US20160040576A1 - Extruded honeycomb catalyst - Google Patents
Extruded honeycomb catalyst Download PDFInfo
- Publication number
- US20160040576A1 US20160040576A1 US14/827,918 US201514827918A US2016040576A1 US 20160040576 A1 US20160040576 A1 US 20160040576A1 US 201514827918 A US201514827918 A US 201514827918A US 2016040576 A1 US2016040576 A1 US 2016040576A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- extruded
- honeycomb
- carrier
- zeolite
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 190
- 239000010457 zeolite Substances 0.000 claims abstract description 48
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 6
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract 4
- 150000003624 transition metals Chemical class 0.000 claims abstract 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003681 vanadium Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000011068 loading method Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 229910052878 cordierite Inorganic materials 0.000 description 8
- 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 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- PLQRBFAACWRSKF-LJTMIZJLSA-M sodium;n-methyl-n-[(2s,3r,4r,5r)-2,3,4,5,6-pentahydroxyhexyl]carbamodithioate Chemical compound [Na+].[S-]C(=S)N(C)C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO PLQRBFAACWRSKF-LJTMIZJLSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
- F01N3/208—Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
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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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- 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
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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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- F01N2240/25—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an ammonia generator
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- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
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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
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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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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
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- Y02T10/12—Improving ICE efficiencies
Definitions
- the invention concerns an extruded honeycomb catalyst, in particular for exhaust gas cleaning, especially in the domain of motor vehicles, where it is used in particular for nitrogen oxide reduction according to the selective catalytic reduction (SCR) method, i.e. the reduction of oxides of nitrogen using a nitrogenous reductant.
- SCR selective catalytic reduction
- the invention also concerns a set of such variously embodied honeycomb catalysts and a method for producing honeycomb catalysts.
- Extruded honeycomb catalysts are one-piece, monolithic objects, which have a plurality of channels through which the exhaust gas flows during operation. These channels have an opening width of just a few millimetres. The webs delimiting the individual channels also typically have a width of just 300 ⁇ m.
- extruded honeycomb catalysts in which the solid material is catalytically active, a high proportion by volume of the solid body consists of catalytically active components. The result of this is that any modifications of the catalytic components, for example to make adaptations to different requirements and in general to pursue refinements, have a critical effect on extrudability. Altogether, this makes the development period for a new extruded honeycomb catalyst, in which the solid material is catalytically active, expensive.
- WO 2010/099395 A1 discloses extruded honeycomb catalyst bodies and methods of manufacturing them.
- the catalyst body includes a first oxide selected from the group consisting of tungsten oxides, vanadium oxides and combinations thereof, a second oxide selected from the group consisting of cerium oxides, lanthanum oxides, zirconium oxides and combinations thereof and a zeolite.
- an extruded zeolite core is coated with a layer of a mixture of a cerium oxide, a zirconium oxide and a tungsten oxide.
- the invention is based on the problem of specifying a honeycomb catalyst which can be adapted to new requirements with low development costs.
- the honeycomb catalyst as a whole is formed from an extruded, active carrier in honeycomb form, which has at least one catalytically active component and on which in addition a catalytically active coating, in particular a washcoat coating, is applied, which thus likewise has at least one catalytic component.
- honeycomb catalysts which differ in terms of their functionality, but which each have an identical carrier, and by a method for producing honeycomb catalysts of this type.
- This embodiment is based on the idea of developing and providing a carrier which can be used universally for several domains of application and making specific adaptations to the respective requirements via the special washcoat coating.
- the particular advantage is to be seen in the fact that a different extrusion mass does not have to be developed and provided for different honeycomb catalysts.
- the entire catalytic activity can be adapted and designed as appropriate.
- this provides the option, firstly, of developing the catalyst with a view to a technically optimised functionality or alternatively with a view to a catalyst optimised in terms of cost. In order to achieve the latter, in particular, provision is made that the proportion of the catalytically active component in the carrier is reduced by comparison with conventional catalytically active solid extrudates.
- Preferred embodiments can be derived from the sub-claims.
- the carrier and the washcoat coating are both formed as SCR catalysts.
- SCR catalysts there are three different known types of catalysts with application in the present invention:
- the rest of the solid extrudate is formed by catalytically inactive components, such as binders, fillers if necessary to increase strength and optionally a plasticiser for support during extrusion.
- catalytically inactive components such as binders, fillers if necessary to increase strength and optionally a plasticiser for support during extrusion.
- the proportion by volume of the active components in the carrier is lower than in conventional solid extrudate catalysts, in which the proportions lie in the range of the upper limits stated above. All in all, the proportion by volume in the carrier can be adjusted from 10 vol. % to the upper limit stated above. In particular, however, a range under 50 vol. % or a range between 10 and 60 or 10 and 40% is set. In some variant embodiments, therefore, the greater proportion by volume of the catalyst is formed by inactive components.
- this is preferably replaced by components which are neutral with respect to the extrusion process.
- these are easily extrudable masses and/or materials. These include, in particular, clays (this means sheet silicates with a grain diameter of less than 2 ⁇ m), aluminium oxide or else kaolin.
- the honeycomb catalyst according to the invention in particular the second SCR catalyst washcoat coating, is free from noble metals, at least in the front area.
- a noble metal coating is applied, especially as a washcoat, onto a rear—viewed in the direction of flow of the exhaust gas during operation—area. This serves to prevent ammonia slip.
- the rear area therefor forms what is known as an ASC catalyst (ammonia slip catalyst).
- this noble metal coating is thereby embedded in the form of a sandwich between the carrier and a washcoat coating extending over the entire length, which is in particular embodied as an SCR catalyst. That is, the noble metal-containing washcoat is applied as a layer directly onto the carrier and the second SCR catalyst washcoat layer is applied over an entire length of the extruded active carrier, including the noble metal-containing washcoat.
- This arrangement has the benefit that ammonia which slips past the upstream zone of the first and second SCR catalysts can be oxidised to NO x on the lower, noble metal layer and this NO x then passes through the second SCR catalyst layer to exit the catalyst structure and contacts in-coming ammonia, whereby the NO x is reduced to N 2 on the second SCR catalyst.
- the washcoat coating has a relatively high porosity, so that the exhaust gas to be cleaned also comes into contact with the catalytically active carrier.
- the carrier In order to achieve a good catalytic activity, the carrier also has a high porosity. Both the carrier and the washcoat coating typically have a large BET surface area in the range of about 40 to 80 m 2 /g.
- the layer thickness of the washcoat coating preferably lies in the range of 30 to 100 ⁇ m, in particular in the range of about 40 to 60 ⁇ m.
- a single washcoat coating is applied to the carrier. Because the carrier is also active, a multi-layered washcoat coating is not necessary and preferably not provided. It is, however, possible.
- the web width of the webs of the honeycomb structure can be reduced.
- the web widths are in the range of about 300 ⁇ m. This is preferably reduced to a range of about 150 to 220 ⁇ m, in particular to a range of about 180 ⁇ m.
- the individual catalysts differ firstly from an economic viewpoint with respect to their price.
- the copper-zeolite catalyst is the most expensive, while the vanadium catalyst is the cheapest.
- NOx-activity across the temperature range is especially important, i.e. the capacity for NOx-reduction at both low and high temperatures.
- sulphur tolerance and in particular NO 2 tolerance are of particular importance.
- the temperature stability of different materials is also relevant.
- an exhaust system for a vehicular lean burn internal combustion engine comprising an extruded honeycomb catalyst according to the invention disposed in a flow conduit thereof.
- the exhaust system comprises means for injecting a nitrogenous reductant or a precursor thereof into the exhaust gas upstream of the extruded honeycomb catalyst.
- a lean burn internal combustion engine comprising an exhaust system according to the invention comprising a catalyst for generating NH 3 in situ in exhaust gas upstream of the extruded honeycomb catalyst and control means for changing an exhaust gas composition to a composition which promotes in situ NH 3 on the catalyst for generating NH 3 in situ.
- the catalyst for generating NH 3 in situ in exhaust gas upstream of the extruded honeycomb catalyst is a diesel oxidation catalyst or a NO x absorber catalyst and in particular comprises a platinum group metal and preferably also a lanthanide element, preferably cerium optionally in combination with one or more stabilisers such as zirconia and/or a rare earth element.
- a vehicle comprising an exhaust system according to the invention or a lean burn internal combustion engine according to the invention.
- FIG. 1 is a graph showing the NO x conversion activity at various temperatures for an extruded honeycomb catalyst according to the present invention comprising an extruded active carrier comprising a V 2 O 5 /WO 3 /TiO 2 or Fe—ZSM-5 (MFI) zeolite first SCR catalyst washcoated with a WO 3 /CeO 2 —ZrO 2 second SCR catalyst compared with the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carriers without the second SCR catalyst coating;
- an extruded active carrier comprising a V 2 O 5 /WO 3 /TiO 2 or Fe—ZSM-5 (MFI) zeolite first SCR catalyst washcoated with a WO 3 /CeO 2 —ZrO 2 second SCR catalyst compared with the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carriers without the second SCR catalyst coating
- MFI Fe—ZSM-5
- FIG. 2 is a graph showing the NO x conversion activity at various temperatures for an extruded honeycomb catalyst according to the present invention comprising an extruded active carrier comprising a Fe—ZSM-5 (MFI) zeolite first SCR catalyst washcoated with a Cu—SAPO-34 (CHA) second SCR catalyst compared with the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carrier without the second SCR catalyst coating;
- MFI Fe—ZSM-5
- CHA Cu—SAPO-34
- FIG. 3 is a graph showing the NO x conversion activity at various temperatures for an extruded honeycomb catalyst according to the present invention comprising an extruded active carrier comprising a Fe-Beta zeolite first SCR catalyst washcoated with a Cu—SSZ-13 (CHA) second SCR catalyst at two different washcoat loadings compared with the same loadings of the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carrier without the second SCR catalyst coating; and
- an extruded active carrier comprising a Fe-Beta zeolite first SCR catalyst washcoated with a Cu—SSZ-13 (CHA) second SCR catalyst at two different washcoat loadings compared with the same loadings of the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carrier without the second SCR catalyst coating
- CHA Cu—SSZ-13
- FIG. 4 is a graph showing the NO x conversion activity at various temperatures for an extruded honeycomb catalyst according to the present invention comprising an extruded active carrier comprising a V 2 O 5 /WO 3 /TiO 2 first SCR catalyst washcoated with a Cu—SSZ-13 (CHA) second SCR catalyst at two different washcoat loadings compared with the same loadings of the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carrier without the second SCR catalyst coating.
- an extruded active carrier comprising a V 2 O 5 /WO 3 /TiO 2 first SCR catalyst washcoated with a Cu—SSZ-13 (CHA) second SCR catalyst at two different washcoat loadings compared with the same loadings of the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carrier without the second SCR catalyst coating.
- CHA Cu—SSZ-13
- Powdered commercially available Beta zeolite in hydrogen form is mixed with iron oxide (Fe—O), glass fibres, Kaolin, powdered synthetic boehmite and the plasticisers polyethylene oxide (2.25 wt. %) and oleic acid (1.62 wt. %) (both based on 100% of the total inorganic solids content) and is processed in an aqueous solution with a pH-value of 5-6 into a shapeable and flowable slip.
- cellulose is added at 2.25 wt % based on 100% of the total inorganic solids content.
- the quantitative proportions of the starting materials are selected in such a way that the active material of the finished solid catalyst body contains 70.34% by weight of zeolite, iron and iron compounds; 2.76% by weight of the Kaolin; 15.94% by weight of ⁇ -Al 2 O 3 ; and 4.84% by weight of glass fibers.
- the shapeable mixture is extruded into a flow-through honeycomb catalyst body, i.e. with continuous channels and with a circular cross-section exhibiting a cell density of 400 cpsi (cells per square inch).
- the catalyst body is freeze dried for 1 hour at 2 mbar according to the method described in WO 2009/080155 (the entire contents of which is incorporated herein by reference) and calcined at a temperature of 580° C. to form a solid catalyst body. It is found that by using the method described that at least some of the iron introduced into the mixture becomes ion-exchanged with the zeolite.
- Powdered commercially available tungsten-containing TiO 2 at 10 wt. % tungsten is mixed with glass fibres, Kaolin, a low alkaline clay filler and powdered synthetic boehmite Ammonium metavanadate: 1.88 wt. %; 2-Aminoethanol: 1.5 litres; Lactic acid 90%; 0.48 wt %; Ammonia 25%: 8.97 wt % and the plasticisers polyethylene oxide (0.86 wt. %) and oleic acid (0.14 wt. %) (all based on 100% of the total inorganic solids content) and is processed in an aqueous solution with a pH-value of 5-6 into a shapeable and flowable slip.
- the mixture When the mixture is well plasticised, cellulose is added at 0.86 wt % based on 100% of the total inorganic solids content.
- the quantitative proportions of the starting materials are selected in such a way that the active material of the finished solid catalyst body contains approximately 72 wt % V 2 O 5 /WO 3 /TiO 2 ; silica 1.20 wt %; Kaolin 2.85 wt %; clay 2.85 wt. %; and glass fibres 6.93 wt. %.
- the shapeable mixture is extruded into a flow-through honeycomb catalyst body, i.e. with continuous channels and with a circular cross-section exhibiting a cell density of 400 cpsi (cells per square inch).
- the catalyst body is freeze dried for 1 hour at 2 mbar according to the method described in WO 2009/080155 (the entire contents of which is incorporated herein by reference) and calcined at a temperature of 580° C. to form a solid catalyst body.
- the powdered ZSM-5 zeolite is mixed with glass fibers and powdered synthetic boehmite and is processed in an acetous aqueous solution with a pH-value of 3.5 into a shapeable and flowable slip by admixture of cellulose, and oleic acid and polyethylene glycol plasticizers.
- the quantitative proportions of the starting materials are selected in such a way that the active material of the finished solid catalyst body contains 75% by weight of zeolite containing the iron and iron compounds; 11.8% by weight of ⁇ -Al 2 O 3 and 8% by weight of glass fibers.
- the shapeable mixture is extruded into a honeycomb catalyst body with continuous channels and with a round cross-section exhibiting a cell density of 400 cpsi (cells per square inch). Subsequently, the catalyst body is dried at a temperature of 90° C. and calcined to form a solid catalyst body at a temperature of 600° C.
- a catalyst comprising 15 wt % tungsten supported on a ceria-zirconia mixed oxide comprising 50:50 weight % of ceria and zirconia was prepared by an incipient wetness impregnation method comprising dissolving sufficient ammonium metatungstate to give the desired 15 wt % W loadings in deionised H 2 O.
- the total volume of solution was equivalent to the pore volume of the support sample (incipient wetness technique).
- the solution was added to the mixed oxide support material and the resultant mixture was dried overnight at 105° C. and then calcined at 700° C. for 3 hours.
- Extruded active carriers of Example 1 were coated with a washcoat comprising the second SCR catalyst of Example 2 using the method disclosed in WO 99/47260, i.e. comprising the steps of (a) locating a containment means on top of a extruded active carrier support, (b) dosing a pre-determined quantity of a liquid component into said containment means, either in the order (a) then (b) or (b) then (a), and (c) by applying pressure or vacuum, drawing said liquid component into at least a portion of the extruded active carrier support, and retaining substantially all of said quantity within the extruded active carrier support.
- the coated extruded active carriers were then dried in air at 100° C. for 1 hour and calcined at 500° C. for 2 hours.
- a 2.54 cm ⁇ 14 cm core was cut from each of the extruded honeycomb catalysts of Example 3 and the catalysts were tested at steady state at the following temperature points: 180° C., 215° C., 250° C., 300° C., 400° C. and 500° C. in a synthetic catalytic activity test laboratory apparatus using the following synthetic gas mixture: O 2 9.3%; H 2 O 7.0%; NO x 100 ppm (NO only); NH 3 100 ppm; Balance N 2 (Swept Volume: 60.000 litres/hr).
- FIG. 1 shows the results for Examples 3A and 3B compared with an identical washcoat composition (i.e. Example 2C) coated on an inert cordierite honeycomb carrier at 400 cpsi at 3.4 g/in 3 loading; and the extruded catalyst carriers of Examples 1B and 1C per se.
- Example 2C an identical washcoat composition coated on an inert cordierite honeycomb carrier at 400 cpsi at 3.4 g/in 3 loading
- Examples 1B and 1C show increased NO x conversion performance across the full temperature range.
- FIG. 2 shows the results for Example 3C compared with an identical washcoat composition (i.e. Example 2A) coated on an inert cordierite honeycomb carrier at 400 cpsi at 1.8 g/in 3 loading; and the extruded catalyst carrier of Example 1C per se.
- Example 2A an identical washcoat composition coated on an inert cordierite honeycomb carrier at 400 cpsi at 1.8 g/in 3 loading; and the extruded catalyst carrier of Example 1C per se.
- FIG. 3 shows the results for Examples 3D1 and 3D2 compared with identical washcoat compositions (i.e. Example 2B) coated on an inert cordierite honeycomb carrier at 400 cpsi at 1.5 g/in 3 and 0.5 g/in 3 loadings; and the extruded catalyst carrier of Example 1A per se.
- Example 3D1 and 3D2 show increased NO x conversion performance at ⁇ 300° C. and >400° C.
- FIG. 4 shows the results for Examples 3E1 and 3E2 compared with identical washcoat compositions (i.e. Example 2B) coated on an inert cordierite honeycomb carrier at 400 cpsi at 1.5 g/in 3 and 0.5 g/in 3 loadings; and the extruded catalyst carrier of Example 1B per se.
- Example 3E1 and 3E2 show increased NO x conversion performance at >400° C.
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Abstract
An extruded honeycomb catalyst for nitrogen oxide reduction according to the selective catalytic reduction (SCR) method in exhaust gases from motor vehicles includes an extruded active carrier in honeycomb form having a first SCR catalytically active component and with a plurality of channels through which the exhaust gas flows during operation, and a washcoat coating having a second SCR catalytically active component being applied to the extruded body, wherein the first SCR catalytically active component and the second SCR catalytically active component are each independently one of:
-
- (i) vanadium catalyst with vanadium as catalytically active component;
- (ii) mixed-oxide catalyst with one or more oxides, in particular those of transition metals or lanthanides as catalytically active component; and
- (iii) an Fe- or a Cu-zeolite catalyst.
Description
- The invention concerns an extruded honeycomb catalyst, in particular for exhaust gas cleaning, especially in the domain of motor vehicles, where it is used in particular for nitrogen oxide reduction according to the selective catalytic reduction (SCR) method, i.e. the reduction of oxides of nitrogen using a nitrogenous reductant. The invention also concerns a set of such variously embodied honeycomb catalysts and a method for producing honeycomb catalysts.
- Extruded honeycomb catalysts are one-piece, monolithic objects, which have a plurality of channels through which the exhaust gas flows during operation. These channels have an opening width of just a few millimetres. The webs delimiting the individual channels also typically have a width of just 300 μm. In extruded honeycomb catalysts, in which the solid material is catalytically active, a high proportion by volume of the solid body consists of catalytically active components. The result of this is that any modifications of the catalytic components, for example to make adaptations to different requirements and in general to pursue refinements, have a critical effect on extrudability. Altogether, this makes the development period for a new extruded honeycomb catalyst, in which the solid material is catalytically active, expensive.
- WO 2010/099395 A1 discloses extruded honeycomb catalyst bodies and methods of manufacturing them. The catalyst body includes a first oxide selected from the group consisting of tungsten oxides, vanadium oxides and combinations thereof, a second oxide selected from the group consisting of cerium oxides, lanthanum oxides, zirconium oxides and combinations thereof and a zeolite. In one embodiment, an extruded zeolite core is coated with a layer of a mixture of a cerium oxide, a zirconium oxide and a tungsten oxide.
- On that basis, the invention is based on the problem of specifying a honeycomb catalyst which can be adapted to new requirements with low development costs.
- The problem is solved according to the invention by claim 1. According to this claim, provision is made that the honeycomb catalyst as a whole is formed from an extruded, active carrier in honeycomb form, which has at least one catalytically active component and on which in addition a catalytically active coating, in particular a washcoat coating, is applied, which thus likewise has at least one catalytic component.
- The problem is further solved according to the invention by a set of honeycomb catalysts which differ in terms of their functionality, but which each have an identical carrier, and by a method for producing honeycomb catalysts of this type.
- This embodiment is based on the idea of developing and providing a carrier which can be used universally for several domains of application and making specific adaptations to the respective requirements via the special washcoat coating. The particular advantage is to be seen in the fact that a different extrusion mass does not have to be developed and provided for different honeycomb catalysts. At the same time, because of the option of different combinations between the active carrier and the likewise catalytically active coatings, the entire catalytic activity can be adapted and designed as appropriate. In principle, this provides the option, firstly, of developing the catalyst with a view to a technically optimised functionality or alternatively with a view to a catalyst optimised in terms of cost. In order to achieve the latter, in particular, provision is made that the proportion of the catalytically active component in the carrier is reduced by comparison with conventional catalytically active solid extrudates.
- Also it is possible to improve SCR activity of a catalyst which is otherwise sensitive to gas composition, e.g. ratio of NO2:NO (see Fe/ZSM-5 (MFI) SCR in EP 1147801).
- Preferred embodiments can be derived from the sub-claims.
- The carrier and the washcoat coating are both formed as SCR catalysts. In particular, there are three different known types of catalysts with application in the present invention:
-
- a catalyst referred to below as a vanadium catalyst, with vanadium as catalytically active component. This usually contains, as main components, vanadium oxide, titanium oxide and tungsten oxide. In conventional catalytically active solid extrudates the proportion by volume of these catalytically active main components is about 75 to 85 vol. %.
- The second type of catalyst is a mixed oxide catalyst with one or more oxides or lanthanides as catalytically active components. Typically-used metal oxides are, for example, cerium oxide, zirconium oxide or tungsten oxide, which in conventional catalysts have a proportion by volume of about 75 to 85%. Mixed oxide catalysts of this type are usually free from zeolites and also free from vanadium.
- As third SCR catalyst type, metal-zeolite catalysts are known with a metal zeolite as catalytically active component. In particular, this is an iron-zeolite or copper-zeolite. In a zeolite catalyst of this type, the proportion by volume of these active components lies in the range of about 60 to 70% in conventional solid extrudates.
- The rest of the solid extrudate is formed by catalytically inactive components, such as binders, fillers if necessary to increase strength and optionally a plasticiser for support during extrusion.
- Advantageously, the proportion by volume of the active components in the carrier is lower than in conventional solid extrudate catalysts, in which the proportions lie in the range of the upper limits stated above. All in all, the proportion by volume in the carrier can be adjusted from 10 vol. % to the upper limit stated above. In particular, however, a range under 50 vol. % or a range between 10 and 60 or 10 and 40% is set. In some variant embodiments, therefore, the greater proportion by volume of the catalyst is formed by inactive components.
- In the variant embodiments with the reduced catalytically active proportion, this is preferably replaced by components which are neutral with respect to the extrusion process. This means that these are easily extrudable masses and/or materials. These include, in particular, clays (this means sheet silicates with a grain diameter of less than 2 μm), aluminium oxide or else kaolin.
- The honeycomb catalyst according to the invention, in particular the second SCR catalyst washcoat coating, is free from noble metals, at least in the front area. In one preferred embodiment, a noble metal coating is applied, especially as a washcoat, onto a rear—viewed in the direction of flow of the exhaust gas during operation—area. This serves to prevent ammonia slip. The rear area therefor forms what is known as an ASC catalyst (ammonia slip catalyst).
- Advantageously this noble metal coating is thereby embedded in the form of a sandwich between the carrier and a washcoat coating extending over the entire length, which is in particular embodied as an SCR catalyst. That is, the noble metal-containing washcoat is applied as a layer directly onto the carrier and the second SCR catalyst washcoat layer is applied over an entire length of the extruded active carrier, including the noble metal-containing washcoat. This arrangement has the benefit that ammonia which slips past the upstream zone of the first and second SCR catalysts can be oxidised to NOx on the lower, noble metal layer and this NOx then passes through the second SCR catalyst layer to exit the catalyst structure and contacts in-coming ammonia, whereby the NOx is reduced to N2 on the second SCR catalyst.
- For all variant embodiments, the washcoat coating has a relatively high porosity, so that the exhaust gas to be cleaned also comes into contact with the catalytically active carrier.
- In order to achieve a good catalytic activity, the carrier also has a high porosity. Both the carrier and the washcoat coating typically have a large BET surface area in the range of about 40 to 80 m2/g.
- The layer thickness of the washcoat coating preferably lies in the range of 30 to 100 μm, in particular in the range of about 40 to 60 μm. Advantageously, only a single washcoat coating is applied to the carrier. Because the carrier is also active, a multi-layered washcoat coating is not necessary and preferably not provided. It is, however, possible.
- In particular, in the case of catalytically active solid extrudates with a reduced proportion of active components in the solid extrudate, the web width of the webs of the honeycomb structure can be reduced. In conventional extruded honeycomb catalysts made from a catalytically active solid extrudate, the web widths are in the range of about 300 μm. This is preferably reduced to a range of about 150 to 220 μm, in particular to a range of about 180 μm.
- Using the concept of an active washcoat coating on a carrier, different active honeycomb catalysts can be designed according to requirements to meet different needs.
- These different combinations take into account the various advantages and disadvantages of the individual catalysts, which are preferably combined in such a way that their advantages are increased and their disadvantages are reduced. So the individual catalysts differ firstly from an economic viewpoint with respect to their price. Here, for example, the copper-zeolite catalyst is the most expensive, while the vanadium catalyst is the cheapest. With respect to their technical characteristics, NOx-activity across the temperature range is especially important, i.e. the capacity for NOx-reduction at both low and high temperatures. Furthermore, sulphur tolerance and in particular NO2 tolerance are of particular importance. Finally, the temperature stability of different materials is also relevant.
- Depending on the intended use, the following preferred combination possibilities are suitable:
-
- a) Embodiment of the carrier as a mixed oxide catalyst with a washcoat coating, which can be either an Fe- or a Cu-zeolite catalyst. The advantage of the mixed oxide catalyst here lies in its low storage capacity, in particular ammonia storage capacity. Ammonia is regularly used in the SCR method as a typical reducing agent. This enables simple dosing as a function of the current demand. The mixed oxide catalyst displays weaknesses in the higher temperature range, which are equalised by the washcoat coating. Conversely, in the lower temperature range it is better by comparison with the Fe-zeolites, so that, overall, improved activity is achieved over the entire temperature range.
- b) A washcoat coating made from a vanadium catalyst is applied to a carrier made from a mixed oxide catalyst. The advantage of the vanadium catalyst consists in its good sulphur tolerance, which is, conversely, a weakness of the mixed oxide catalyst. Conversely, the mixed oxide catalyst has higher activity at lower temperatures. A further advantage of the mixed oxide catalyst can be seen in its good NO2 tolerance.
- c) A washcoat made from a copper-zeolite is applied to a carrier made from an Fe-zeolite. The very good activity in the lower temperature range of the copper zeolite is supplemented by the good sulphur tolerance of the iron zeolite. Also, a combination of this type is especially tolerant to NO2, since iron has especially good activity when there are medium and high NO2 levels, while copper has a very good activity when there are low NO2 levels in the exhaust gas.
- d) An Fe-zeolite is applied to a Cu-zeolite as washcoat. Here, the same advantages apply as in the aforementioned combination.
- e) A vanadium catalyst as washcoat is applied to an Fe-zeolite as carrier. This combination has improved sulphur resistance and a high NO2 tolerance, since the iron-zeolite catalyst has high activity when there are high NO2 levels in the exhaust gas, contrary to the vanadium catalyst.
- f) The combination of identical catalysts, for example Fe-zeolite catalyst with Fe-zeolite catalyst. This increases catalytic activity overall.
- g) An Fe-zeolite catalyst is applied to a carrier made from a vanadium catalyst. This achieves a very good activity over a wide range of NO2/NOx-ratios.
- The concept described here, namely the provision of an active carrier in combination with an active washcoat coating, therefore also finds expression in the method according to the invention. To produce honeycomb catalysts with different characteristics, therefore, a carrier type is supplied and stored which is then provided, depending on the domain of application, with different washcoat coatings.
- According to a further aspect, there is provided an exhaust system for a vehicular lean burn internal combustion engine comprising an extruded honeycomb catalyst according to the invention disposed in a flow conduit thereof.
- In one embodiment, the exhaust system comprises means for injecting a nitrogenous reductant or a precursor thereof into the exhaust gas upstream of the extruded honeycomb catalyst.
- According to a further aspect according to the present invention, there is provided a lean burn internal combustion engine comprising an exhaust system according to the invention comprising a catalyst for generating NH3 in situ in exhaust gas upstream of the extruded honeycomb catalyst and control means for changing an exhaust gas composition to a composition which promotes in situ NH3 on the catalyst for generating NH3 in situ.
- In one embodiment, the catalyst for generating NH3 in situ in exhaust gas upstream of the extruded honeycomb catalyst is a diesel oxidation catalyst or a NOx absorber catalyst and in particular comprises a platinum group metal and preferably also a lanthanide element, preferably cerium optionally in combination with one or more stabilisers such as zirconia and/or a rare earth element.
- According to a further aspect, there is provided a vehicle comprising an exhaust system according to the invention or a lean burn internal combustion engine according to the invention.
- In order that the present invention may be more fully understood, the following Examples are provided by way of illustration only and with reference to the accompanying drawings, wherein:
-
FIG. 1 is a graph showing the NOx conversion activity at various temperatures for an extruded honeycomb catalyst according to the present invention comprising an extruded active carrier comprising a V2O5/WO3/TiO2 or Fe—ZSM-5 (MFI) zeolite first SCR catalyst washcoated with a WO3/CeO2—ZrO2 second SCR catalyst compared with the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carriers without the second SCR catalyst coating; -
FIG. 2 is a graph showing the NOx conversion activity at various temperatures for an extruded honeycomb catalyst according to the present invention comprising an extruded active carrier comprising a Fe—ZSM-5 (MFI) zeolite first SCR catalyst washcoated with a Cu—SAPO-34 (CHA) second SCR catalyst compared with the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carrier without the second SCR catalyst coating; -
FIG. 3 is a graph showing the NOx conversion activity at various temperatures for an extruded honeycomb catalyst according to the present invention comprising an extruded active carrier comprising a Fe-Beta zeolite first SCR catalyst washcoated with a Cu—SSZ-13 (CHA) second SCR catalyst at two different washcoat loadings compared with the same loadings of the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carrier without the second SCR catalyst coating; and -
FIG. 4 is a graph showing the NOx conversion activity at various temperatures for an extruded honeycomb catalyst according to the present invention comprising an extruded active carrier comprising a V2O5/WO3/TiO2 first SCR catalyst washcoated with a Cu—SSZ-13 (CHA) second SCR catalyst at two different washcoat loadings compared with the same loadings of the second SCR catalyst coated on an inert cordierite honeycomb and the extruded active carrier without the second SCR catalyst coating. - Powdered commercially available Beta zeolite in hydrogen form is mixed with iron oxide (Fe—O), glass fibres, Kaolin, powdered synthetic boehmite and the plasticisers polyethylene oxide (2.25 wt. %) and oleic acid (1.62 wt. %) (both based on 100% of the total inorganic solids content) and is processed in an aqueous solution with a pH-value of 5-6 into a shapeable and flowable slip. When the mixture is well plasticised, cellulose is added at 2.25 wt % based on 100% of the total inorganic solids content. The quantitative proportions of the starting materials are selected in such a way that the active material of the finished solid catalyst body contains 70.34% by weight of zeolite, iron and iron compounds; 2.76% by weight of the Kaolin; 15.94% by weight of γ-Al2O3; and 4.84% by weight of glass fibers. The shapeable mixture is extruded into a flow-through honeycomb catalyst body, i.e. with continuous channels and with a circular cross-section exhibiting a cell density of 400 cpsi (cells per square inch). Subsequently, the catalyst body is freeze dried for 1 hour at 2 mbar according to the method described in WO 2009/080155 (the entire contents of which is incorporated herein by reference) and calcined at a temperature of 580° C. to form a solid catalyst body. It is found that by using the method described that at least some of the iron introduced into the mixture becomes ion-exchanged with the zeolite.
- Powdered commercially available tungsten-containing TiO2 at 10 wt. % tungsten is mixed with glass fibres, Kaolin, a low alkaline clay filler and powdered synthetic boehmite Ammonium metavanadate: 1.88 wt. %; 2-Aminoethanol: 1.5 litres;
Lactic acid 90%; 0.48 wt %; Ammonia 25%: 8.97 wt % and the plasticisers polyethylene oxide (0.86 wt. %) and oleic acid (0.14 wt. %) (all based on 100% of the total inorganic solids content) and is processed in an aqueous solution with a pH-value of 5-6 into a shapeable and flowable slip. When the mixture is well plasticised, cellulose is added at 0.86 wt % based on 100% of the total inorganic solids content. The quantitative proportions of the starting materials are selected in such a way that the active material of the finished solid catalyst body contains approximately 72 wt % V2O5/WO3/TiO2; silica 1.20 wt %; Kaolin 2.85 wt %; clay 2.85 wt. %; and glass fibres 6.93 wt. %. The shapeable mixture is extruded into a flow-through honeycomb catalyst body, i.e. with continuous channels and with a circular cross-section exhibiting a cell density of 400 cpsi (cells per square inch). Subsequently, the catalyst body is freeze dried for 1 hour at 2 mbar according to the method described in WO 2009/080155 (the entire contents of which is incorporated herein by reference) and calcined at a temperature of 580° C. to form a solid catalyst body. - An ion-exchanged, synthetic ZSM-5 zeolite, the active material of which contains 5% by weight of iron, is selected as zeolite. The powdered ZSM-5 zeolite is mixed with glass fibers and powdered synthetic boehmite and is processed in an acetous aqueous solution with a pH-value of 3.5 into a shapeable and flowable slip by admixture of cellulose, and oleic acid and polyethylene glycol plasticizers. The quantitative proportions of the starting materials are selected in such a way that the active material of the finished solid catalyst body contains 75% by weight of zeolite containing the iron and iron compounds; 11.8% by weight of γ-Al2O3 and 8% by weight of glass fibers. The shapeable mixture is extruded into a honeycomb catalyst body with continuous channels and with a round cross-section exhibiting a cell density of 400 cpsi (cells per square inch). Subsequently, the catalyst body is dried at a temperature of 90° C. and calcined to form a solid catalyst body at a temperature of 600° C.
- Commercially available SAPO-34 (CHA) (Example 2A) and SSZ-13 (CHA) (Example 2B) were NH4 + ion exchanged in a solution of NH4NO3, then filtered. The resulting materials were added to an aqueous solution of Cu(NO3)2 with stirring. The slurry was filtered, then washed and dried. The procedure can be repeated to achieve a desired metal loading. The final product was calcined.
- A catalyst comprising 15 wt % tungsten supported on a ceria-zirconia mixed oxide comprising 50:50 weight % of ceria and zirconia was prepared by an incipient wetness impregnation method comprising dissolving sufficient ammonium metatungstate to give the desired 15 wt % W loadings in deionised H2O. The total volume of solution was equivalent to the pore volume of the support sample (incipient wetness technique). The solution was added to the mixed oxide support material and the resultant mixture was dried overnight at 105° C. and then calcined at 700° C. for 3 hours.
- Extruded active carriers of Example 1 were coated with a washcoat comprising the second SCR catalyst of Example 2 using the method disclosed in WO 99/47260, i.e. comprising the steps of (a) locating a containment means on top of a extruded active carrier support, (b) dosing a pre-determined quantity of a liquid component into said containment means, either in the order (a) then (b) or (b) then (a), and (c) by applying pressure or vacuum, drawing said liquid component into at least a portion of the extruded active carrier support, and retaining substantially all of said quantity within the extruded active carrier support. The coated extruded active carriers were then dried in air at 100° C. for 1 hour and calcined at 500° C. for 2 hours.
- The following combinations of extruded active carrier and washcoat were prepared.
-
TABLE 1 Extruded Catalyst Washcoat Extruded Honeycomb Carrier Example Example Washcoat Catalyst Example No. Component Component Loading (g/in3) 3A 1B 2C 3.1 3B 1C 2C 3.1 3C 1C 2A 1.8 3D1 1A 2B 1.5 3D2 1A 2B 0.5 3E1 1B 2B 0.5 3E2 1B 2B 1.5 - A 2.54 cm×14 cm core was cut from each of the extruded honeycomb catalysts of Example 3 and the catalysts were tested at steady state at the following temperature points: 180° C., 215° C., 250° C., 300° C., 400° C. and 500° C. in a synthetic catalytic activity test laboratory apparatus using the following synthetic gas mixture: O2 9.3%; H2O 7.0%; NOx 100 ppm (NO only);
NH 3 100 ppm; Balance N2 (Swept Volume: 60.000 litres/hr). - The results including comparative data are shown in
FIGS. 1 to 4 . -
FIG. 1 shows the results for Examples 3A and 3B compared with an identical washcoat composition (i.e. Example 2C) coated on an inert cordierite honeycomb carrier at 400 cpsi at 3.4 g/in3 loading; and the extruded catalyst carriers of Examples 1B and 1C per se. As can be seen from the results, Examples 3A and 3B show increased NOx conversion performance across the full temperature range. -
FIG. 2 shows the results for Example 3C compared with an identical washcoat composition (i.e. Example 2A) coated on an inert cordierite honeycomb carrier at 400 cpsi at 1.8 g/in3 loading; and the extruded catalyst carrier of Example 1C per se. As can be seen from the results, there is a positive effect in the 200-500° C. temperature range tested. -
FIG. 3 shows the results for Examples 3D1 and 3D2 compared with identical washcoat compositions (i.e. Example 2B) coated on an inert cordierite honeycomb carrier at 400 cpsi at 1.5 g/in3 and 0.5 g/in3 loadings; and the extruded catalyst carrier of Example 1A per se. As can be seen from the results, Examples 3D1 and 3D2 show increased NOx conversion performance at <300° C. and >400° C. -
FIG. 4 shows the results for Examples 3E1 and 3E2 compared with identical washcoat compositions (i.e. Example 2B) coated on an inert cordierite honeycomb carrier at 400 cpsi at 1.5 g/in3 and 0.5 g/in3 loadings; and the extruded catalyst carrier of Example 1B per se. As can be seen from the results, Examples 3E1 and 3E2 show increased NOx conversion performance at >400° C. - For the avoidance of any doubt the entire contents of all documents cited herein are incorporated herein by reference in their entirety.
Claims (28)
1. Extruded honeycomb catalyst for nitrogen oxide reduction according to the selective catalytic reduction (SCR) method in exhaust gases from motor vehicles, comprising an extruded active carrier in honeycomb form comprising a first SCR catalytically active component and with a plurality of channels through which the exhaust gas flows during operation, and a washcoat coating comprising a second SCR catalytically active component being applied to the extruded body, wherein the first SCR catalytically active component and the second SCR catalytically active component are each independently selected from the group consisting of:
(i) vanadium catalyst with vanadium as catalytically active component;
(ii) mixed-oxide catalyst with one or more oxides, in particular those of transition metals or lanthanides as catalytically active component; and
(iii) an Fe- or a Cu-zeolite catalyst.
2. Honeycomb catalyst according to claim 1 , wherein in the extruded catalyst carrier the
vanadium catalyst has, as active main components, vanadium oxide, titanium oxide, tungsten oxide in a proportion by volume of 10 to 85%
the mixed oxide catalyst contains as main components mixed oxides in particular of lanthanides or of transition metals, in particular cerium oxide, zirconium oxide and tungsten oxide in a proportion by volume of 10 to 85% and is free from zeolites and from vanadium
the metal zeolite catalyst contains an Fe-zeolite or a Cu-zeolite in a proportion by volume of 10 to 70%,
and wherein the rest is formed in each case by catalytically inactive components such as binders, fillers as required and, when the active components are reduced, a component which is neutral with respect to the extrusion process.
3. Honeycomb catalyst according to claim 1 , wherein the proportion of active components in the extruded carrier is reduced by comparison with a conventional uncoated extruded honeycomb catalyst and lies in particular in the range between 10 and 60 vol. %, preferably in the range between 10 and 40 vol. %.
4. Honeycomb catalyst according to claim 1 , wherein the reduced proportion of the catalytically active component by comparison with a conventional uncoated honeycomb catalyst is replaced by a component which is neutral with respect to the extrusion process, in particular clay.
5. Honeycomb catalyst according to claim 1 , wherein the proportion of the neutral component lies in the range of 10 to 70 vol. %, in particular in the range of 20-50 vol. %.
6. Honeycomb catalyst according to claim 1 , wherein the washcoat coating, at least in a frontal area—in relation to a direction of flow of the exhaust gas during operation—is free from noble metals.
7. Honeycomb catalyst according to claim 1 , wherein the carrier has a rear area—in relation to a direction of flow of the exhaust gas during operation—on which there is preferably a noble metal coating to prevent ammonia slip.
8. Honeycomb catalyst according to claim 7 , wherein the washcoat coating extends over the entire length of the carrier and also covers the noble metal coating, in particular in the rear area.
9. Honeycomb catalyst according to claim 1 , wherein the washcoat coating and in particular also the carrier have a high porosity, in particular a BET surface area in the range of about 40-80 m2/g.
10. Honeycomb catalyst according to claim 1 , wherein the layer thickness of the washcoat coating lies in the range of 30 to 100 jam, in particular in the range of about 40-60 μm.
11. Honeycomb catalyst according to claim 1 , wherein the honeycomb structure has webs and the web width is reduced by comparison with a conventional uncoated extruded honeycomb catalyst and in particular lies in the range of about 150-220 μm.
12. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier is a mixed oxide catalyst and the washcoat coating is a metal-zeolite catalyst, in particular an Fe- or a Cu-catalyst.
13. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier is a mixed oxide catalyst and the washcoat coating is a vanadium catalyst.
14. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier is an Fe-zeolite catalyst and the washcoat coating is a Cu-zeolite catalyst.
15. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier is a Cu-zeolite catalyst and the washcoat coating is an Fe-zeolite catalyst.
16. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier is an Fe-zeolite catalyst and the washcoat coating is a vanadium catalyst.
17. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier and the washcoat coating are formed from the same catalyst, in particular each being in the form of an Fe-zeolite catalyst.
18. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier and the washcoat coating are formed from the same catalyst, in particular each being in the form of a Cu-zeolite catalyst.
19. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier and the washcoat coating are formed from the same catalyst, in particular each being in the form of a vanadium catalyst.
20. Honeycomb catalyst according to claim 1 , wherein the extruded catalyst carrier and the washcoat coating are formed from the same catalyst, in particular each being in the form of a mixed-oxide catalyst with one or more oxides, in particular those of transition metals or lanthanides as catalytically active component.
21. Honeycomb catalyst according to claim 1 , wherein the carrier is a vanadium catalyst and the washcoat coating is an Fe-zeolite catalyst.
22. A set of variously embodied extruded honeycomb catalysts according to claim 1 , wherein all the honeycomb catalysts in the set have an identical carrier.
23. Method for producing a set of variously embodied extruded honeycomb catalysts according to claim 1 , wherein identically-embodied carriers are provided and coated with different washcoats.
24. An exhaust system for a vehicular lean burn internal combustion engine comprising an extruded honeycomb catalyst according to claim 1 disposed in a flow conduit thereof.
25. An exhaust system according to claim 24 , comprising means for injecting a nitrogenous reductant or a precursor thereof into the exhaust gas upstream of the extruded honeycomb catalyst.
26. A lean burn internal combustion engine comprising an exhaust system according to claim 24 comprising a catalyst for generating NH3 in situ in exhaust gas upstream of the extruded honeycomb catalyst and control means for changing an exhaust gas composition to a composition which promotes in situ NH3 on the catalyst for generating NH3 in situ.
27. A lean burn internal combustion engine according to claim 26 , wherein the catalyst for generating NH3 in situ in exhaust gas upstream of the extruded honeycomb catalyst is a diesel oxidation catalyst or a NOx absorber catalyst.
28. A vehicle comprising an exhaust system according to claim 24 .
Priority Applications (2)
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US14/827,918 US20160040576A1 (en) | 2011-08-03 | 2015-08-17 | Extruded honeycomb catalyst |
US15/789,387 US10443472B2 (en) | 2011-08-03 | 2017-10-20 | Extruded honeycomb catalyst |
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US201261599124P | 2012-02-15 | 2012-02-15 | |
PCT/GB2012/051857 WO2013017873A1 (en) | 2011-08-03 | 2012-07-31 | Extruded honeycomb catalyst |
US201313817364A | 2013-02-15 | 2013-02-15 | |
US14/827,918 US20160040576A1 (en) | 2011-08-03 | 2015-08-17 | Extruded honeycomb catalyst |
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GB2493449B (en) | 2014-01-15 |
GB201318053D0 (en) | 2013-11-27 |
US10443472B2 (en) | 2019-10-15 |
RU2014107900A (en) | 2015-09-10 |
US9138731B2 (en) | 2015-09-22 |
DE102012213639A1 (en) | 2013-02-07 |
CN110193363A (en) | 2019-09-03 |
GB2506776A (en) | 2014-04-09 |
GB2493449A (en) | 2013-02-06 |
EP2739389B1 (en) | 2020-01-08 |
US20180298801A1 (en) | 2018-10-18 |
GB2504024B (en) | 2014-03-12 |
RU2017131859A3 (en) | 2020-11-16 |
GB201322431D0 (en) | 2014-02-05 |
RU2017131859A (en) | 2019-02-06 |
US20140157763A1 (en) | 2014-06-12 |
GB2504024A (en) | 2014-01-15 |
CN105363497A (en) | 2016-03-02 |
RU2637510C2 (en) | 2017-12-05 |
WO2013017873A1 (en) | 2013-02-07 |
BR112014002409B1 (en) | 2020-03-10 |
GB201213634D0 (en) | 2012-09-12 |
KR20140044907A (en) | 2014-04-15 |
JP2014525833A (en) | 2014-10-02 |
EP2739389A1 (en) | 2014-06-11 |
GB2506776B (en) | 2016-01-06 |
JP2017060945A (en) | 2017-03-30 |
BR112014002409A2 (en) | 2017-03-28 |
CN103842076A (en) | 2014-06-04 |
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