US20080034741A1 - Device For Purifying Exhaust Gases Of An Internal Combustion Engine - Google Patents
Device For Purifying Exhaust Gases Of An Internal Combustion Engine Download PDFInfo
- Publication number
- US20080034741A1 US20080034741A1 US11/629,251 US62925105A US2008034741A1 US 20080034741 A1 US20080034741 A1 US 20080034741A1 US 62925105 A US62925105 A US 62925105A US 2008034741 A1 US2008034741 A1 US 2008034741A1
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- United States
- Prior art keywords
- recited
- iron
- supporting material
- catalytically active
- containing material
- Prior art date
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- Abandoned
Links
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 title abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 65
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 239000004071 soot Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000019391 nitrogen oxide Nutrition 0.000 description 3
- 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
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
-
- 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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
-
- 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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
- F01N3/0231—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using special exhaust apparatus upstream of the filter for producing nitrogen dioxide, e.g. for continuous filter regeneration systems [CRT]
-
- 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
- F01N2250/00—Combinations of different methods of purification
- F01N2250/02—Combinations of different methods of purification filtering and catalytic conversion
-
- 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
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
-
- 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
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/065—Surface coverings for exhaust purification, e.g. catalytic reaction for reducing soot ignition temperature
Definitions
- the present invention relates to a device for purifying exhaust gases of an internal combustion engine.
- the present invention relates to an exhaust system for an internal combustion engine.
- German Published Patent Application No. 37 16 446 describes a catalytic diesel particulate filter, which has a catalytically active coating of metallically doped zeolite.
- the zeolite is preferably loaded with a metal of group IB, IIB, VB, VIB or VIIB of the periodic system or a combination of the same, nickel, copper, manganese, vanadium, silver, or a combination of the same being preferably used.
- German Published Patent Application No. 37 31 889 describes a diesel particulate filter, which has a filter element as a supporting material for a catalyst manufactured using at least one metallic oxide.
- the supporting material is made of a ceramic body or dross, e.g. metallic-oxide, body whose pore surfaces are coated throughout with one or more metallic oxides of the groups Ib, Vb, Vib, VIIb, or the Fe group.
- metallic-oxide e.g. metallic-oxide
- an additional reducing agent such as urea or a hydrocarbon
- urea or a hydrocarbon is often necessary to achieve the conversion of NO x , which is associated, however, with additional outlay and higher costs.
- the object of the present invention is to provide a device for purifying exhaust gases of an internal combustion engine, which even exhibits a very good purifying efficacy at relatively low temperatures, and in the case of which the need for an additional reducing agent is eliminated.
- an iron-containing material in the form of a catalytically active substance which is joined to the supporting material and present on the surface of the same, has a very good efficacy with regard to the conversion of the exhaust gases.
- the composition of the catalytically active coating according to the present invention induces nitrogen oxides to react with the soot particles present in the exhaust gas, reduction of NO x to N 2 , i.e. nitrogen formation, already having been detected at temperatures of app. 220° C., and almost no more harmful NO molecules being contained in the exhaust gas leaving the device, and the need for an additional reducing agent being eliminated.
- the soot particles contained in the exhaust gas are retained at the particle filter in a manner known per se and thus prevented from leaving the exhaust pipe in which the device of the present invention is preferably installed.
- the soot particles retained at the pores of the particle filter are used for the above-described reduction of the nitrogen oxides, which means that the amount of soot increases much less sharply than in the case of known particle filters, and accordingly, regeneration of the same is necessary considerably less often.
- the catalytic coating having the iron-containing material advantageously brings about a reduction in the ignition temperature of the soot, as well.
- the supporting material is an aluminosilicate or a silicon oxide, a very fine distribution of the iron-containing material present on the surface of the supporting material is achieved, which means that a considerable increase in the reactivity is achieved.
- soot-NO x conversion may be obtained, when a zeolite is used as a supporting material.
- a silicon oxide whose skeletal structure is of the type MCM41 or MCM48, may also be used as a supporting material. Good results regarding the soot-NO x conversion were also achieved with this.
- iron oxide is a highly effective oxidation catalyst for soot and is advantageously nontoxic.
- the iron-containing material is made of up to 100% iron oxide.
- the iron-containing material includes pure iron.
- the iron-containing material prefferably be made of up to 100% pure iron.
- the noble metals platinum and, in particular, palladium have proven to be particularly effective.
- FIG. 1 shows an internal combustion engine having an exhaust pipe, in which a device of the present invention for purifying the exhaust gas of the internal combustion engine is situated.
- FIG. 2 shows a schematic representation of the layer construction of a preferred embodiment according to the present invention.
- An internal combustion engine 1 is provided with an exhaust system 2 that has an exhaust pipe 2 a , through which the exhaust gases produced in internal combustion engine 1 in a manner known per se are discharged.
- a device 3 for purifying the exhaust gases of internal combustion engine 1 is situated in exhaust pipe 2 a , the device being described in more detail in the following.
- Internal combustion engine 1 is preferably an engine, which functions according to the diesel principle, and in whose exhaust gas soot particles are contained in addition to other pollutants.
- Device 3 includes a particle filter 4 , which is represented in a highly schematic manner and is preferably made of ceramic, such as silicon carbide, but may also be made of aluminum oxide or another suitable material.
- particle filter 4 has a plurality of intake ports 5 and exhaust ports 6 , which are alternately closed. Therefore, it is a two-way duct system. Alternatively, an open system having any duct shape and geometry would also be possible.
- Intake ports 5 and exhaust ports 6 are separated from each other by specific walls 7 indicated by dashed lines, which means that the exhaust gases must flow through walls 7 in order to travel from intake ports 5 into exhaust ports 6 and leave particle filter 4 in this manner.
- the material of walls 7 of particle filter 4 is designed to be porous in a manner known per se, so that the gaseous exhaust-gas components may pass through walls 7 , but the soot particles remain at the same and are deposited.
- particle filter 4 or walls 7 forming the same are provided with a catalytically active coating 8 , which includes a supporting material 9 and an iron-containing material 10 , which is joined to supporting material 9 and is present on the surface of the same.
- Supporting material 9 of catalytically active coating 8 is joined to particle filter 4 by an adhesive agent 1 , preferably silicon oxide.
- aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), cerium oxide (CeO 2 ), zirconium oxide (ZrO 2 ), or another suitable material may also be used as an adhesive agent 11 , which, on one side, bonds itself to the material of particle filter 4 and, on the other side, gives sufficient support to catalytically active coating 8 .
- Methods which are known per se and are therefore not explained below in further detail, may be used for joining catalytically active coating 8 to particle filter 4 via adhesive agent 11 . It is also possible to dispense with adhesive agent 11 .
- the layer thicknesses represented in FIG. 2 are to be regarded as purely exemplary.
- iron-containing material 10 may include iron oxide; in this connection, it is also possible for iron-containing material 10 to be made of up to 100% iron oxide. As an alternative, it is equally possible for iron-containing material 10 to include pure iron or to be made of up to 100% pure iron. In addition, a mixture of iron oxide and pure iron for forming iron-containing material 10 is also possible. Furthermore, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, zirconium, niobium, tungsten, and/or rhenium may be included in iron-containing material 10 , iron oxide or pure iron always forming the largest part of iron-containing material 10 .
- the ion-exchange method known per se may be used for joining iron-containing material 7 to supporting material 9 ; however, it is also possible to join supporting material 9 to iron-containing material 10 with the aid of a coating method.
- catalytically active coating 8 has, in addition to supporting material 9 and iron-containing material 10 , a noble metal 12 , which, in the represented case, is applied to catalytically active coating 8 as an additional layer. It is also possible to distribute noble metal 12 in catalytically active coating 8 in a manner not shown.
- Palladium or platinum is preferably used as a noble metal 12 , but ruthenium, rhodium, silver, osmium, iridium, or gold may also be used.
- Noble metal 12 may be present as an oxide or as a pure element.
- Supporting material 9 is preferably made of an amorphous or crystalline aluminosilicate, for example a ⁇ -zeolite, a zeolite of the type Y, or a zeolite of the type ZSM5.
- This porous supporting material 9 having a very large surface area is modified, using iron-containing material 10 , so that iron-containing material 10 is finely distributed over at least nearly the entire surface of supporting material 9 .
- a crystalline ⁇ -zeolite has proven to be particularly suitable in practice, especially since it does not decompose, even after a long period of time in which it is exposed to the exhaust gas, and it produces, especially with iron-containing material 10 , an exceptionally good efficacy of the catalytically active coating 8 .
- amorphous silicon oxide (SiO 2 ) for supporting material 9 , its skeletal structure being able to be of type MCM41, for example.
- the mode of operation of device 3 is as follows: the soot particles contained in the exhaust gas deposit on particle filter 4 and reduce the NO 2 and NO molecules contained in the exhaust gas to N 2 molecules by the action of catalytically active coating 8 , the carbon essentially forming the soot particles being simultaneously oxidized to form CO 2 .
- the following reaction equations, or at least one of the same, apply in this case: 2N0+C ⁇ >N 2 +CO 2 and 2NO 2 +2C ⁇ >N 2 +2CO 2
- device 3 may be coupled to an additional, commercially obtainable, upstream, e.g. platinum-based and/or palladium-based, oxidation catalytic converter 13 , in order to produce the more reactive NO 2 from the NO present in the exhaust gas.
- a further task of oxidation catalytic converter 13 may be to oxidize hydrocarbons and CO. Since hydrocarbons could particularly be stored in the zeolite, the risk of deactivating the zeolite is prevented in this manner.
Abstract
A device for purifying exhaust gases of an internal combustion engine has a particle filter, which is provided with a catalytically active coating. The catalytically active coating includes a supporting material and an iron-containing material, which is joined to the supporting material and is present on at least the surface of the same. The supporting material is an aluminosilicate or a silicon oxide.
Description
- The present invention relates to a device for purifying exhaust gases of an internal combustion engine. In addition, the present invention relates to an exhaust system for an internal combustion engine.
- German Published Patent Application No. 37 16 446 describes a catalytic diesel particulate filter, which has a catalytically active coating of metallically doped zeolite. The zeolite is preferably loaded with a metal of group IB, IIB, VB, VIB or VIIB of the periodic system or a combination of the same, nickel, copper, manganese, vanadium, silver, or a combination of the same being preferably used.
- In the case of this known filter, it is problematic, however, that the desired effect only sets in when a reducing agent is added, which, however, constitutes a relatively high degree of expenditure. A further disadvantage of this known particle filter is the fact that NO molecules contained in the exhaust gas are only converted to N2 above a temperature of 400° C., which makes it necessary to either situate this particle filter very close to the engine or generate high temperatures in the exhaust pipe.
- German Published Patent Application No. 37 31 889 describes a diesel particulate filter, which has a filter element as a supporting material for a catalyst manufactured using at least one metallic oxide. The supporting material is made of a ceramic body or dross, e.g. metallic-oxide, body whose pore surfaces are coated throughout with one or more metallic oxides of the groups Ib, Vb, Vib, VIIb, or the Fe group. However, the efficacy of this particle filter with regard to decreasing NOx is also not satisfactory.
- In the case of methods and devices for exhaust-gas purification known from the general related art, an additional reducing agent, such as urea or a hydrocarbon, is often necessary to achieve the conversion of NOx, which is associated, however, with additional outlay and higher costs.
- Therefore, the object of the present invention is to provide a device for purifying exhaust gases of an internal combustion engine, which even exhibits a very good purifying efficacy at relatively low temperatures, and in the case of which the need for an additional reducing agent is eliminated.
- It was unexpectedly determined that an iron-containing material in the form of a catalytically active substance, which is joined to the supporting material and present on the surface of the same, has a very good efficacy with regard to the conversion of the exhaust gases. Thus, it was able to be determined that the composition of the catalytically active coating according to the present invention induces nitrogen oxides to react with the soot particles present in the exhaust gas, reduction of NOx to N2, i.e. nitrogen formation, already having been detected at temperatures of app. 220° C., and almost no more harmful NO molecules being contained in the exhaust gas leaving the device, and the need for an additional reducing agent being eliminated.
- In this context, the soot particles contained in the exhaust gas are retained at the particle filter in a manner known per se and thus prevented from leaving the exhaust pipe in which the device of the present invention is preferably installed. At the same time, the soot particles retained at the pores of the particle filter are used for the above-described reduction of the nitrogen oxides, which means that the amount of soot increases much less sharply than in the case of known particle filters, and accordingly, regeneration of the same is necessary considerably less often. In addition to triggering these reactions, the catalytic coating having the iron-containing material advantageously brings about a reduction in the ignition temperature of the soot, as well.
- In this connection, the following reaction equations are produced:
2N0+C−>N2+C0 2
and
2NO2+2C−>N2+2CO2 - The effect of the simultaneous nitrogen-oxide reduction and the soot oxidation in the exhaust gas of the internal combustion engine, which results in particularly effective purification of the exhaust gas and therefore allows more stringent exhaust-gas limiting values to be met, should be particularly emphasized.
- Since the supporting material is an aluminosilicate or a silicon oxide, a very fine distribution of the iron-containing material present on the surface of the supporting material is achieved, which means that a considerable increase in the reactivity is achieved.
- Particularly good results regarding the soot-NOx, conversion may be obtained, when a zeolite is used as a supporting material.
- However, as an alternative, a silicon oxide, whose skeletal structure is of the type MCM41 or MCM48, may also be used as a supporting material. Good results regarding the soot-NOx conversion were also achieved with this.
- It has proven to be particularly advantageous with regard to the catalytic reactions, when the iron-containing material includes iron oxide. Iron oxide is a highly effective oxidation catalyst for soot and is advantageously nontoxic.
- In this connection, it may be particularly advantageous when the iron-containing material is made of up to 100% iron oxide.
- As an alternative, a good purifying effect is also to be expected when the iron-containing material includes pure iron.
- In this case, it is also analogously conceivable for the iron-containing material to be made of up to 100% pure iron.
- Improved reaction of the exhaust-gas components and, therefore, a particularly good purifying effect was able to be observed when the catalytically active coating included a noble metal.
- In this context, the noble metals platinum and, in particular, palladium have proven to be particularly effective.
-
FIG. 1 shows an internal combustion engine having an exhaust pipe, in which a device of the present invention for purifying the exhaust gas of the internal combustion engine is situated. -
FIG. 2 shows a schematic representation of the layer construction of a preferred embodiment according to the present invention. - An
internal combustion engine 1 is provided with anexhaust system 2 that has anexhaust pipe 2 a, through which the exhaust gases produced ininternal combustion engine 1 in a manner known per se are discharged. Adevice 3 for purifying the exhaust gases ofinternal combustion engine 1 is situated inexhaust pipe 2 a, the device being described in more detail in the following.Internal combustion engine 1 is preferably an engine, which functions according to the diesel principle, and in whose exhaust gas soot particles are contained in addition to other pollutants. -
Device 3 includes aparticle filter 4, which is represented in a highly schematic manner and is preferably made of ceramic, such as silicon carbide, but may also be made of aluminum oxide or another suitable material. For its part,particle filter 4 has a plurality ofintake ports 5 andexhaust ports 6, which are alternately closed. Therefore, it is a two-way duct system. Alternatively, an open system having any duct shape and geometry would also be possible.Intake ports 5 andexhaust ports 6 are separated from each other byspecific walls 7 indicated by dashed lines, which means that the exhaust gases must flow throughwalls 7 in order to travel fromintake ports 5 intoexhaust ports 6 and leaveparticle filter 4 in this manner. To this end, the material ofwalls 7 ofparticle filter 4 is designed to be porous in a manner known per se, so that the gaseous exhaust-gas components may pass throughwalls 7, but the soot particles remain at the same and are deposited. - As can be seen in the schematic representation according to
FIG. 2 ,particle filter 4 orwalls 7 forming the same are provided with a catalytically active coating 8, which includes a supporting material 9 and an iron-containing material 10, which is joined to supporting material 9 and is present on the surface of the same. Supporting material 9 of catalytically active coating 8 is joined toparticle filter 4 by anadhesive agent 1, preferably silicon oxide. For example, aluminum oxide (Al2O3), titanium oxide (TiO2), cerium oxide (CeO2), zirconium oxide (ZrO2), or another suitable material may also be used as anadhesive agent 11, which, on one side, bonds itself to the material ofparticle filter 4 and, on the other side, gives sufficient support to catalytically active coating 8. Methods, which are known per se and are therefore not explained below in further detail, may be used for joining catalytically active coating 8 toparticle filter 4 viaadhesive agent 11. It is also possible to dispense withadhesive agent 11. Of course, the layer thicknesses represented inFIG. 2 are to be regarded as purely exemplary. - In one specific embodiment of
device 3, iron-containing material 10 may include iron oxide; in this connection, it is also possible for iron-containing material 10 to be made of up to 100% iron oxide. As an alternative, it is equally possible for iron-containing material 10 to include pure iron or to be made of up to 100% pure iron. In addition, a mixture of iron oxide and pure iron for forming iron-containing material 10 is also possible. Furthermore, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, zirconium, niobium, tungsten, and/or rhenium may be included in iron-containing material 10, iron oxide or pure iron always forming the largest part of iron-containing material 10. - The ion-exchange method known per se may be used for joining iron-containing
material 7 to supporting material 9; however, it is also possible to join supporting material 9 to iron-containing material 10 with the aid of a coating method. - In the present case, catalytically active coating 8 has, in addition to supporting material 9 and iron-containing material 10, a
noble metal 12, which, in the represented case, is applied to catalytically active coating 8 as an additional layer. It is also possible to distributenoble metal 12 in catalytically active coating 8 in a manner not shown. Palladium or platinum is preferably used as anoble metal 12, but ruthenium, rhodium, silver, osmium, iridium, or gold may also be used.Noble metal 12 may be present as an oxide or as a pure element. - Supporting material 9 is preferably made of an amorphous or crystalline aluminosilicate, for example a β-zeolite, a zeolite of the type Y, or a zeolite of the type ZSM5. This porous supporting material 9 having a very large surface area is modified, using iron-containing material 10, so that iron-containing material 10 is finely distributed over at least nearly the entire surface of supporting material 9. A crystalline β-zeolite has proven to be particularly suitable in practice, especially since it does not decompose, even after a long period of time in which it is exposed to the exhaust gas, and it produces, especially with iron-containing material 10, an exceptionally good efficacy of the catalytically active coating 8. It would also be alternatively possible to use amorphous silicon oxide (SiO2) for supporting material 9, its skeletal structure being able to be of type MCM41, for example.
- The mode of operation of
device 3 is as follows: the soot particles contained in the exhaust gas deposit onparticle filter 4 and reduce the NO2 and NO molecules contained in the exhaust gas to N2 molecules by the action of catalytically active coating 8, the carbon essentially forming the soot particles being simultaneously oxidized to form CO2. The following reaction equations, or at least one of the same, apply in this case:
2N0+C−>N2+CO2
and
2NO2+2C−>N2+2CO2 - This means that only a considerably reduced amount of NOx molecules, and essentially only N2 molecules, are contained in the exhaust
gas leaving device 3, and that the soot particles are simultaneously deposited onparticle filter 4 and subsequently oxidized by NO and NO2. The action of iron-containingmaterial 7 in catalytically active coating 8 allows the described reactions to already proceed at temperatures of app. 220° C., so that is not necessary to positiondevice 3 particularly close tointernal combustion engine 1 or to introduce additional reducing agents intoexhaust pipe 2 a. Consequently, it is possible to remove the two pollutants NOx and soot from the exhaust gas ofinternal combustion engine 1, using asingle device 3. - In
FIG. 1 , it is also shown thatdevice 3 may be coupled to an additional, commercially obtainable, upstream, e.g. platinum-based and/or palladium-based, oxidationcatalytic converter 13, in order to produce the more reactive NO2 from the NO present in the exhaust gas. A further task of oxidationcatalytic converter 13 may be to oxidize hydrocarbons and CO. Since hydrocarbons could particularly be stored in the zeolite, the risk of deactivating the zeolite is prevented in this manner.
Claims (20)
1-19. (canceled)
20. A device for purifying an exhaust gas of an internal combustion engine, comprising:
a particle filter provided with a catalytically active coating, the catalytically active coating having a supporting material and an iron-containing material that is joined to the supporting material and is at least present on the surface of the same, and the supporting material being an aluminosilicate or a silicon oxide.
21. The device as recited in claim 20 , wherein the supporting material is a zeolite.
22. The device as recited in claim 20 , wherein the supporting material is a silicon oxide, whose skeletal structure is of the type MCM41 or MCM48.
23. The device as recited in claim 20 , wherein the iron-containing material includes iron oxide.
24. The device as recited in claim 23 , wherein the iron-containing material is up to 100% iron oxide.
25. The device as recited in claim 20 , wherein the iron-containing material includes pure iron.
26. The device as recited in claim 25 , wherein the iron-containing material is up to 100% pure iron.
27. The device as recited in claim 20 , wherein the iron-containing material is joined to the supporting material by coating.
28. The device as recited in claim 20 , wherein the iron-containing material is applied to the supporting material by ion exchange.
29. The device as recited in claim 20 , wherein the catalytically active coating includes a noble metal.
30. The device as recited in claim 29 , wherein the noble metal is applied to the catalytically active coating as an additional layer.
31. The device as recited in claim 29 , wherein the noble metal is distributed in the catalytically active coating.
32. The device as recited in claim 29 , wherein the noble metal is platinum or palladium.
33. The device as recited in claim 21 , wherein the zeolite is a β-zeolite.
34. The device as recited in claim 20 , wherein the supporting material is joined to the particle filter with the aid of an adhesive agent.
35. The device as recited in claim 34 , wherein the adhesive agent includes silicon oxide, aluminum oxide, cerium oxide, zirconium oxide, or titanium oxide.
36. The device as recited in claim 20 , wherein the particle filter is made of ceramic or of metal, having a two-way duct system or an open system.
37. An exhaust system for an internal combustion engine, comprising:
an exhaust pipe; and
a device situated in the exhaust pipe and for purifying an exhaust gas of an internal combustion engine, the device including:
a particle filter provided with a catalytically active coating, the catalytically active coating having a supporting material and an iron-containing material that is joined to the supporting material and is at least present on the surface of the same, and the supporting material being an aluminosilicate or a silicon oxide.
38. The exhaust system as recited in claim 37 , wherein the device is coupled to an upstream oxidation catalytic converter.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004028276.5 | 2004-06-11 | ||
DE102004028276A DE102004028276B4 (en) | 2004-06-11 | 2004-06-11 | Device for cleaning exhaust gases of an internal combustion engine |
PCT/EP2005/006219 WO2005121514A1 (en) | 2004-06-11 | 2005-06-09 | Apparatus for purifying exhaust gases of an internal combustion engine |
Publications (1)
Publication Number | Publication Date |
---|---|
US20080034741A1 true US20080034741A1 (en) | 2008-02-14 |
Family
ID=34972921
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/629,251 Abandoned US20080034741A1 (en) | 2004-06-11 | 2005-06-09 | Device For Purifying Exhaust Gases Of An Internal Combustion Engine |
Country Status (7)
Country | Link |
---|---|
US (1) | US20080034741A1 (en) |
EP (1) | EP1759097B1 (en) |
CN (1) | CN101184909B (en) |
AT (1) | ATE411450T1 (en) |
DE (2) | DE102004028276B4 (en) |
ES (1) | ES2312002T3 (en) |
WO (1) | WO2005121514A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2943927A1 (en) * | 2009-04-02 | 2010-10-08 | Peugeot Citroen Automobiles Sa | Particle filter for an internal combustion engine, comprises a catalyst in the form of amorphous iron particles or oxides, hydroxides and/or oxyhydroxides of iron deposited on a part of filtering walls in the form of colloidal suspension |
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- 2005-06-09 EP EP05767079A patent/EP1759097B1/en not_active Not-in-force
- 2005-06-09 ES ES05767079T patent/ES2312002T3/en active Active
- 2005-06-09 WO PCT/EP2005/006219 patent/WO2005121514A1/en active Application Filing
- 2005-06-09 AT AT05767079T patent/ATE411450T1/en not_active IP Right Cessation
- 2005-06-09 CN CN2005800189686A patent/CN101184909B/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
DE502005005700D1 (en) | 2008-11-27 |
DE102004028276A1 (en) | 2006-01-05 |
ATE411450T1 (en) | 2008-10-15 |
DE102004028276B4 (en) | 2008-08-21 |
CN101184909A (en) | 2008-05-21 |
ES2312002T3 (en) | 2009-02-16 |
CN101184909B (en) | 2010-06-23 |
EP1759097A1 (en) | 2007-03-07 |
EP1759097B1 (en) | 2008-10-15 |
WO2005121514A1 (en) | 2005-12-22 |
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