CN101091916A - Catalyst composition for diesel particulate filter - Google Patents
Catalyst composition for diesel particulate filter Download PDFInfo
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- CN101091916A CN101091916A CNA2007101265029A CN200710126502A CN101091916A CN 101091916 A CN101091916 A CN 101091916A CN A2007101265029 A CNA2007101265029 A CN A2007101265029A CN 200710126502 A CN200710126502 A CN 200710126502A CN 101091916 A CN101091916 A CN 101091916A
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- Prior art keywords
- filter
- carbon monoxide
- olefin polymeric
- oxide
- particulate filter
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- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title abstract description 46
- 230000008929 regeneration Effects 0.000 claims abstract description 82
- 238000011069 regeneration method Methods 0.000 claims abstract description 82
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 57
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 48
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 229910018879 Pt—Pd Inorganic materials 0.000 claims abstract description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical group O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 11
- 229930006000 Sucrose Chemical group 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 4
- 239000006229 carbon black Substances 0.000 claims description 59
- 229910052799 carbon Inorganic materials 0.000 claims description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000005720 sucrose Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 238000006424 Flood reaction Methods 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229960004793 sucrose Drugs 0.000 abstract description 10
- 239000004071 soot Substances 0.000 abstract description 4
- 235000013681 dietary sucrose Nutrition 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 238000007599 discharging Methods 0.000 description 20
- 238000006555 catalytic reaction Methods 0.000 description 17
- 229910052878 cordierite Inorganic materials 0.000 description 14
- 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 14
- 239000000446 fuel Substances 0.000 description 13
- 229910010271 silicon carbide Inorganic materials 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 6
- 239000002816 fuel additive Substances 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical class [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Processes For Solid Components From Exhaust (AREA)
- Catalysts (AREA)
Abstract
A catalyst composition is provided for use on a diesel particulate filter which facilitates the oxidation of soot from diesel engine exhaust and which generates low NO2 emissions during regeneration of the filter. The catalyst composition includes a catalytic metal comprising a platinum group metal selected from Pt, Pd, Pt-Pd, or combinations thereof, an active metal oxide component containing Cu and La; and an oxide component selected from oxides of Co, Fe, or combinations thereof. The catalyst composition includes a support selected from alumina, silica, zirconia, or combinations thereof. The catalyst composition may be provided on a diesel particulate filter by impregnating the filter with an alumina, silica or zirconia sol solution modified with glycerol and/or saccharose, impregnating the filter with a stabilizing solution, and impregnating the filter with a solution containing the catalyst metal precursor(s), the active metal oxide precursor(s) and the Co or Fe oxide(s). The resulting catalyst coated diesel particulate filter provides effective soot oxidation, exhibits good thermal stability, has a high BET surface area, exhibits minimal backpressure, and produces low NO2 emissions during filter regeneration.
Description
The cross reference of related application
The application be submitted on March 20th, 2006, part continuation application that sequence number is 11/385,005 U.S. Patent application " carbon black oxidation catalyst and manufacture method thereof (Soot Oxidation Catalyst and Method of Making) ".The complete content of this application is incorporated herein by reference.
Technical field
The present invention relates to be used for the carbon monoxide-olefin polymeric of diesel particulate filter.Specifically be, relate to a kind of oxidation that can help carbon black (soot), but can not produce the NO that increases at the regeneration period of particulate filter
2The carbon monoxide-olefin polymeric of discharging.
Background technology
In recent years, the Environmental Law of the restriction diesel particulate of US and European discharging makes improvement removal particle matter from emissions of diesel engines necessitate.This particulate is made up of the carbonization particulate that exists with the carbon black form usually.At present, the most frequently used method of removing carbon black from engine emission is to use diesel particulate filter (DPF), the filter traps carbon black, and the particulate of oxidation gathering comes regeneration filter at elevated temperatures then.
But a problem during the dpf regeneration is nitrogen dioxide (NO
2) discharging increase.Though the NO of regeneration period
2Discharge at present also not by law-making stipulation NO
2Discharging can produce as injure the health problem of lung.For example, dpf regeneration carries out in the place of the such sealing in for example garage, and a large amount of pollutant increases can occur in the air of motor vehicle environment.In some cases, the discharging of increase can cause pollutant levels to surpass occupational health standard.
The NO that increases during the particulate filter regeneration
2Produce relevant with the mechanism of carbon black burning in the particulate filter.Known have several diverse ways to come regeneration of particle filters.A kind of method is used on-catalytic formula diesel particulate filter.The regeneration that a problem of use on-catalytic formula diesel particulate filter is based on the carbon black oxidation may produce difficulty, the unfavorable carbon black oxidation of low temperature owing to the low temperature (for example, less than 200 ℃) of diesel exhaust gas.Therefore, need the high-temperature filter of the periodic oxidized black at elevated temperatures of regenerating.
Another known micro particle filtering system is auxiliary at the catalyst that the regeneration period of DPF depends in the fuel, promptly comprises catalyst in fuel, and metal normally reduces the temperature of carbon burning as additive.But such system complex and need additional parts for example is used for the additive tank of fuel additive, the basic system of additive sosimetric system and filling additive tank.In addition, the use of additive can cause being accumulated in the formation of the ashes on the filter in the fuel, causes the loss gradually of filter carbon black capacity and reduces the regeneration event interlude.Therefore, after per 80,000 kilometers, need to change filter.
The method of the removal carbon black that another is known is a precipitated catalyst on the wall of DPF, is also referred to as " catalysis type DPF " or " CDPF ".The palladium that the catalysis type carbon black filter generally includes one or more platinum metal catalysts and/or comprises oxidation catalyst comes the carbon black oxidation on the improved filter.Because the catalysis type diesel particulate filter does not have the auxiliary diesel particulate filter complexity of fuel and can obtain effective carbon black oxidation under lower temperature, understand the carbon black oxidation that preferred catalytic formula diesel fuel filter is used in regeneration period usually.But because the high value of platinum group metal, the catalysis type carbon black filter is made costliness usually.
In addition, the NO that produces by these known diesel fuel filter renovation process
2Discharge capacity change.Usually, use the renovation process of the particulate filter that catalyst is assisted in on-catalytic formula diesel particulate filter and the fuel to show low NO
2Generation ratio (that is NO at filter inlet place,
2Amount is higher than exit NO
2Discharge capacity).Because regeneration period NO as follows
2With the reaction of carbon black, the exhaust in the diesel fuel filter downstream that catalyst is assisted in on-catalytic formula or the fuel is compared with inlet concentration has lower NO
2Concentration.
C+NO
2→CO+NO
On the other hand, the catalysis type diesel particulate filter of existing (using the catalyst based on platinum) demonstrates high NO
2Generation ratio, the i.e. NO of filter outlet
2Amount is higher than the NO of filter inlet upstream
2Amount, expression regeneration period NO
2The increase that produces.
Because the catalysis type diesel particulate filter preferably is used in the carbon black oxidation usually, hope can make the NO that produces during the filter regeneration
2Discharging is reduced to low-level that other type filter can obtain, and still can keep the carbon black ignition quality.In addition, also wish to save the use of all or part platinum group metal in filter.
Although attempted suppressing or reducing NO in the diesel particulate filter
2Discharge capacity (that is, using the reducing catalyst be arranged in the exhaust flow path, urea for example, fuel or hydrocarbon) is not also developed and is not a kind ofly used reducing catalyst to reduce NO at regeneration period
2The method of discharging.
Therefore, need a kind of carbon monoxide-olefin polymeric that is used for diesel particulate filter.This carbon monoxide-olefin polymeric can be during periodic high temperature regeneration oxidized black effectively, use and use platinum on a small quantity or not, and can not need reducing agent or optional equipment just can effectively reduce the NO of regeneration period generation
2Discharging.
Summary of the invention
The invention provides a kind of carbon monoxide-olefin polymeric that is used for diesel particulate filter and satisfy the demand, described carbon monoxide-olefin polymeric uses and uses platinum on a small quantity or not, and the efficient oxidation carbon black and produce low NO at regeneration period
2Discharging.
According to an aspect of the present invention, provide a kind of diesel particulate filter that is used for to help the carbon monoxide-olefin polymeric of carbon black oxidation, described composition comprises: comprise from Pt Pd, the catalytic metal of the platinum group metal of selecting in Pt-Pd or its combination; The reactive metal oxides composition that comprises Cu and La; With from the Co oxide, the oxide that Fe oxide or its combination is selected.
The load of the platinum group metal in the composition (PGM) is less than 20g/ft
3Preferably, PGM loads on about 5 to about 15g/ft
3Between.In one embodiment of the invention, the platinum group metal can only comprise palladium.
The reactive metal oxides composition can comprise CuO-La
2CuO
4, the carbon black oxidation susceptibility that it provides carbon monoxide-olefin polymeric.
Carbon monoxide-olefin polymeric also can further comprise from aluminium oxide, silica, the carrier (support) that zirconia and its combination are selected.Described carrier material is preferably by lanthanum, silicon, zirconium, aluminium, or its combinative stability." stablize " and be meant that carrier material can prevent sintering under for example greater than 1000 ℃ to 1200 ℃ high temperature, high temperature can run into during diesel particulate filter regeneration.
Carbon monoxide-olefin polymeric of the present invention can be provided on diesel particulate filter or other porous matrix so that the oxidation that accumulates in carbon black on the filter to be provided.In the method for a catalyst that filter preferably is provided, diesel fuel filter is at first used from alumina sol (sol), silicon dioxide gel, zirconia sol, or sol solution (colloidal solution) dipping of selecting in its combination (impregnate), drying forms the carrier material of catalyst.Sol solution can further comprise from sucrose (saccharose), the organic compound that glycerine (glycerol) and its combination are selected.These organic compounds are used for increasing the surface area of coating.After filter was coated sol solution, the filter of proofing was dried and calcines.
Filter floods to prevent the sintering of regeneration period carrier in stabilizing solution then.When sol solution comprises alumina sol, stabilizing solution comprises the acetic acid zirconium, lanthanum nitrate or its combination.When sol solution comprises and silicon dioxide gel, stabilizing solution comprises the acetic acid zirconium, aluminum nitrate or its combination.When sol solution comprises zirconia sol, stabilizing solution comprises lanthanum nitrate.After having flooded stabilizing solution, the dry again and calcining of the filter of coating.
With the described filter of a kind of solution impregnation, described solution comprises from silver nitrate, palladium nitrate, chloroplatinic acid dihydro (dihydrogen hexachloroplatinate), with the catalytic metal precursor of its combination selection, from the metal oxide precursor of copper nitrate, lanthanum nitrate and its mixing selection; From cobalt nitrate, the oxide composition that ferric nitrate and its combination are selected.The dry again and calcining of the filter of dipping.
After coating the composition that comprises the sol solution of being made up of alumina sol or silicon dioxide gel when diesel particulate filter, the filter of coating preferably has 30-40m at least
2The BET surface area of/g.After coating the composition that includes zirconia sol when filter, the filter of coating preferably has 9-12m at least
2The BET surface area of/g.
The present invention also provides a diesel exhaust gas treatment system, described system comprises diesel particulate filter and proofing the carbon monoxide-olefin polymeric on filter of a reception from the diesel exhaust gas of Diesel engine, wherein carbon monoxide-olefin polymeric comprises from Pt, Pd, the catalytic metal of the platinum group metal of selecting in Pt-Pd or its combination, include the reactive metal oxides composition of Cu and La and from the Co oxide, the oxide composition of selecting in Fe oxide or its combination.In being attached to such diesel exhaust gas treatment system, carbon monoxide-olefin polymeric of the present invention can be at the temperature oxidized black between 550 ℃ and 600 ℃.In addition, carbon monoxide-olefin polymeric can help the low NO of regeneration period
2Discharging, the NO that makes the regeneration period generation
2Amount between 0.40 to 0.70, preferably 0.60, more preferably 0.40.
Therefore, a feature of the present invention provides the carbon monoxide-olefin polymeric that has on a small quantity or do not comprise the platinum load, and said composition provides effective carbon black oxidation and produces low NO at the regeneration period of particulate filter
2Discharging.Further feature and advantage are from following description, and accompanying drawing and claim can obviously be found out.
Description of drawings
Fig. 1 illustrates the NO during on-catalytic formula and the fuel assist type diesel particulate filter regeneration
2Discharging.
Fig. 2 illustrates one with reference to the NO during the catalysis type diesel particulate filter regeneration
2Discharging.
Fig. 3 illustrates an average regeneration efficiency of reducing to idle regeneration (DTIR) with reference to the catalysis type diesel particulate filter.
Fig. 4 is illustrated in the catalyst activity of reference CDPF during the carbon black burning that measures under the stable state regeneration condition.
Fig. 5 illustrates the NO of catalysis type diesel particulate filter (DTIR) regeneration period that comprises carbon monoxide-olefin polymeric of the present invention
2Discharging.
Fig. 6 illustrates average (DTIR) regeneration efficiency of CDPF of the present invention.
Fig. 7 illustrates CDPF of the present invention catalyst activity during the carbon black burning under limit.
The specific embodiment
We find catalytic metal Pt and/or Pd and metal oxide composition CuO-La
2CuO
4The combination catalyst that is used as the carbon black oxidation can reduce the required temperature of carbon black oxidation, allow to reduce the expensive Pt and the load of Pd family metal simultaneously.We also find further to add in carbon monoxide-olefin polymeric and hang down the NO that measures during cobalt/cobalt oxide and/or ferriferous oxide provide filter regeneration
2Discharging.Do not wish to be bound by any theory, we think cobalt/cobalt oxide and/or ferriferous oxide and the metal oxide composition CuO-La that adds
2CuO
4The heat-staple catalyst perovskite-like of combination results (perovskite-like) structure.Carbon monoxide-olefin polymeric of the present invention can make NO
2The NO that the discharging DPF auxiliary with using on-catalytic formula or fuel obtains
2Discharge equally low or lower.
In addition, applied heat endurance, minimized back pressure and the high surface area that the diesel particulate filter of this carbon monoxide-olefin polymeric provides." heat endurance " is meant that catalyst can still can keep activity or oxidation susceptibility after being exposed to high temperature." back pressure " is meant because carbon black accumulation or the coating of catalyst on filter cause filtering holes to stop up or size reduces the flow resistance that causes." minimize back pressure " and be meant when be coated with at filter be covered with catalyst after, catalyst of the present invention only increases the back pressure of filter slightly.
The catalytic metal that optimally is used for carbon monoxide-olefin polymeric of the present invention comprises Pt, Pd, Pt-Pd or its combination.Preferred metal oxide composition has 1: 1 Cu/La ratio, and preferably by CuO-La
2CuO
4Form.Preferably, cobalt/cobalt oxide and ferriferous oxide are Co
3O
4And Fe
2O
3
Carbon monoxide-olefin polymeric of the present invention is preferably supported with the increase surface area by resistant to elevated temperatures (refractory) oxide, thereby increases the activity of carbon black oxidation.The refractory oxide carrier also is used to be increased in the catalyst heat endurance under the high-temperature condition that runs into when diesel particulate filter uses.Be preferred for refractory oxide of the present invention and comprise aluminium oxide, silica and zirconia.
Such refractory oxide is preferably by being immersed in filter from alumina sol, and silicon dioxide gel is in the sol solution of selecting in zirconia sol or its combination and be deposited on the diesel particulate filter.We find to be immersed in the obstruction that the diesel particulate filter that forms in this solution is avoided filter (monolith monolith) hole, cause minimizing back pressure.The coating of filter (monolith) of (as three-way catalyst) that suspension (slurry) is generally used for having catalyst, but the coating of the inapplicable diesel particulate filter of suspension are because the average pore size of silicon carbide-based material approximately is 9 microns.The hole dimension of the size of particulate and filter is quite or greater than the filter hole size in the suspension, and therefore applying such host material with suspension can plugging hole or reduce hole dimension to a great extent.
Though sol solution (sol) is used for the monolith coating of the catalysis that automobile uses, operating weight adheres to lip-deep purpose than the sol solution for about 5% (percentage by weight) to reach big suspended particulates usually.But we find the catalyst coat of the high surface area that sol solution itself can provide on porous filtering modulator material (for example diesel particulate filter).
The average particle size of sol solution is silicon dioxide gel solution preferably: the 0.004-0.01 micron; Alumina sol solution: 0.05 micron and zirconia sol solution: 0.005-0.001 micron.Being used for preferred sol solution of the present invention can commercially obtain from A Faaisha (Alfa Aesar) company.The porosity that the amount of used sol solution depends on host material changes.Usually, the sol solution of about 520-550 milliliter is used to have the standard filter that 65% porosity (being made by cordierite) is of a size of 5.66 inches * 6 inches, and about 350 milliliters sol solution is used to have the carborundum filter of 42% porosity.
We find typical porous filtering modulator material (making diesel particulate filter by cordierite or carborundum) behind the sol solution that has adsorbed about 300-550 milliliter (5.66 inches * 6 inches filters), the BET surface area at primary coating be 24-30m behind 20% alumina sol and 30% the silicon dioxide gel
2/ g.Preferably, the particle size of sol solution at least than little two orders of magnitude of hole dimension of filter to avoid the obstruction in hole.
We find that in addition the surface area of catalyst coat obviously improves (seeing Table 2) at the organic compound that has added as glycerine and sucrose behind sol solution.Such organic compound also prevents aluminium oxide, silica, the increase of main particle size in the zirconia sol.Sucrose is as template agent (templating agent), and glycerine is used for preventing the adhesion of main particle.Two compounds reduce the crystalization of aluminium and break (collapse) of the monolith structure during the drying steps in addition.Should note to use sugar rather than sucrose and obtain the same result.Preferably, the glycerine of the sucrose of 5-10g and 10-30ml is added in 1 liter the sol solution.Though high concentration can further increase surface area, we find that high concentration also increases solution viscosity.This is unfavorable to applying purpose.
By be immersed on the filter use sol solution after, filter preferably under about 77 ℃ to 100 ℃ temperature dry and about 285 ℃ temperature lower calcination 1 hour to form catalyst carrier.
For the surface area that keeps the sol solution coating with prevent carrier (for example, high regeneration temperature to 1200 ℃) sintering at high temperature, after being coated to monolith and drying/calcining, preferably stablize aluminium oxide, silica and Zirconia carrier material.When carrier comprises aluminium oxide, stablize aluminium oxide with dipping zirconium and/or lanthanum precursor, preferably use acetic acid zirconium and lanthanum nitrate.
Preferably use 10-15% zirconium (to aluminium mol%) and 3-5%La (to aluminium mol%).When carrier comprises silica, preferably stablize with zirconium acetate solution.Preferably use 10-20% zirconium (to silicon mol%).In addition, can add the heat endurance that the aluminium (aluminum nitrate) that is limited to about 5mol% further increases carrier.When carrier comprises zirconia, use lanthanum solution.Preferably use 3-5%La (to zirconium mol%).After having used stabilizing solution, the filter of coating about 77 ℃ to 100 ℃ dry again and about 800 ℃ of calcinings two hours.
After stable, use washcoated layer solution (washcoat solution) immersion filtration device then, washcoated layer solution comprises from silver nitrate, palladium nitrate, the catalytic metal precursor that chloroplatinic acid dihydro and its combination are selected, from copper nitrate, lanthanum nitrate and its mix the reactive metal oxides precursor of selecting, from cobalt nitrate, the oxide precursor composition that ferric nitrate and its combination are selected.
Washcoated layer solution preferably further comprises a spot of citric acid, the every filter of 35-40g preferably, its auxiliary catalyst uniform deposition on filter that provides.
Washcoated layer solution also comprises from yttrium nitrate (yttrium nitrate) one or more nitrate that magnesium nitrate (magnesium nitrate) and cerous nitrate (cerium nitrate) are selected.These nitrate preferably add to come further stable carrier and/or catalyst to prevent sintering with about 1-4g slightly.
After having flooded the catalyst wash coating, the filter of coating is preferably about 16 hours of about 750 ℃ of calcinings.
Like this, carbon monoxide-olefin polymeric of the present invention is provided to diesel particulate filter by three step process: 1) proofing sol solution, 2) the dipping stabilizing solution, 3) the washcoated layer of impregnated catalyst.Though carbon monoxide-olefin polymeric described herein is applied on the diesel particulate filter, should understand said composition and also can be provided on other porous matrix, as mullite, aluminium titanates, aluminium oxide etc.Carbon monoxide-olefin polymeric preferably is coated on the diesel particulate filter of being made up of porous cordierite and carborundum.
When diesel particulate filter was made up of carborundum, the filter of catalyst-coated preferably had 30-40m at least
2The BET surface area of/g, and carrier material comprises aluminium oxide or silica.When carrier material comprises zirconia, the about 9-12m of BET surface area
2/ g.
The diesel particulate filter that includes this carbon monoxide-olefin polymeric can be used for the diesel exhaust gas treatment system provides effective carbon black oxidation.Between 550 ℃-600 ℃ of object regeneration temperature, this carbon monoxide-olefin polymeric preferably provides the carbon black oxidation of 60-100%, preferably, provides the carbon black oxidation of about 80-100%.
In regeneration therebetween, additional fuel is spurted into engine usually, and the additional fuel of diesel oxidation catalyst burning that is arranged on the diesel particulate filter upstream causes heat to discharge.The heat that discharges increases the temperature of diesel particulate filter to about 600 ℃, any carbon black of accumulating on the enough oxidation filters of this temperature, the NO that regeneration period produces
2Be emitted between about 0.40 to 0.70 preferably 0.60, more preferably 0.40.
Though the present invention mainly describes for removing carbon black from Diesel engine, should understand this carbon monoxide-olefin polymeric and can be used for the coal combustion application.
For the present invention is more readily understood, with reference to following example, example only is used for explaining invention, but does not limit its scope.
Example 1
The preparation of catalysis type diesel particulate filter
The diesel particulate filter for preparing a plurality of uses carbon monoxide-olefin polymeric of the present invention.
Cordierite filters (quality m=1048 gram) is via 250 milliliters of acetic acid zirconiums, 30 milliliters of glycerine, 17 gram sucrose and 5 gram lanthanum acetates and distilled water is formed and cumulative volume is 550 milliliters a solution impregnation, with the washcoated layer of preparation lanthanum stabilizing zirconia (zirconia).Sample is dry under 117 ℃ then, calcines three hours down at 750 ℃ subsequently.Then with the solution impregnation diesel particulate filter that comprises chloroplatinic acid dihydro, copper nitrate, lanthanum nitrate, ferric nitrate, cobalt nitrate and cerous nitrate.The Pt load is 1.76 grams (corresponding to 20 gram/cubic feet concentration), and the CuO load is 17.5 grams, La
2O
3Load is 34.9 grams, Fe
2O
3Load is 22.0 grams, Co
3O
4Load is 12.4 grams, and CeO
2Load is 8.0 grams.The catalysis type diesel particulate filter is dry under 100 ℃ temperature, calcines 16 hours down at 750 ℃ then.The final weight of filter is 1301 grams.
Carborundum (SiC) filter (quality m=1921 gram) floods through 10% alumina sol, adds 10 milliliters of glycerine and 2.7 gram sucrose modifications, calcines one hour down 100 ℃ of down dry a whole nights and at 285 ℃.Filter is through containing the solution impregnation of lanthanum nitrate (5mol% aluminium oxide) and acetic acid zirconium (15mol% aluminium oxide) then, and is dry down and 800 ℃ temperature lower calcination two hours at 100 ℃ then.Filter is through containing the solution impregnation of chloroplatinic acid (IV) dihydro, copper nitrate, lanthanum nitrate, a spot of yttrium nitrate and magnesium nitrate and citric acid (38 gram) then.The Pt load is 1.32 grams (15 gram/cubic feet), and the CuO load is 4.4 grams, La
2O
3Load is 6.4 grams, and the MgO load is 1.6 grams, and Y
2O
3Load is 1.9 grams.This filter was calcined 16 hours down at 750 ℃ then.The final weight of filter is 1995 grams.
Prepare carborundum (SiC) filter (quality m=1919 gram) in the described mode of sample filter # 55, but use 8% alumina sol in this case, and La and Zr load are 3mol% and 10mol% alumina weight.The Pt-Pd/CuO-La that mixes
2CuO
4Carbon monoxide-olefin polymeric forms by containing the solution that palladium nitrate, chloroplatinic acid dihydro, copper nitrate, lanthanum nitrate and a spot of ferric nitrate form.The Pt load is 0.44 gram (5 gram/cubic feet), and the Pd load is 0.88 gram (10 gram/cubic feet), and the CuO load is 3.6 grams, La
2O
3Load be 4.7 the gram and Fe
2O
3Load is 1.5 grams.The final weight of filter is 1979 grams.
Cordierite filters (quality m=1665 gram) at first through adding 375 milliliters 10% alumina sol dipping of 10 milliliters of glycerine and 2.7 gram sucrose modifications, continues calcining three hours down 100 ℃ of down dry a whole nights and at 295 ℃ then.Filter is through containing the solution impregnation of lanthanum nitrate (5mol% aluminium oxide) and acetic acid zirconium (15mol% aluminium oxide) then, and filter was calcined two hours down 100 ℃ of following dryings and at 800 ℃ then.Filter is through containing the solution impregnation of palladium nitrate, chloroplatinic acid dihydro, copper nitrate, lanthanum nitrate, cobalt nitrate, cerous nitrate, ferric nitrate and citric acid (32 gram) then.The Pt load is 0.44 gram (5 gram/cubic feet), and the Pt load is 0.88 gram (10 gram/cubic feet), and the CuO load is 7.8 grams, La
2O
3Load is 6.0 grams, Fe
2O
3Load is 2.0 grams, Co
3O
4Load is 2.4 grams, and CeO
2Load is 1.1 grams.In drying under 100 ℃ and after 750 ℃ are calcined 16 hours down, the final weight of filter is 1741 grams.
Cordierite filters (quality m=1663 gram) uses alumina sol to be coated with in the mode identical with sample # 63 and is covered with washcoated layer, stablizes by lanthana and zirconia then.Filter is by the solution impregnation that contains palladium nitrate, chloroplatinic acid dihydro, copper nitrate, lanthanum nitrate, cobalt nitrate, ferric nitrate and citric acid (32 gram) then.The Pd load is 1.23 grams (14 gram/cubic feet), and the Pt load is 0.09 gram (1 gram/cubic feet), and the CuO load is 9.4 grams, La
2O
3Load is 6.9 grams, Fe
2O
3Load is 2.0 grams, and Co
3O
4Load is 2.8 grams.100 ℃ down dry and after 750 ℃ temperature lower calcination 16 hours, the final weight of filter is 1737 grams.
By as above sample 63 described modes being prepared cordierite filters (quality m=1645 gram), but in precursor solution, do not add platinum and cerium compound in this case.The Pd load is 0.44 gram (5 gram/cubic feet), and the CuO load is 12.6 grams, La
2O
3Load is 17.2 grams, Fe
2O
3Load is 2.5 grams, and Co
3O
4Load is 5.1 grams.The final weight of filter is 1743 grams.
Example 2
Test comes comparison with reference to (commerce) sample according to the sample filter of example 1 preparation, on-catalytic formula (no coating) DPF sample, the DPF (ADPF) that fuel is auxiliary.Test is carried out on the engine power meter that is connected with 2.0 liters of common rail (CR) Diesel engines.Engine is equipped with the commercial diesel oxidation catalyst (DOC) that is positioned at the close-coupled position determines the NO that produces during the filter regeneration
2Amount.
Use two kinds of dissimilar regeneration: reduce to idle regeneration (DTIR) and stable state regeneration (SSR).DTIR means by back pressure and reduces to determine after the regeneration beginning, engine is switched to idling mode, provide by the low discharge of filter and high oxygen concentration (the peak-peak temperature when causing regenerating) and assess the filter regeneration under the worst-case, promptly help in DPF, producing the situation of peak-peak temperature.SSR means and keeps 500 ℃ steady temperature at regeneration period.This regeneration is used for assessing the initial activity and the residual activity of catalyst in the carbon black burning.
Though concerning the regeneration of DTIR type, oxygen is the basic oxidant that is used for carbon black, concerning SSR, NO
2The contribution of auxiliary regeneration is significant:
C+O
2→CO，CO
2
C+NO
2→CO+NO
Testing procedure is as follows: 1) under the predetermined engine speed/load with after be injected in 600 ℃
-6The high-temperature cleaning filter reaches 30 minutes under 10 ℃ the temperature; 2) (about 200 ℃) carry out Pressure Drop Characteristicsization to filter and weigh (tolerance+0.1 gram) under warm conditions; 3) carbon black loads on predetermined speed/load and is issued to predetermined load limitations; 4) under warm conditions, filter is carried out Pressure Drop Characteristicsization and weigh; 5) regenerate according to DTIR regeneration or SSR; With 6) under warm conditions, filter is carried out Pressure Drop Characteristicsization and weigh.
DTIR regeneration is carried out by following mode: 1) switch to predetermined engine speed/load and stablize delivery temperature; 2) spray the beginning back, and through-flow parameter (mg/ stroke) increases to maximum from zero in the predetermined time interval, and target is to reach 610 ℃ ± 10 ℃ temperature at the filter inlet place; 3) keep maximum back emitted dose, keep 610 ℃ ± 10 ℃ temperature simultaneously at the filter inlet place, until moment X (definition of moment X: keep constant or begin descending in the pressure differential of striding DPF, promptly (dP (X-n)＞...＞dP (X-1)＞dP (X)) first data point of locating); 4) when moment X, make engine reduce to idling (mass flowrate is about 30 kilograms/hour); Reduce the back and spray, with 1 second interval record data, the temperature until the DPF downstream reached 200 ℃.
SSR regeneration is carried out by following mode: 1) switch to predetermined engine speed/load and stablize delivery temperature; 2) spray the beginning back, and through-flow parameter (mg/ stroke) is increased to maximum from zero in the predetermined time interval, and target is to reach predetermined 500 ℃ temperature at the filter inlet place; 3) during the predetermined time period, keep target temperature; 4) have no progeny in and spray and equilibrium temperature.
The NO of regeneration period
2Discharging is calculated by following mode:
NO
2Output=mean value (average in single test) [NO in the DPF outlet
2NO on (Grams Per Second)/DPF inlet
2(Grams Per Second)].Regeneration efficiency as the burning among the regeneration period DPF carbon black recently calculate with respect to the percentage of initial carbon black load.By DPF before regeneration and afterwards weight difference determine this amount.Carbon black load (gram) also by DPF before the carbon black load and weight difference afterwards determine.
To each specimen, regeneration efficiency is assessed as all performed regeneration mean values.Diesel particulate filter more of the present invention then and the commercial on-catalytic formula that get (no coating) DPF of conduct with reference to DPF, the DPF (ADPF) and the catalysis type DPF (CDPF) of the auxiliary regeneration of fuel additive.These samples and test data table 1 below thereof are showed to table 3.
Table 1: no coating (DPF) and fuel additive assist type (ADPF)
| Sample type | Test loop | The carbon black load |
| No coating SiC DPF (A) | 5DTIR | 3.4-12.7 grams per liter |
| No coating cordierite DPF (B) | 5DTIR | 2.6-8.1 grams per liter |
| SiC-ADPF(A10) | 12DTIR | 4.0-17.2 grams per liter |
| SiC-ADPF(B10) | 8DTIR | 4.8-13.3 grams per liter |
| SiC-ADPF(C) | 6DTIR | 3.8-14.9 grams per liter |
| SiC-ADPF(D) | 7DTIR | 4.2-12.2 grams per liter |
| SiC-ADPF(E10) | 7DTIR | 3.9-13.3 grams per liter |
Table 2: catalysis type (reference) DPF (CDPF)
| Sample type | Test loop | The carbon black load |
| Cordierite-Pt-CDPF (B) | 5DTIR | 2.2-8.3 grams per liter |
| Cordierite-Pt-CDPF (C) | 6DTIR | 2.6-10.1 grams per liter |
| Cordierite-Pt-CDPF (D) | 4DTIR | 2.4-7.2 grams per liter |
| SiC-Pt-Pd(2/1)CDPF (DE) | 3DTIR | 5.0-9.0 grams per liter |
| SiC CDPF(D) | 6DTIR | 2.3-9.6 grams per liter |
| Cordierite Pt CDPF (F) | 4DTIR | 2.2-7.2 grams per liter |
| Cordierite Pt CDPF (G) | 6DTIR | 1.1-5.7 grams per liter |
Table 3: catalysis type DPF (the present invention)
| Sample type | Test loop | The carbon black load |
| Cordierite Pt CDPF (32) | 4DTIR | 2.2-7.0 grams per liter |
| SiC Pt CDPF(55) | 4DTIR | 3.9-10.4 grams per liter |
| SiC Pt-Pd(1/2)CDPF (56) | 4DTIR | 5.0-10.9 grams per liter |
| Cordierite Pt-Pd (1/2) |
5DTIR | 2.4-8.3 grams per liter |
| Cordierite Pt-Pd (1/14) CDPF (64) | 5DTIR | 2.2-8.7 grams per liter |
| Cordierite Pd-CDPF (65) | 5DTIR | 2.8-8.6 grams per liter |
Figure 1 illustrates no coating DPF and fuel additive assist type (ADPF) filter test result at regeneration period.Can find out that regeneration period has only on a small quantity or do not have NO substantially
2The increase of generation.At regeneration period, NO
2Amount in the DPF outlet is the NO that enters DPF
2In the value 0.40-0.70 of amount (having only two exceptions), mean value is approximately 0.60.
On the contrary, as shown in Figure 2, during the catalysis type DPF filter regeneration that commerce is made, there is significant NO
2The increase of amount, the NO at the filter outlet place
2Content exceeds about 30-90% than filter inlet place usually.Also can find out, add Pd can't reduce regeneration period to Pt emission of nitrogen oxide amount in the carbon monoxide-olefin polymeric.
As shown in Figure 3, by the CDPF sample of prior art for preparing in the average regeneration efficiency of DTIR regeneration period usually in the 80-90% mass percent.
The result of Fig. 2 shows, compares the NO that produces during the existing catalysis type dpf regeneration with on-catalytic formula and fuel assist type DPF
2Discharging is unacceptable.
Fig. 4 is illustrated in the catalyst activity of the CDPF of the reference during the carbon black burning of measuring during the stable state regeneration (500 ℃ following 20 minutes) in addition, and with it as overall rate constants k 0 (global rate constant) assessment, this makes by using following model:
1. the desirable isothermal reactor that stirs
The A Leiniwusi correlation of speed constant (Arrhenius dependence): k (T)=
k0*T*exp(-Ea/T)
3. reaction rate: r (T)=k (T) * M
m* 0 °, wherein
R=reaction rate [gram carbon black/L DPF/ second]
The absolute temperature of T=DPF porch [K]
The average carbon black load of M=[gram carbon black/L DPF]
The dynamics progression [-] of m=carbon black
O=oxygen flow [Grams Per Second]
The dynamics progression [-] of o=oxygen
Ea=activation energy [K]
K0=pre-exponential factor ≡ overall situation speed constant
Should notice that higher K0 reflects higher catalyst activity during the carbon black burning.
Use following step to assess the correlation of average carbon black load with respect to experimental period:
1) measures initial carbon black load by weighing
2) measure final carbon black load by weighing
3) use is to pressure drop interpolation between initial and final carbon black load of exhaust volume flow rate and temperature standardization.
By with k0 as adjusting parameter, above-mentioned model of match and experiment measuring to data calculate k0.
It should be noted that and compare by the burn idle regeneration (600 ℃) of reducing to of carbon black of oxygen basically, because lower temperature (500 ℃), these stable states regeneration more are NO
2Auxiliary regeneration.
CDPF sample according to the present invention is at the NO of regeneration period
2Generation as shown in Figure 5.Can see having the CDPF of the noble metal load in the 5-15 gram/cubic feet scope, average N O
2Generation is 0.59, the value that promptly very approaching no coating and fuel additive assist type DPF observe.Therefore, use carbon monoxide-olefin polymeric of the present invention can cause existing on the DPF NO
2The minimizing of amount, that is, and the NO of regeneration period DPF outlet
2The amount average specific enters the NO of DPF
2Amount low 40%.
As shown in Figure 5, the sample that is added with Co oxide or Co-Fe oxide produces lower level NO
2Discharging.For only containing Pd or containing the sample 64 and the sample 65 of Pd-Pt (having only the only very low Pt load of 1 gram/cubic feet), NO
2Discharge value only is 0.4 and is lower than the emission level of on-catalytic formula DPF and fuel additive formula DPF filter.
Use shown in Figure 6 CDPF of the present invention reduces to the average regeneration efficiency of idling (DTIR).Can find out that regeneration efficiency is in the 80-100% mass percent.Filter 64 and 65 (have low-down Pt (#64) and do not contain Pt (#65) fully) for based on Pd observes high regeneration efficiency.Because the price of Pt surpasses four times of the Pd price usually, because the low NO during lower cost, high regeneration efficiency and the dpf regeneration
2Discharging, such carbon monoxide-olefin polymeric based on Pd is optimal.
In Fig. 7, show CDPF of the present invention aflame catalyst activity of carbon black under limit (500 ℃/20 minutes), it is assessed as overall rate constants k 0.Can expect, for such NO
2Assist type regeneration is because NO
2The low activity that forms, activity should substandard CDPF.Yet, find that unexpectedly filter #63 can also compare with most standard CDPF after the regeneration many times with filter #64.It should be noted that the activity of fresh sample more as shown in Figure 7 and aging sample, the activity of filter # 63 and filter # 64 is improved after a series of regeneration, as shown in Figure 7.This shows that carbon monoxide-olefin polymeric of the present invention has high heat stability.
Though some representational embodiment and details show for explaining purpose of the present invention, and those skilled in the art be it is evident that and can make variation and not depart from scope of the present invention several different methods disclosed herein and device.Scope of the present invention is defined by claim.
Claims (26)
1. one kind is used for the carbon monoxide-olefin polymeric that diesel particulate filter helps the carbon black oxidation, and described carbon monoxide-olefin polymeric comprises:
Comprise from Pt Pd, Pt-Pd, or the catalytic metal of the platinum group metal of its combination selection;
The reactive metal oxides composition that comprises Cu and La; With
From the Co oxide, Fe oxide, or the oxide components of its combination selection.
2. carbon monoxide-olefin polymeric as claimed in claim 1 is characterized in that the load of described platinum group metal is less than 20g/ft
3
3. carbon monoxide-olefin polymeric as claimed in claim 1 is characterized in that, described platinum group metal loads on 5 to 15g/ft
3Between.
4. carbon monoxide-olefin polymeric as claimed in claim 1 is characterized in that described catalytic metal only comprises palladium.
5. carbon monoxide-olefin polymeric as claimed in claim 1 is characterized in that, described reactive metal oxides composition comprises CuO-La
2CuO
4
6. carbon monoxide-olefin polymeric as claimed in claim 1 is characterized in that, described Co oxide components comprises Co
3O
4
7. carbon monoxide-olefin polymeric as claimed in claim 1 is characterized in that, described Fe oxide components comprises Fe
2O
3
8. carbon monoxide-olefin polymeric as claimed in claim 1 also comprises from aluminium oxide, silica, the carrier that zirconia and its combination are selected.
9. carbon monoxide-olefin polymeric as claimed in claim 8 is characterized in that, described carrier is by lanthanum, zirconium, aluminium or its combinative stability.
10. a method that is provided for the carbon monoxide-olefin polymeric of diesel particulate filter comprises
Diesel particulate filter is provided;
With from alumina sol, silicon dioxide gel, the sol solution that zirconia sol and its combination are selected floods described filter;
Flood described filter with stabilizing solution; And
With the described filter of a kind of solution impregnation, described solution comprises the metal oxide precursor of selecting from copper nitrate, lanthanum nitrate and its mixing; From ferric nitrate, cobalt nitrate or its close and mix the oxide precursor of selecting; With from silver nitrate, palladium nitrate, the catalytic metal precursor that chloroplatinic acid dihydro and its combination is selected.
11. method as claimed in claim 10 is included in the described sol solution of dipping, floods described stabilizing solution, after dipping comprises the described solution of described metal oxide precursor and described catalytic metal precursor, and the dry and described filter of calcining.
12. method as claimed in claim 10 is characterized in that, described sol solution comprises also that from sucrose glycerine or its close and mix the organic compound of selecting.
Described stabilizing solution comprises the acetic acid zirconium, lanthanum nitrate or its combination 13. method as claimed in claim 10 is characterized in that, described sol solution comprises alumina sol.
Described stabilizing solution comprises the acetic acid zirconium, aluminum nitrate or its combination 14. method as claimed in claim 10 is characterized in that, described sol solution comprises silicon dioxide gel.
Described stabilizing solution comprises lanthanum nitrate 15. method as claimed in claim 10 is characterized in that, described sol solution comprises zirconia sol.
16. the diesel particulate filter that applies as method as described in the claim 10.
17. the diesel exhaust gas treatment system comprises:
Reception is from the diesel particulate filter of Diesel engine diesel exhaust gas; With
Be coated in the carbon monoxide-olefin polymeric on the described filter, described carbon monoxide-olefin polymeric comprises and comprising from Pt, Pd, Pt-Pd, or the catalytic metal of the platinum group metal of its combination selection; The reactive metal oxides that comprises Cu and La; With from the Co oxide, Fe oxide, or the oxide components selected of its combination.
18. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, the described platinum group metal load in the described carbon monoxide-olefin polymeric is less than 20g/ft
3
19. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, described platinum group metal loads on 5 to 15g/ft
3Between.
20. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, described carbon monoxide-olefin polymeric also comprises from aluminium oxide, silica, the carrier that zirconia or its combination are selected.
21. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, described reactive metal oxides composition comprises CuO-La
2CuO
4
22. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, the carbon black that described carbon monoxide-olefin polymeric helps oxidation to capture on described filter between the temperature of 550 ℃ and 600 ℃.
23. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, described carbon monoxide-olefin polymeric helps 60% to 100% in the carbon black that oxidation captures on described filter.
24. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, during comprising the diesel particulate filter regeneration of described carbon monoxide-olefin polymeric, and the NO of generation
2Amount be between 0.40 to 0.70.
25. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, during comprising the diesel particulate filter regeneration of described carbon monoxide-olefin polymeric, and the NO of generation
2Amount be 0.60.
26. diesel exhaust gas treatment system as claimed in claim 17 is characterized in that, during comprising the diesel particulate filter regeneration of described carbon monoxide-olefin polymeric, and the NO of generation
2Amount be 0.40.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06115850.7A EP1837076B1 (en) | 2006-03-20 | 2006-06-22 | Diesel particulate filter catalyst with low no2 emissions |
| EP06115850.7 | 2006-06-22 |
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| Publication Number | Publication Date |
|---|---|
| CN101091916A true CN101091916A (en) | 2007-12-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101265029A Pending CN101091916A (en) | 2006-06-22 | 2007-06-22 | Catalyst composition for diesel particulate filter |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101564646B (en) * | 2008-04-22 | 2012-11-14 | 赫多特普索化工设备公司 | Method for purification of an exhaust gas from a diesel engine |
| CN103328098A (en) * | 2010-11-02 | 2013-09-25 | 赫多特普索化工设备公司 | Method for the preparation of a catalysed particulate filter and catalysed particulate filter |
| CN108087071A (en) * | 2017-12-05 | 2018-05-29 | 南京依柯卡特排放技术股份有限公司 | To the determination methods of DPF carbon carrying capacity |
| CN109225239A (en) * | 2018-09-03 | 2019-01-18 | 金华职业技术学院 | CO oxidation catalyst and preparation method thereof under a kind of steam and carbon dioxide atmosphere |
| CN109225210A (en) * | 2018-09-30 | 2019-01-18 | 中自环保科技股份有限公司 | A kind of low noble metal diesel vehicle oxidation catalyst preparation method and its catalyst of preparation |
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2007
- 2007-06-22 CN CNA2007101265029A patent/CN101091916A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101564646B (en) * | 2008-04-22 | 2012-11-14 | 赫多特普索化工设备公司 | Method for purification of an exhaust gas from a diesel engine |
| CN103328098A (en) * | 2010-11-02 | 2013-09-25 | 赫多特普索化工设备公司 | Method for the preparation of a catalysed particulate filter and catalysed particulate filter |
| CN103328098B (en) * | 2010-11-02 | 2015-06-17 | 赫多特普索化工设备公司 | Method for the preparation of a catalysed particulate filter and catalysed particulate filter |
| US9339844B2 (en) | 2010-11-02 | 2016-05-17 | Haldor Topsoe A/S | Method for the preparation of a catalysed particulate filter and catalysed particulate filter |
| CN108087071A (en) * | 2017-12-05 | 2018-05-29 | 南京依柯卡特排放技术股份有限公司 | To the determination methods of DPF carbon carrying capacity |
| CN108087071B (en) * | 2017-12-05 | 2021-09-28 | 南京依柯卡特排放技术股份有限公司 | Method for judging carbon loading of DPF |
| CN109225239A (en) * | 2018-09-03 | 2019-01-18 | 金华职业技术学院 | CO oxidation catalyst and preparation method thereof under a kind of steam and carbon dioxide atmosphere |
| CN109225210A (en) * | 2018-09-30 | 2019-01-18 | 中自环保科技股份有限公司 | A kind of low noble metal diesel vehicle oxidation catalyst preparation method and its catalyst of preparation |
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