WO2011125050A1 - Catalyseur à zéolithes mixtes fe-bea/fe-mfi et procédé de traitement de nox dans des courants gazeux à l'aide de ce catalyseur - Google Patents

Catalyseur à zéolithes mixtes fe-bea/fe-mfi et procédé de traitement de nox dans des courants gazeux à l'aide de ce catalyseur Download PDF

Info

Publication number
WO2011125050A1
WO2011125050A1 PCT/IB2011/051526 IB2011051526W WO2011125050A1 WO 2011125050 A1 WO2011125050 A1 WO 2011125050A1 IB 2011051526 W IB2011051526 W IB 2011051526W WO 2011125050 A1 WO2011125050 A1 WO 2011125050A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
zeolites
exhaust gas
bea
structure type
Prior art date
Application number
PCT/IB2011/051526
Other languages
English (en)
Inventor
Susanne Stiebels
Claudia Wendt
Torsten Neubauer
Edith Schneider
Original Assignee
Basf Se
Basf China Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se, Basf China Company Limited filed Critical Basf Se
Priority to CA2795522A priority Critical patent/CA2795522A1/fr
Priority to CN2011800268611A priority patent/CN102958610A/zh
Priority to EP11765158.8A priority patent/EP2555867A4/fr
Priority to BR112012025744A priority patent/BR112012025744A2/pt
Priority to KR1020127029118A priority patent/KR20130091638A/ko
Priority to JP2013503212A priority patent/JP2013523442A/ja
Priority to MX2012011540A priority patent/MX2012011540A/es
Publication of WO2011125050A1 publication Critical patent/WO2011125050A1/fr
Priority to ZA2012/08258A priority patent/ZA201208258B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7215—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9205—Porosity

Definitions

  • the present invention relates to a catalyst which is preferably for use in selective catalytic reduction (SCR), as well as to an exhaust gas treatment system comprising said catalyst, and to a process for the treatment of a gas stream comprising NO x .
  • SCR selective catalytic reduction
  • the present invention is concerned with a method of catalyzing the reduction of nitrogen oxides, and espe- 10 cially with the selective reduction of nitrogen oxides with ammonia in the presence of oxygen, using metal-promoted zeolite catalysts.
  • the emissions present in the exhaust gas of a motor vehicle can be divided into two groups.
  • primary emission refers to pollutant gases which form directly through the combustion process of the fuel in the engine and are already present in the untreated emission before it passes through an exhaust gas treatment system.
  • Secondary emission refers to those pollutant gases which can form as by-products in the exhaust gas treatment system.
  • the exhaust gas of lean engines comprises, as well as the customary primary emissions of carbon monoxide CO, hydrocarbons HC and nitrogen oxides NO x , a relatively high oxygen content of up to 15% by volume.
  • the customary primary emissions of carbon monoxide CO, hydrocarbons HC and nitrogen oxides NO x a relatively high oxygen content of up to 15% by volume.
  • NSCs nitrogen oxide storage catalysts
  • SCR selective catalytic reduction
  • the cleaning action of nitrogen oxide storage catalysts is based on the nitrogen oxides being stored in a lean operating phase of the engine by the storage material of the storage catalyst, L0 predominantly in the form of nitrates.
  • the catalyst has to be regenerated in a subsequent rich operating phase of the engine. This means that the nitrates formed beforehand are decomposed and the nitrogen oxides released again are reacted with the reducing exhaust gas components over the storage catalyst to give nitrogen, carbon dioxide and water.
  • the alternative SCR method is preferably used for denitrification of diesel motor vehicle exhaust 10 gases.
  • this method according to the engine design and construction of the exhaust gas system, a distinction is made between “active” and “passive” SCR methods, “passive” SCR methods involving use of ammonia secondary emissions generated deliberately in the exhaust gas system as a reducing agent for denitrification.
  • U.S. Pat. No. 6,345,496 B1 describes a method for cleaning engine exhaust gases, in which repeatedly alternating lean and rich air/fuel mixtures are established and the exhaust gas thus produced is passed through an exhaust gas system which comprises, on the inflow side, a catalyst which converts NO x to NH 3 only under rich exhaust gas conditions, while a further catalyst arranged on the outflow side adsorbs or stores NO x in the lean ex-
  • an NH 3 adsorption and oxidation catalyst may be arranged on the outflow side, which stores NH 3 under rich conditions, desorbs it under lean conditions and oxidizes it with oxygen to give nitrogen and water. Further disclosures of such methods are known. Like the use of the nitrogen oxide storage catalysts, however, such "passive" SCR methods have the disadvantage that one of their essential constituents is the provision of rich exhaust gas con- 5 ditions, which are generally required for in situ generation of ammonia as a reducing agent.
  • the reducing agent is metered into the exhaust gas Sine from an addition tank carried in the vehicle by means of an injection nozzle.
  • a reducing agent used may, apart from ammonia, also be a compound readily decomposable to
  • L0 ammonia for example urea or ammonium carbamate.
  • Ammonia has to be supplied to the exhaust gas at !east in a stoichiometric ratio relative to the nitrogen oxides. Owing to the greatly varying operation conditions of the motor vehicles, the exact metered addition of the ammonia is not straightforward. This leads in some cases to considerable ammonia breakthroughs downstream of the SCR catalyst. To prevent secondary ammonia emission, an oxi-
  • L 5 dation catalyst is usually arranged downstream of the SCR catalyst, which is intended to oxidize ammonia which breaks through to nitrogen.
  • Such a catalyst is referred to hereinafter as an ammonia slip catalyst.
  • oxidation catalyst-containing coating serves to lower the activation energy for oxygen-based particulate burnoff (soot combustion) and hence to lower the soot ignition temperature on the filter, to improve the passive regeneration performance by oxidation of nitrogen monoxide present in the exhaust gas to nitrogen dioxide, and to suppress breakthroughs of 5 hydrocarbon and carbon monoxide emissions.
  • WO 99/39809 describes an exhaust aftertreatment system wherein an oxidation catalyst for oxidation of NO in NO x to N0 2 , a particulate filter, a metering unit for a reducing agent and an SCR catalyst follow on each other.
  • an additional ammonia slip catalyst is generally required downstream of the SCR cata!yst, and continues the series of cataiysts on the outflow side of the SCR catalyst.
  • Zeolites are aluminosilicate crystalline materials having rather uniform pore sizes which, depending upon the type of zeolite and the type and amount of cations included in the zeolite lattice, may range from about 3 to 10 angstroms in diameter.
  • EP 1 961 933 A1 relates to a diesel particulate filter for treating exhaust gas comprising a filter body having provided thereon an oxidation catalyst coating, an SCR-active coating, and an ammonia storage material.
  • zeo- iites selected from beta zeolite, Y-zeoiite, faujasite, mordenite and ZSM-5 which may be exchanged with iron or copper.
  • EP 1 147 801 A1 relates to a process for reducing nitrogen oxides present in a lean exhaust gas from an internal combustion engine by SCR using ammonia, wherein the reduction catalyst preferably contains ZSM-5 zeolite exchanged with copper or iron.
  • Said document further concerns an SCR catalyst having a honeycomb substrate and deposited thereon a coating containing ZSM-5 zeolite exchanged with iron.
  • EP 2 123 614 A2 for its part concerns a honeycomb structure containing zeolites and an inor- ganic binder.
  • a first zeolite included in said structure is ion-exchange with a metal including Cu, Mn, Ag, and V
  • a second zeolite is further included which is exchanged with a metal including Fe, Ti, and Co.
  • zeolites used for the first and second zeolite these include zeolite beta, zeolite Y, ferrierite, ZSM-5 zeolite, mordenite, faujasite, zeolite A, and zeolite L.
  • US 7,332, 148 B2 describes a stabilized aluminosilicate zeolite containing copper or iron, wherein the stabilized zeolite includes ZSM-5, ZSM-8, ZSM-1 1 , ZSM-12, zeoiite X, zeolite Y, zeolite beta, mordenite, and erionite.
  • the prior art relates an awareness of the utility of metai-promoted zeolite catalysts including, among others, iron-promoted and copper-promoted zeolite catalysts, in particular for the selective catalytic reduction of nitrogen oxides with ammonia.
  • the NEDC As opposed to the old European driving cycle (ECE-15) driving cycle, a particular feature of the NEDC is that it integrates a so-called extra-urban driving cycle, such that testing may better represent the typical usage of a car in Europe, and, accordingly, the typical emission pattern linked thereto. More specifically, in the NEDC, the old European driving cycle ECE-15 is performed in the time period of 0 to 800 seconds, after which the extra-urban driving cycle is conducted in the time period up to 1200 seconds.
  • an improved catalyst may be provided.
  • a catalyst comprising zeolites of both the MFI and of the BEA structure type, wherein both the MFI-and BEA-type zeolites respectively contain iron, display clearly im- proved catalytic properties, in particular when used in SCR applications.
  • the present invention relates to a catalyst, preferably for use in selective catalytic reduction (SCR), said catalyst comprising
  • At least part of the one or more zeolites of the MFI structure type and at least part of the one or more zeolites of the BEA structure type respectively contain iron (Fe).
  • SCR selective caiatytic reduction
  • reductant any catalytic process involving the reaction of nitrogen oxides NO x with a reductant.
  • SCR refers to reduction reactions, wherein NO x is transformed to a reduction product thereof, which is preferably N 2 .
  • reductant said term refers to any suitable reducing agent for the SCR process, wherein preferably ammonia and/or any ammonia precursor such as urea and/or. ammonium carbamate is preferred, urea being preferably comprised in the ammonia precursor. Even more preferably, the term “reductant” refers to ammonia.
  • reductant may, however, further include hydrocarbons and/or hydrocarbon derivatives such as oxygenated hydrocarbons, such as for example those which may be found in motor vehicle fuels and/or in motor vehicle exhaust gas, in particular in diesel fuel and/or diesel exhaust gas.
  • hydrocarbons and/or hydrocarbon derivatives such as oxygenated hydrocarbons, such as for example those which may be found in motor vehicle fuels and/or in motor vehicle exhaust gas, in particular in diesel fuel and/or diesel exhaust gas.
  • any conceivable zeolite of the MFI or of the BEA structure type may be used, respectively, provided that it displays the typical structural characteristics of that structure-type.
  • these may for example comprise one or more zeolites selected from the group consisting of ZSM-5, [As- Si-0]-MFI, [Fe-Si-OI-MFI, [Ga-Si-0]-MFI , AMS-1 B, AZ-1 , Bor-C, Boralite C, Enciiite, FZ-1 , LZ-105, Monoclinic H-ZSM-5, Mutinaite, NU-4, NU-5, Silicaiite, TS-1 , TSZ, TSZ-I I I, TZ-01 , USC-4, USI-108, ZBH, ZKQ-1 B, ZMQ-TB, organic-free ZSM-5, and mixtures of two or more thereof.
  • ZSM-5 ZSM-5
  • [As- Si-0]-MFI [Fe-S
  • these may comprise one or more 5 zeolites selected from the group consisting of, Beta,
  • the one or more zeolites of the BEA structure type include zeolite Beta.
  • the one or more zeolites of the MFI structure type include ZSM-5 and the one or more zeolites of the BEA structure type include zeolite Beta, wherein according to particularly preferred embodiments, the one or more zeolites of the MFI structure type is ZSM-5 and the one or more zeolites of the BEA structure type is zeolite Beta.
  • At least part of the one or more MFI-type zeolites and at least part of the one or more BEA-type zeolites respectively contain iron .
  • iron contained in at least part of the one or more MFI-type zeolites and at least part of the one or more BEA-type zeolites said metal may respectively be contained 0 therein in any conceivable fashion and in any conceivable state.
  • iron displays a positive state of oxidation in the respective zeolite.
  • iron may be contained on the zeolite surface and/or within the por-
  • iron may be included in the zeolite framework, for example by isomorphous substitution. According to preferred embodiments, the iron is supported on the respective zeolite surface and/or within the porous structure thereof, and even more preferably both on the respective zeolite surface and within
  • iron is respectively contained in at least part of the one or more zeolites of the MFI and BEA structure type in a positive oxidation state, wherein said iron is supported on the surface of the respective zeolite, including being contained within the porous structure thereof.
  • the catalyst according to the present invention may comprise the one or more zeolites of the 5 MFI structure type and the one or more zeolites of the BEA structure type in any conceivable weight ratio, wherein it is preferred that the weight ratio of the one or more zeolites of the MFI structure type relative to the one or more zeolites of the BEA structure type ranges from 1 : 1 0 to 10 : 1 , more preferably from 1 : 5 to 5 : 1 , more preferably form 1 : 2 to 2 : 1 , more preferably from 0.7 : 1 to 1 : 0.7, more preferably from 0.8 : 1 to 1 : 0.8, and even more preferably L0 from 0.9 : 1 to 1 : 0.9.
  • the weight ratio of the MFI-type zeolites to the BEA-type zeolites is approximately 1 : 1 .
  • the one or more zeolites of the MFI L 5 structure type and/or the one or more zeolites of the BEA structure type respectively comprise both Al and Si in their frameworks, wherein it is more preferred that both the zeolites of the MFI structure type and the zeolites of the BEA structure type respectively comprise both Al and Si in their frameworks.
  • zeolites comprise both Al and Si in their respective frameworks
  • said zeolites may in principle display any possible ratio of Al to Si.
  • the molar ratio of silica to alumina (SAR) in the one or more zeolites of the MFI structure type ranges from 5 to 1 50, more preferably from 1 5 to 100, more preferably from 20 to 50, more preferably from 23 to 30, and even more preferably from 25 to 27.
  • SAR silica to alumina
  • the SAR in the one or more zeolites of the BEA structure type ranges from 5 to 150, preferably from 20 to 100, more preferably from 30 to 70, more preferably from 35 to 45, and even more preferably from 38 to 42.
  • the SAR in the one or more MFI-type zeolites ranges from 5 to 150
  • the one or more BEA-type zeolites ranges from 5 to 150, more preferably
  • the one or more BEA-type zeolites ranges from 20 to 100, more preferably that the SAR in the one or more MFI-type zeolites ranges from 20 to 50, and the one or more BEA-type zeolites ranges from 30 to 70, more preferably that the SAR in the one or more MFi-type zeolites ranges from 23 to 30, and the one or more BEA-type zeolites ranges from 35 to 45, and even more preferably
  • the amount of iron (Fe) in the one or more zeolites of the MFI structure type is comprised in the range of from 0, 1 to 1 5 wt.-% based on the weight of said one or more zeolites of the MFI structure type, wherein more preferably the amount of Fe ranges from 0.5 to 10 wt.-%, more preferably from 1 .0 to 7.0 wt.-%, more preferably from 2.5 to 5.5 wt.-%, more preferably from 3.5 to 4.2 wt.-%, and even more
  • the amount of iron (Fe) in the one or more zeolites of the BEA structure type ranges from 0.05 to 10 wt.-% based on the weight of said one or more zeolites of the BEA structure type, wherein more preferably the amount of Fe ranges from 0.1 to 5 wt.-%, more preferably from 0.5 to 2 wt.-%, and even more preferably from 1 .0 to 1 .6 wt.-%.
  • Fe iron
  • the amount of iron in the one or more MFI- type zeolites ranges from 0.1 to 15 wt.-%
  • the amount of iron in the one or more BEA-type zeolites ranges from 0.05 to 1 0 wt.-%, wherein more preferably the amount of iron in the one or more MFI-type zeolites ranges from 1 .0 to 7.0 wt.-%
  • the amount of iron in the one or more BEA-type zeolites ranges from 0.1 to 5 wt.-%, more preferably the amount of iron in the
  • one or more MFi-type zeolites ranges from 2.5 to 5.5 wt.-%, and the amount of iron in the one or more BEA-type zeolites ranges from 0.5 to 2 wt.-%, more preferably the amount of iron in the one or more MFi-type zeolites ranges from 3.5 to 4.2 wt.-%, and the amount of iron in the one or more BEA-type zeolites ranges from 0.5 to 2 wt.-%, and even more preferably, the amount of iron in the one or more MFI-type zeolites ranges from 3.7 to 4.0 wt.-%, and the amount of iron in the one or more BEA-type zeolites ranges from 1 .0 to 1 .6 wt.-%.
  • the catalyst may be provided in any conceivable form, such as by way of example in the form of a powder, a granulate, or a monolith.
  • the catalyst further comprises a substrate, onto which the one or more zeolites are provided.
  • the substrate can be made from materials commonly known in the art.
  • porous materials are preferably used as the substrate ma-
  • L0 terial in particular ceramic and ceramic-like materials such as cordierite, a-alumina, an alumi- nosilicate, cordierite-alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mul- lite, zircon, zircon mullite, zircon silicate, sillimanite, a magnesium silicate, petalite, spodu- mene, alumina-silica-magnesia and zirconium silicate, as well as porous refractory metals and oxides thereof.
  • "refractory metal” refers to one or more
  • the substrate may also be formed of ceramic fiber composite materials. According to the present invention, the substrate is preferably formed from cordierite, silicon carbide, and/or from aluminum titanate, and even more preferably from cordierite and/or silicon carbide.
  • the substrates useful for the catalysts of embodiments of the present invention may also be metallic in nature and be composed of one or more metals or metal alloys.
  • the metallic substrates may be employed in various shapes such as corrugated sheet or monolithic form.
  • Suitable metallic supports include the heat resistant metals and metal ailoys such as titanium and stainless steel as well as other alloys in which iron is a substantial or major component.
  • Such ailoys may contain one or more of nickel, chromium and/or aluminum, and the total amount of these metals may advantageously comprise at least 15 wt,-% of the alloy, e.g. , 10- 25 wt.-% of chromium, 3-8 wt.-% of aluminum and up to 20 wt.-% of nickel.
  • the alloys may also contain small or trace amounts of one or more other metals such as manganese, copper, vanadium, titanium and the like.
  • the surface or the metai substrates may be oxidized at high
  • the substrate according to the present invention may be of any conceivable shape, provided that it allows for the fluid contact with at least a portion of the respective one or more zeolites of the MFI and BEA structure types present thereon.
  • the substrate is a monolith, wherein more preferably the mono!iih is a flow-through monolith.
  • Suitable 5 substrates include any of those materials typically used for preparing catalysts, and will usually comprise a ceramic or metal honeycomb structure.
  • the monolithic substrate contains fine, parallel gas flow passages extending from an inlet to an outlet face of the substrate, such that passages are open to fluid flow (referred to as honeycomb flow through substrates).
  • honeycomb flow through substrates The passages, which are essentially straight paths from their fluid inlet to their fluid
  • L0 outlet are defined by walls onto which the one or more zeolites of the MFI and BEA structure types are respectively disposed, so that the gases flowing through the passages may contact them.
  • the flow passages of the monolithic substrate are thin-walled channels, which can be of any suitable cross-sectional shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, or circular.
  • Such structures may contain up to 900 gas inlet openings
  • L5 i.e., cells
  • structures preferably have from 50 to 600 openings per square inch, more preferably from 300 to 500, and even more preferably from 350 to 400.
  • the catalyst comprises a 20 substrate which is a monolith, and preferably a honeycomb substrate.
  • the substrate is a wail flow monolith.
  • the substrate is preferably a honeycomb wall flow filter, wound or packed fiber filter, open-cell foam, or sintered metal filter, wherein wall flow fil-
  • useful wall flow substrates have a plurality of fine, substantially parallel gas flow passages extending along the longitudinal axis of the substrate. Typically, each passage is blocked at one end of the substrate body, with alternate passages blocked at opposite end-faces.
  • Particularly preferred wall flow substrates for use in the present invention include thin porous walled honey-
  • Ceramic wall flow substrates used in the present invention are preferably formed of a material having a porosity of at least 40%, pre- ferably from 40 to 70%, and having a mean pore size of af least 5 microns, preferably from 5 to 30 microns. Further preferred are substrates having a porosity of at least 50% and having a mean pore size of at least 10 microns.
  • the substrate preferably comprised in the catalyst is preferably selected from the group consisting of flow-through substrates and wall-flow substrates, more preferably from the group consisting of cordierite f!ow-through substrates and wall-flow substrates, and silicon carbide flow-through substrates and wall-flow substrates.
  • the zeolites may be provided thereon in any conceivable fashion, wherein they are preferably provided thereon in the form of one or more layers which are preferably washcoat layers.
  • the catalyst comprises a substrate and two or more layers provided thereon
  • the zeolites may be provided in said two or more layers in any possible manner.
  • the present invention includes, for example, such preferred embodiments wherein the zeolites are contained in only a single of the two or more layers, as well as embodiments wherein the zeolite is contained in more than one of the two or more layers.
  • the zeolites are contained in a single layer, irrespective of the number of layers present on the substrate.
  • the catalyst comprises a substrate
  • the catalyst comprises one or more layers, preferably washcoat layers, provided on the substrate, the zeolites being contained in one single layer or two or more separate layers, wherein preferably the zeolites are contained in one single layer.
  • the zeolites are contained in more than one of said layers
  • the MFI- and BEA-type zeolites are respectively contained in each of the layers which contain zeolites, or that, alternatively, only part of the layers containing zeolites contain both MFI- and BEA-type zeolites.
  • no single layer contains both MFI- and BEA-type zeolites, -said zeolites being accordingly contained in separate layers of the catalyst.
  • at ieast one of the layers in such embodiments contains both MFi- and BEA-type zeolites, wherein it is even more preferred that each of the two or more layers of said embodiments containing the zeolites also contains both the MFI- and BEA-type zeolites.
  • the one or more zeolites of the MFI and of the BEA structure type may be respectively present in the catalyst in any conceivable amount, provided that an improved catalyst according to the present invention may be obtained.
  • either the one or more zeolites of the MFI structure type, or the one or more zeolites of the BEA structure type, or both the one or more zeolites of the MFi structure type and the one or more zeolites of the BEA structure type may respectively be present in the catalyst in a loading ranging from 0.1 to 5.0 g/in 3 , wherein their loading preferably ranges from 0.7 to 2.0 g/in 3 , more preferably from 1 .0 to 1 .7 g/in 3 , more preferably from 1 .1 5 to 1.55 g/in 3 , more preferably from 1 .25 to 1 .45 g/in 3 , more preferably from 1 .32 to 1 .38 g/in 3 , and even more preferably from 1 .34 to 1 ,36 g/in 3 .
  • the respective loadings of the MFI- and BEA-type zeolites may be independent from one another, in the sense that the preferred loading ranges may apply either to the MFi- or to the BEA-type zeolites, wherein the loading of the one or more zeolites belonging to the other structure type is respectively not particularly limited, and may therefore be present in any loading, or may be limited to a different range of loadings.
  • the present invention also comprises embodiments wherein, for example, the loading of the MF!-type zeolites ranges from 0.1 to 5.0 g/in 3 , and the loading of the BEA-type zeolites ranges from 1 .34 to 1 .36 g/in 3 , or embodiments wherein, for example, the loading of the MFI-type zeolites ranges from 0.7 to 2.0 g/in 3 , and the loading of the BEA-type zeolites ranges from 1 .32 to 1 .38 g/in 3 , or embodiments wherein, for example, the loading of the MFI-type zeolites ranges from 1 .0 to 1 .7 g/in 3 , and the loading of the BEA-type zeolites ranges from 1 .25 to 1 .45 g/in 3 , or embodiments wherein, for example, the loading of the MFI-type zeolites ranges from 1 .15 to 1 .55 g/in 3 , and
  • the present invention also relates to a treatment system for an exhaust gas stream.
  • the treatment system of the present invention comprises an internal combustion engine which is preferably a lean burn engine, and even more preferably a diesel engine.
  • an internal combustion engine which is preferably a lean burn engine, and even more preferably a diesel engine.
  • the treatment system according to the present invention comprises an exhaust gas conduit which is in fluid communication with the interna! combustion engine.
  • any conceivable conduit may be used, provided that it is capable of conducting exhaust gas from an internal combustion engine, and may sufficiently resist the temperatures and the chemical species encountered in the exhaust gas of an internal combustion engine, in particular of a lean burn engine such as a diesel engine.
  • the fluid communication provided between the exhaust gas conduit and the internal combus- tion engine signifies that the treatment system allows for the constant passage of exhaust gas from the engine to the conduit.
  • the catalyst is present in the exhaust gas conduit.
  • the catalyst may be provided in the exhaust gas conduit in any conceivable fashion, provided that it is present within the exhaust gas conduit in the sense that it may be contacted by the exhaust gas passing through said conduit.
  • the catalyst is provided in the exhaust gas conduit on a substrate as outlined in the present application, and in particular on a honeycomb substrate, which is preferably either a flow-through or a wall-flow honeycomb substrate.
  • the present invention also relates to an exhaust gas treatment system comprising an internal combustion engine and an exhaust gas conduit in fluid communication with the inter- nal combustion engine, wherein the catalyst according to the present invention is present in the exhaust gas conduit, and wherein the internal combustion engine is preferably a lean burn engine, and more preferably a diesel engine.
  • the present invention also relates to embodiments wherein the inventive catalyst is comprised in an exhaust gas treatment system comprising an internal combustion engine and an exhaust gas conduit in fluid communication with the internal combustion engine, wherein said catalyst is present in the exhaust gas conduit, and wherein the internal combustion engine is preferably a lean burn engine, and more preferably L 0 a diesel engine.
  • the exhaust gas treatment system further comprises a means of introducing a reductant into the exhaust gas stream, wherein said means is located upstream from the inventive MFi/BEA-zeolite catalyst.
  • a means of introducing a reductant into the exhaust gas stream wherein said means is located upstream from the inventive MFi/BEA-zeolite catalyst.
  • L 5 is preferred that a means of introducing ammonia and/or urea into the exhaust gas conduit is provided.
  • any means known to the skilled person may be provided, in particular those commonly applied to exhaust gas treatment systems operating with active SCR methods necessitating the direct introduction of said reductants.
  • the reductant which preferabiy comprises ammonia and/or urea is intro-
  • the exhaust gas treatment system may suitably further comprise any further components for the effective treatment of an exhaust gas.
  • said system preferably further comprises an oxidation catalyst or a catalyzed soot filter (CSF) or both an oxidation catalyst and a CSF.
  • the oxidation catalyst and/or the CSF are aiso present within the exhaust gas conduit.
  • the CSF of the present invention preferably comprises a substrate coated with a washcoat layer containing one or more catalysts for burning off trapped soot and/or oxidizing exhaust gas stream emissions.
  • the soot burning catalyst can be any known catalyst for combustion of soot.
  • the CSF can be coated with a one or more high surface area refractory oxides (such as e.g. alumina, silica, silica alumina, zirconia, and zirconia alumina) and/or with an oxidation catalyst (such as e.g.
  • the soot burning catalyst is an oxidation catalyst comprising one or more precious metal catalysts, said one or more precious metal catalysts preferably comprising one or more metals selected from the group consisting of platinum, palladium, and rhodium.
  • any oxidation catalyst may be used to this effect which is suitable for oxidizing unburned hydrocarbons, CO, and/or NO* comprised in the exhaust gas.
  • oxidation catalysts are preferred which comprise one or more precious metal catalysts, and more preferably one or more precious metals selected from the group conssst-
  • the oxidation catalyst is preferably a diesel oxidation catalyst.
  • a diesel oxidation catalyst refers to any oxidation catalyst which is particularly well adapted to the oxidation of diesel exhaust gas, 0 in particular with respect to the temperatures and to the composition of diesel exhaust gas encountered in the treatment thereof.
  • the exhaust gas treatment system further comprises a CSF, and even more preferably both a CSF and an oxidation catalyst. Even 15 more preferably, the exhaust gas treatment system further comprises a CSF and a diesel oxidation catalyst.
  • said further components may be present in the exhaust gas 50 conduit in any order and at any emplacement therein, provided that the effective treatment of an exhaust gas may be provided.
  • the presence and/or order and/or location of said further components may depend on the type, on the state, in particular with respect to the temperature and pressure thereof, and on the average composition of the exhaust gas which is treated.
  • the present invention includes preferred embodiments wherein the oxidation catalyst and/or the CSF are located upstream or downstream from the inventive MFI/BEA-zeolite cata- 5 lyst, as well as preferred embodiments comprising both an oxidation catalyst and a CSF, wherein the oxidation catalyst is located upstream and the CSF downstream thereof, or wherein, vice versa, the CSF is located upstream, and the oxidation catalyst downstream thereof;
  • the oxidation catalyst and/or the CSF are located upstream from the inventive MFI/BEA-zeolite catalyst, to wherein even more preferably, the exhaust gas treatment system comprises both an oxidation catalyst and a CSF upstream from the inventive MF!/BEA-zeolite catalyst.
  • upstream and "downstream” relates to the direction of flow of the exhaust gas through the exhaust gas conduit in fluid communication with the internal combustion engine.
  • the present invention also relates to an exhaust gas treatment system as defined in the foregoing, said exhaust gas treatment system further comprising an oxidation catalyst and/or a cataiyzed soot filter (CSF), wherein the oxidation catalyst and/or the CSF are preferably located upstream from the inventive MFI/BEA-zeolite catalyst, and wherein the oxidation cata- 10 lyst is a diesel oxidation catalyst (DOC) in instances where the internal combustion engine is a diesei engine.
  • CSF cataiyzed soot filter
  • the exhaust gas treatment system preferably further includes a means of introducing a reductant into the exhaust gas conduit, said means being
  • the present invention also relates to an exhaust gas treatment system wherein in addition to or instead of further comprising an oxidation catalyst and/or a catalyzed soot filter (CSF) respectively preferably located upstream from the inventive MFI/BEA-zeolite
  • the oxidation catalyst being a diesel oxidation catalyst (DOC) in instances where the internal combustion engine is a diesel engine
  • said system further comprises a means of in- troducing a reductant preferably comprising ammonia and/or urea into the exhaust gas conduit, said means being located upstream of the inventive MFI/BEA-zeolite catalyst.
  • DOC diesel oxidation catalyst
  • the exhaust gas treat- 5 ment system further comprises an ammonia slip catalyst located downstream of the MFI/BEA- zeolite cataiyst for oxidizing excess ammonia and/or urea which has not reacted in the SCR.
  • said catalyst may be provided in the exhaust gas conduit in any manner commonly known in the art, provided that it may effectively oxidize said excess ammonia and/or urea.
  • said preferred embodiments involve an ex- L0 haust gas treatment systems according to the present invention which include a means of introducing a reductant into the exhaust gas conduit as defined in the foregoing.
  • the present invention further concerns a process for the treatment of a gas stream comprising
  • any suitable gas stream comprising NO x may be employed, provided that its state and composition are both suited for being treated when contacted with a MFI/BEA-zeolite catalyst according to the present invention, wherein preferably said treatment at least in part involves the selective catalytic reduction of at least part of the NO x contained in said gas.
  • inventive process preferably contains at least one reductant, which is preferably ammonia and/or any ammonia precursor such as urea and/or ammonium carbamate, urea being preferably comprised in the ammonia precursor.
  • reductant which is preferably ammonia and/or any ammonia precursor such as urea and/or ammonium carbamate, urea being preferably comprised in the ammonia precursor.
  • the gas stream used may also contain hydrocarbons and/or hydrocarbon derivatives such as oxygenated hydrocarbons, such as for example those which may be
  • the present invention also relates to a process for the treatment of a gas stream comprising NO x as defined in the present application, wherein the gas stream comprises ammonia and/or urea.
  • said reductant preferably comprising ammonia and/or urea
  • said reductant preferably comprising ammonia and/or urea
  • said content does not considerably derive from the amount of reductant necessary for the maxima! conversion of NO x by the L0 catalyst.
  • the maximal conversion reflects the maximum amount of NO x which may be converted by SCR at a given time point in the inventive process, i.e.
  • the maximal convert s sion of NO* directly reflects the maximum amount of reductant, and preferably of ammonia and/or urea, which may react with NO x in the SCR process at a given time point.
  • the gas stream used in the inventive process is preferably an exhaust gas stream comprising NO x .
  • the gas stream used in the inventive process is preferably an exhaust gas stream comprising NO x .
  • the exhaust gas stream is an exhaust gas stream resulting from an internal combustion engine, and even more preferably from a lean
  • the exhaust gas stream is a diesel engine exhaust gas stream.
  • the gas stream is contacted with the inventive MFI/BEA-zeolite catalyst for treatment thereof, wherein said contacting is achieved by J O either conducting the gas stream over the catalyst, or conducting the gas stream through the catalyst. Said contacting may, however, also be achieved by conducting the gas stream both over and through the inventive catalyst.
  • the gas stream is either conducted over the catalyst, wherein the catalyst preferably comprises a fiow-through substrate for this purpose, or the gas stream is conducted through the catalyst, wherein in this case the catalyst preferably comprises a wall-flow substrate.
  • the catalyst used in the inventive process either comprises a wall-flow honeycomb substrate or a flow-through honeycomb substrate,
  • the present invention also relates to a process for the treatment of a gas stream comprising NO x comprising conducting said gas stream over and/or through an MFI/BEA-zeolite catalyst according to the present invention, wherein the gas stream is preferably an exhaust gas stream, more preferably an exhaust gas stream resulting from an internal combustion engine, and even more preferably a diesel exhaust gas stream.
  • the amount of NO x contained in the gas stream there is no particular limitation as to the amount of NO x contained in the gas stream, wherein preferably, the amount thereof in the gas streams used in the inventive process does not exceed 10 wt.-% based on the total weight of the exhaust gas, and more preferably does not exceed 1 wt.-%, more preferably 0.5 wt.-%, more preferably 0.1 wt- 10 %, more preferably 0.05 wt-.%, more preferably 0.03 wt-.%, and even more preferably does not exceed 0.01 wt.-%.
  • the N0 2 -content relative to the total NO x -content is 90 wt.-% or less based on 100 wt.-% of NO x , wherein more preferably, the N0 2 content is comprised in the range of from 10 to 80 wt.-%, more preferably of from 30 to 70 wt.-%, more preferably of from 35 to 65 wt.-%, more preferably of from 40 to 60 wt.-%, and even more preferably of
  • the composition of the gas stream used in the inventive process as defined in the present application refers to the gas stream prior to its use in the inventive process, and in particular prior to the contacting thereof with the catalyst.
  • said composition refers to the gas stream's composition immediately prior to contacting the catalyst, i.e. 5 immediately before treatment thereof begins by catalyzed chemical conversion thereof.
  • the present invention also relates to a process for the treatment of a gas stream comprising NO* as defined in the present application, wherein prior to the contacting of the catalyst with the gas stream, the N0 2 content thereof is 90 wt.-% or less based on 100 wt.-% of L0 NO x , wherein more preferably, the N0 2 content is comprised in the range of from 10 to 80 wt.- %, more preferably of from 30 to 70 wt.-%, more preferably of from 35 to 65 wt.-%, more preferably of from 40 to 60 wt.-%, and even more preferably of from 45 to 55 wt.-%.
  • washcoat has its usual meaning in the art of a thin, adherent coating of a catalytic or other material applied to a substrate carrier material, such as a honeycomb-type carrier member, which is preferably sufficiently porous to permit the passage there through of the gas stream being treated.
  • the several zeolite components of the catalyst may be applied to the substrate as mixtures of one or more components in sequential steps in a manner which will be readily apparent to those skilled in the art of catalyst manufacture.
  • a typical method of manufacturing the catalyst of the present invention is to respectively provide the at least one zeolite of the MFI structure .5 type, and the at least one further zeolite of the BEA structure type as a coating or washcoat layer on the walls of a particularly preferred flow-through or wall-flow honeycomb substrate.
  • the zeolites are provided in a single washcoat on the substrate.
  • the catalyst according to the present invention is however preferably prepared by further using at least one binder, wherein any conceivable binder used in the art of catalyst manufacture, and in particular in the art of automotive SCR catalyst manufacture, may be used.
  • a silica-alumina binder is for example preferably used for the preparation of the inventive catalyst, wherein said binder may be provided together with one or more of the zeoiite components, and is preferably provided together with the zeolite components in one or more coatings on a substrate, more preferably in one or more washcoat layers.
  • the components of one or possibly more washcoat layers may respectively be processed to a slurry, preferably to an aqueous slurry.
  • the substrate may then be sequentially immersed into the respective slurries for applying the individual wash- coats, after which excess slurry is removed to provide a thin coating of the two or more slur-
  • L 0 ries on the walls of the substrate.
  • the coated substrate is then dried and preferably calcined to provide an adherent coating of the respective component to the walls of the substrate.
  • the resulting coated substrate may then be immersed into a further slurry to form a second washcoat layer deposited over the first washcoat
  • the substrate may then be dried and/or calcined and eventually coated with a third washcoat, which again may subsequently be dried and/or calcined to provide a finished catalyst
  • a third washcoat which again may subsequently be dried and/or calcined to provide a finished catalyst
  • any possible temperature may be used therein, provided that the process leads to the desired transformations in the catalyst without causing any notable or substantial deterioration of the catalysts stability, in particular with regard to
  • the temperature of calcination will not exceed 700°C, preferably 650°C, more preferably 600°C, and even more preferably will not exceed 550°C.
  • calcination may for example be conducted at a temperature comprised in the range of from 500°C to 650°C, preferably 550°C to 600°C, more preferably 570°C to 590°C, more preferably , and even more preferably at a temperature comprised in the range of from 575°C to
  • the catalyst of the present invention may be prepared according to a process comprising
  • Figure 1 displays results from NEDC testing of the catalyst compositions according to
  • Example 1 and Comparative Example 2, wherein the testing period in seconds _5 is plotted on the x-axis, and the NO x emissions in grams NO x is plotted on the y-axis, and wherein the background displays the legally prescribed course of NEDC testing over the time period in terms of the variation of the motor vehicle's speed as laid down in the European Union Directive 70/220/EEC,
  • a catalyst composition was prepared comprising 1 .35 g/in 3 of a zeolite of the BEA structure type, said BEA-type zeolite having a silica to alumina ratio (SAR) of approximately 40 and containing 1 .3 wt.-% of iron based on the total weight of the BEA-type zeolite, 1 .35 g/in 3 of a 5 zeolite of the MFI structure type, said Fl-type zeolite having a silica to alumina ratio of approximately 26 and containing 3.8 wt.-% of iron based on the total weight of the MFl-type zeolite, and 0.3 g/in 3 of a silica-alumina binder.
  • SAR silica to alumina ratio
  • a catalyst composition was prepared comprising 2.7 g/in 3 of a zeolite of the BEA structure type, said BEA-type zeolite having a silica to alumina ratio (SAR) of approximately 40 and containing 1 .3 wt.-% of iron based on the total weight of the BEA-type zeolite, and 0.3 g/in 3 of a silica-alumina binder.
  • SAR silica to alumina ratio
  • DeNO x Performance of the SCR Catalysts were evaluated in transient conditions using the New European Driving Cycle, also referred to as the MVEG (Motor Vehicle Emissions Group) cycle.
  • MVEG Mobile Vehicle Emissions Group
  • testing conditions were such, that the NO x fraction of the exhaust gas stream contained approximately 50 wt.-% of N0 2 based on the total NO x -content.
  • the catalyst compositions according to Examples 1 and Comparative Example 2 were respectiveiy coated onto a 5.66"x5:66"x6" flow-through honeycomb substrate having a volume of 2.5 L, a cell density of 400 cells per square inch, and a wail thickness of approximately 100pm (4 mil).
  • the catalyst samples prepared in this fashion were then tested in an !5 exhaust gas treatment system with a diesel oxidation catalyst (DOC) and a catalyzed soot filter (CSF) respectively located upstream from the tested catalyst.
  • DOC diesel oxidation catalyst
  • CSF catalyzed soot filter
  • the inventive catalyst according to Example 1 which contains a combination of S O BEA- and MFl-type zeolites displays a clearly improved performance compared to the catalyst sample of Comparative Example 2, which only contains BEA-type zeolite.
  • the inventive catalyst shows a superior conversion performance compared to Comparative Example 2 during the period from 0 to 800s corresponding to the old European driving cycie (ECE-1.5).
  • ECE-1.5 European driving cycie
  • the catalyst according to the present invention shows a clearly superior performance in SCR compared to a catalyst according to the prior art represent by Comparative 10 Example 2, in particular with respect to the actual driving conditions encountered in motor vehicle use, as reflected in NEDC testing.
  • these excellent results may be attributed to the use of a specific combination of zeolite materials as defined by the catalyst of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

La présente invention concerne un catalyseur destiné à être utilisé, de préférence, dans une réduction catalytique sélective (SCR), ce catalyseur comprenant une ou plusieurs zéolithes de type de structure MFI, et une ou plusieurs zéolithes de type de structure BEA, au moins une partie d'une ou des zéolithes de type de structure MFI, et au moins une partie d'une ou des zéolithes de type de structure BEA, respectivement, contenant du fer (Fe). En outre, la présente invention concerne un système de traitement de gaz d'échappement comprenant ledit catalyseur, ainsi qu'un procédé de traitement d'un courant gazeux comprenant NOx utilisant également ledit catalyseur.
PCT/IB2011/051526 2010-04-08 2011-04-08 Catalyseur à zéolithes mixtes fe-bea/fe-mfi et procédé de traitement de nox dans des courants gazeux à l'aide de ce catalyseur WO2011125050A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CA2795522A CA2795522A1 (fr) 2010-04-08 2011-04-08 Catalyseur a zeolithes mixtes fe-bea/fe-mfi et procede de traitement de nox dans des courants gazeux a l'aide de ce catalyseur
CN2011800268611A CN102958610A (zh) 2010-04-08 2011-04-08 Fe-BEA/Fe-MFI混合沸石催化剂和使用其处理气流中的NOx的方法
EP11765158.8A EP2555867A4 (fr) 2010-04-08 2011-04-08 Catalyseur à zéolithes mixtes fe-bea/fe-mfi et procédé de traitement de nox dans des courants gazeux à l'aide de ce catalyseur
BR112012025744A BR112012025744A2 (pt) 2010-04-08 2011-04-08 catalisador, sistema de tratamento de gás de escape, e, processo para o tratamento de uma corrente de gás
KR1020127029118A KR20130091638A (ko) 2010-04-08 2011-04-08 Ｆｅ-ＢＥＡ/Ｆｅ-ＭＦＩ 혼합 제올라이트 촉매 및 이를 사용하여 가스 스트림 내의 ＮＯｘ를 처리하는 방법
JP2013503212A JP2013523442A (ja) 2010-04-08 2011-04-08 Ｆｅ−ＢＥＡ／Ｆｅ−ＭＦＩ混合ゼオライト触媒及びガス流中のＮＯＸ処理方法
MX2012011540A MX2012011540A (es) 2010-04-08 2011-04-08 Catalizador de zeolita mixta de fe-bea/fe-mfi y proceso para tratar nox en corrientes de gas usando el mismo.
ZA2012/08258A ZA201208258B (en) 2010-04-08 2012-11-05 Fe-bea/fe-mfi mixed zeolite catalyst and process for the treatment of nox in gas streams

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10159369.7 2010-04-08
EP10159369 2010-04-08

Publications (1)

Publication Number Publication Date
WO2011125050A1 true WO2011125050A1 (fr) 2011-10-13

Family

ID=44762074

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2011/051526 WO2011125050A1 (fr) 2010-04-08 2011-04-08 Catalyseur à zéolithes mixtes fe-bea/fe-mfi et procédé de traitement de nox dans des courants gazeux à l'aide de ce catalyseur

Country Status (9)

Country Link
EP (1) EP2555867A4 (fr)
JP (1) JP2013523442A (fr)
KR (1) KR20130091638A (fr)
CN (1) CN102958610A (fr)
BR (1) BR112012025744A2 (fr)
CA (1) CA2795522A1 (fr)
MX (1) MX2012011540A (fr)
WO (1) WO2011125050A1 (fr)
ZA (1) ZA201208258B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015204012A1 (de) 2015-03-05 2016-09-08 Clariant International Ltd. SCR-Katalysator mit verbesserter Haftung
CN111954577A (zh) * 2018-04-11 2020-11-17 巴斯夫公司 含有混合沸石的scr催化剂

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6294127B2 (ja) * 2014-03-31 2018-03-14 株式会社キャタラー Ｓｃｒ用触媒及び排ガス浄化触媒システム
US11298692B2 (en) * 2017-10-09 2022-04-12 Umicore Ag & Co. Kg Active SCR catalyst
CN109289508B (zh) * 2018-10-24 2021-09-24 昆山工统环保科技有限公司 一种高疏水性沸石材料的制备方法
CN109592687B (zh) * 2018-12-03 2023-06-06 南京理工大学 利用tob制备多孔二氧化硅材料的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1395501A (zh) * 2000-01-14 2003-02-05 犹德有限公司 用于去除NOx和N2O的工艺
CN1711135A (zh) * 2002-11-18 2005-12-21 株式会社Ict 废气净化用催化剂与废气净化方法
CN1735451A (zh) * 2002-11-25 2006-02-15 亚拉国际有限公司 多金属沸石催化剂的制备和活化方法、催化剂组合物和用于减少n2o的应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5676912A (en) * 1995-02-22 1997-10-14 Mobil Oil Corporation Process for exhaust gas NOx, CO, and hydrocarbon removal
JP2001087646A (ja) * 1999-08-25 2001-04-03 Praxair Technol Inc 窒素を別のガスから選択的に吸着させるための新規の吸着剤
US8580216B2 (en) * 2005-02-28 2013-11-12 Ecs Holdings, Inc. Catalyst and method for reducing nitrogen oxides in exhaust streams with hydrocarbons or alcohols
DE102006020158B4 (de) * 2006-05-02 2009-04-09 Argillon Gmbh Extrudierter Vollkatalysator sowie Verfahren zu seiner Herstellung
CN101134172B (zh) * 2006-08-31 2010-10-27 中国石油化工股份有限公司 一种烃类转化催化剂
CN101190866B (zh) * 2006-11-21 2011-08-17 中国石油化工股份有限公司 低乙苯副产物的芳烃烷基转移和脱烷基反应方法
JP5110954B2 (ja) * 2007-05-09 2012-12-26 エヌ・イーケムキャット株式会社 選択還元型触媒を用いた排気ガス浄化触媒装置並びに排気ガス浄化方法
DE102007057305A1 (de) * 2007-11-28 2009-06-04 Süd-Chemie AG Beschichtungszusammensetzung für Dieseloxidationskatalysatoren
JP2009262098A (ja) * 2008-04-28 2009-11-12 Ne Chemcat Corp 選択還元触媒を用いた排気ガス浄化方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1395501A (zh) * 2000-01-14 2003-02-05 犹德有限公司 用于去除NOx和N2O的工艺
CN1711135A (zh) * 2002-11-18 2005-12-21 株式会社Ict 废气净化用催化剂与废气净化方法
CN1735451A (zh) * 2002-11-25 2006-02-15 亚拉国际有限公司 多金属沸石催化剂的制备和活化方法、催化剂组合物和用于减少n2o的应用

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015204012A1 (de) 2015-03-05 2016-09-08 Clariant International Ltd. SCR-Katalysator mit verbesserter Haftung
WO2016139102A1 (fr) * 2015-03-05 2016-09-09 Clariant International Ltd Catalyseur scr présentant une meilleure adhérence de la couche catalytique contenant des zéolites
US10150103B2 (en) * 2015-03-05 2018-12-11 Clariant International Ltd. SCR catalyst having improved adhesion of the zeolite-containing catalytic layer
CN111954577A (zh) * 2018-04-11 2020-11-17 巴斯夫公司 含有混合沸石的scr催化剂
EP3774033A4 (fr) * 2018-04-11 2021-12-29 BASF Corporation Catalyseur à réduction catalytique sélective contenant une zéolite mixte

Also Published As

Publication number Publication date
EP2555867A1 (fr) 2013-02-13
BR112012025744A2 (pt) 2016-06-28
CN102958610A (zh) 2013-03-06
ZA201208258B (en) 2014-01-29
CA2795522A1 (fr) 2011-10-13
KR20130091638A (ko) 2013-08-19
EP2555867A4 (fr) 2014-12-10
MX2012011540A (es) 2012-11-16
JP2013523442A (ja) 2013-06-17

Similar Documents

Publication Publication Date Title
US9352307B2 (en) Cu-CHA/Fe-MFI mixed zeolite catalyst and process for the treatment of NOx in gas streams
EP2555866B1 (fr) Catalyseur comprenant les zéolithes Cu-CHA et Fe-MFI et procédé DE TRAITEMENT DE NOX DANS DES COURANTS GAZEUX
JP6348212B2 (ja) ガス流中のＮＯｘを処理するためのＣｕ−ＣＨＡ／Ｆｅ−ＢＥＡ混合ゼオライト触媒および方法
CN111742121B (zh) 具有上游scr催化剂的排气处理系统
US9999877B2 (en) Cu-CHA/Fe-BEA mixed zeolite catalyst and process for the treatment of NOx in gas streams
US11154815B2 (en) Exhaust gas treatment system
EP2790813B1 (fr) Système d'échappement pour moteur à combustion interne à mélange pauvre comprenant un catalyseur de scr
KR101951515B1 (ko) Ｓｃｒ 촉매를 포함하는 기판 모노리스
EP3554697B1 (fr) Catalyseur adsorbeur des nox
WO2010075345A2 (fr) Systèmes et procédés de traitement d'émissions employant un filtre rcs catalysé et un catalyseur rcs aval
US9079162B2 (en) Fe-BEA/Fe-MFI mixed zeolite catalyst and process for the treatment of NOX in gas streams
KR20190036543A (ko) 배기 가스 촉매 및 필터 기재에 대한 촉매 결합제
EP2555867A1 (fr) Catalyseur à zéolithes mixtes fe-bea/fe-mfi et procédé de traitement de nox dans des courants gazeux à l'aide de ce catalyseur
KR20230079420A (ko) 비스무트를 함유하는 디젤 산화 촉매

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180026861.1

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11765158

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 8443/CHENP/2012

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2795522

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: MX/A/2012/011540

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2013503212

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 1201005307

Country of ref document: TH

ENP Entry into the national phase

Ref document number: 20127029118

Country of ref document: KR

Kind code of ref document: A

REEP Request for entry into the european phase

Ref document number: 2011765158

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011765158

Country of ref document: EP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112012025744

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112012025744

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20121008