greater than 80 m2/g;
b) impregnating the support material with a solution of at least one precursor compound of at least one member selected from the group consisting of an alkaline earth metal and a rare earth metal;
c) drying the resulting impregnated support material, and,
d) calcining the dried support material at a temperature below 800° C.;
e) repeating steps b) through d) until a desired loading with the at least one basic oxide is achieved; and
f) impregnation of the loaded support material with a solution of at least one precursor compound of the at least one catalytically active noble metal; and,
g) final drying and calcining to obtain the powdered catalyst material product.
13. The process according to claim 12 , wherein the stabilized aluminum oxide provided as support material in step a) has a concentration of 1 to 20 wt. % of the at least one basic oxide.
14. A process according to claim 13 , wherein the at least one member selected from the group consisting of an alkaline earth metal and a rare earth metal additionally incorporated into the support material in step b) amounts to 0.5 to 15 wt. %, with respect to the total weight of support material.
15. A powdered support material of aluminum oxide, at least one basic metal oxide, and at least one noble metal, obtained by a process comprising:
a) providing as support material a powdered aluminum oxide stabilized with at least one basic oxide, and having a a specific surface area of more than 80 m2/g;
b) impregnating the support material with a solution of at least one precursor compound of at least one member selected from the group consisting of an alkaline earth metal and a rare earth metal;
c) drying the impregnated support material; and
d) calcining the dried support material at a temperature below 800° C.; and,
e) repeating process steps b) through d) until a desired loading with the at least one basic oxide is achieved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/177,074 US20020187894A1 (en) | 1999-02-26 | 2002-06-19 | Catalyst material and a process for its preparation |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19908394A DE19908394A1 (en) | 1999-02-26 | 1999-02-26 | Catalyst material and process for its manufacture |
| DE19908394.0 | 1999-02-26 | ||
| US09/513,341 US6475951B1 (en) | 1999-02-06 | 2000-02-25 | Catalyst material |
| US10/177,074 US20020187894A1 (en) | 1999-02-26 | 2002-06-19 | Catalyst material and a process for its preparation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/513,341 Continuation US6475951B1 (en) | 1999-02-06 | 2000-02-25 | Catalyst material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20020187894A1 true US20020187894A1 (en) | 2002-12-12 |
Family
ID=7898985
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/513,341 Expired - Lifetime US6475951B1 (en) | 1999-02-06 | 2000-02-25 | Catalyst material |
| US10/177,074 Abandoned US20020187894A1 (en) | 1999-02-26 | 2002-06-19 | Catalyst material and a process for its preparation |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/513,341 Expired - Lifetime US6475951B1 (en) | 1999-02-06 | 2000-02-25 | Catalyst material |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US6475951B1 (en) |
| EP (1) | EP1031377A3 (en) |
| JP (1) | JP2000246105A (en) |
| KR (1) | KR100714663B1 (en) |
| BR (1) | BR0000664A (en) |
| CA (1) | CA2299602C (en) |
| DE (1) | DE19908394A1 (en) |
| MX (1) | MXPA00001894A (en) |
| ZA (1) | ZA200000911B (en) |
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- 2000-02-24 ZA ZA200000911A patent/ZA200000911B/en unknown
- 2000-02-25 CA CA002299602A patent/CA2299602C/en not_active Expired - Lifetime
- 2000-02-25 US US09/513,341 patent/US6475951B1/en not_active Expired - Lifetime
- 2000-02-25 KR KR1020000009291A patent/KR100714663B1/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030139639A1 (en) * | 2001-09-28 | 2003-07-24 | Kenji Otsuka | Decompositionally treating agent and decompositionally treating method for fluorocarbons |
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| US20100285956A1 (en) * | 2007-08-29 | 2010-11-11 | Pacific Industrial Development | Rare earth alumina particulate manufacturing method and application |
| US8629077B2 (en) * | 2007-08-29 | 2014-01-14 | Yunkui Li | Rare earth alumina particulate manufacturing method and application |
| CN107764626A (en) * | 2017-11-03 | 2018-03-06 | 中自环保科技股份有限公司 | A kind of quick aging method of catalyst |
| WO2021012107A1 (en) * | 2019-07-19 | 2021-01-28 | Rhodia Operations | Mixed oxide based on cerium and zirconium |
| US12214333B2 (en) | 2019-07-19 | 2025-02-04 | Rhodia Operations | Mixed oxide based on cerium and zirconium |
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA00001894A (en) | 2002-03-08 |
| JP2000246105A (en) | 2000-09-12 |
| US6475951B1 (en) | 2002-11-05 |
| ZA200000911B (en) | 2000-09-13 |
| CA2299602C (en) | 2007-09-11 |
| EP1031377A2 (en) | 2000-08-30 |
| KR20010014507A (en) | 2001-02-26 |
| EP1031377A3 (en) | 2001-06-27 |
| DE19908394A1 (en) | 2000-08-31 |
| CA2299602A1 (en) | 2000-08-26 |
| BR0000664A (en) | 2000-08-29 |
| KR100714663B1 (en) | 2007-05-07 |
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