WO2008132452A2 - Transition metal/zeolite scr catalysts - Google Patents

Transition metal/zeolite scr catalysts Download PDF

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Publication number
WO2008132452A2
WO2008132452A2 PCT/GB2008/001451 GB2008001451W WO2008132452A2 WO 2008132452 A2 WO2008132452 A2 WO 2008132452A2 GB 2008001451 W GB2008001451 W GB 2008001451W WO 2008132452 A2 WO2008132452 A2 WO 2008132452A2
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
catalyst
transition metal
zeolites
small pore
Prior art date
Application number
PCT/GB2008/001451
Other languages
French (fr)
Other versions
WO2008132452A3 (en
Inventor
Paul Joseph Andersen
Jillian Elaine Bailie
John Leonello Casci
Hai-Ying Chen
Joseph Michael Fedeyko
Rodney Kok Shin Foo
Raj Rao Rajaram
Original Assignee
Johnson Matthey Public Limited Company
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=38814668&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2008132452(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to KR1020187011116A priority Critical patent/KR20180043406A/en
Priority to EP08762186.8A priority patent/EP2150328B1/en
Priority to EP19206118.2A priority patent/EP3626329B1/en
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Priority to EP17200920.1A priority patent/EP3300791B1/en
Priority to KR1020197000095A priority patent/KR102089480B1/en
Priority to EP12177705.6A priority patent/EP2517778B2/en
Priority to JP2010504833A priority patent/JP5777339B2/en
Priority to CA2685009A priority patent/CA2685009C/en
Priority to US12/597,707 priority patent/US20100290963A1/en
Priority to EP12177604.1A priority patent/EP2517773B2/en
Priority to KR1020157010306A priority patent/KR20150052335A/en
Priority to KR1020167033642A priority patent/KR101965943B1/en
Priority to MX2009011443A priority patent/MX2009011443A/en
Priority to EP21204033.1A priority patent/EP3981502A1/en
Priority to DK08762186.8T priority patent/DK2150328T5/en
Priority to EP17189358.9A priority patent/EP3278863B1/en
Priority to CN2008800217622A priority patent/CN101730575B/en
Priority to RU2009143682/05A priority patent/RU2506989C2/en
Priority to EP12177690.0A priority patent/EP2517776B2/en
Priority to BRPI0810133-7A priority patent/BRPI0810133B1/en
Publication of WO2008132452A2 publication Critical patent/WO2008132452A2/en
Publication of WO2008132452A3 publication Critical patent/WO2008132452A3/en
Priority to US13/164,150 priority patent/US8603432B2/en
Priority to US13/567,698 priority patent/US20120301379A1/en
Priority to US13/567,703 priority patent/US20120301380A1/en
Priority to US13/567,692 priority patent/US20120301378A1/en
Priority to US13/567,705 priority patent/US8906820B2/en
Priority to US14/552,161 priority patent/US20150078968A1/en
Priority to US14/587,793 priority patent/US20150110682A1/en
Priority to US14/587,709 priority patent/US20150118115A1/en
Priority to US14/587,613 priority patent/US20150118114A1/en
Priority to US14/587,653 priority patent/US20150118121A1/en
Priority to US15/252,376 priority patent/US20160367939A1/en
Priority to US15/991,565 priority patent/US11478748B2/en

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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    • B01D53/34—Chemical or biological purification of waste gases
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • 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
    • 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
    • B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
    • 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
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a method of converting nitrogen oxides in a gas, such as an exhaust gas of a vehicular lean-burn internal combustion engine, to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a transition metal-containing zeolite catalyst.
  • SCR Selective catalytic reduction
  • nitrogenous compounds such as ammonia or urea
  • SCR technology was first used in thermal power plants in Japan in the late 1970s, and has seen widespread application in Europe since the mid-1980s.
  • SCR systems were introduced for gas turbines in the 1990s and have been used more recently in coal-fired powerplants.
  • SCR applications include plant and refinery heaters and boilers in the chemical processing industry, furnaces, coke ovens, municipal waste plants and incinerators.
  • NO x reduction systems based on SCR technology are being developed for a number of vehicular (mobile) applications in Europe, Japan, and the USA, e.g. for treating diesel exhaust gas.
  • reaction (1) Several chemical reactions occur in an NH 3 SCR system, all of which represent desirable reactions that reduce NO x to nitrogen. The dominant reaction is represented by reaction (1).
  • reaction (2) Competing, non-selective reactions with oxygen can produce secondary emissions or may unproductively consume ammonia.
  • One such non-selective reaction is the complete oxidation of ammonia, shown in reaction (2).
  • reaction (3) may lead to undesirable products such as N 2 O, as represented by reaction (3).
  • Aluminosilicate zeolites are used as catalysts for SCR of NO x with NH 3 .
  • One application is to control NO x emissions from vehicular diesel engines, with the reductant obtainable from an ammonia precursor such as urea or by injecting aramor ⁇ aper se.
  • transition metals are incorporated into the aluminosilicate zeolites.
  • the most commonly tested transition metal zeolites are Cu/ZSM-5, Cu/Beta, Fe/ZSM-5 and Fe/Beta because they have a relatively wide temperature activity window. In general, Cu-based zeolite catalysts show better low temperature NO x reduction activity than Fe-based zeolite catalysts.
  • ZSM-5 and Beta zeolites have a number of drawbacks. They are susceptible to dealumination during high temperature hydrothe ⁇ al ageing resulting in a loss of acidity, especially with Cu/Beta and Cu/ZSM-5 catalysts. Both Beta- and ZSM-5-based catalysts are also affected by hydrocarbons which become adsorbed on the catalysts at relatively low temperatures and ar,e oxidised as the temperature of the catalytic system is raised generating a significant exotherm, which can thermally damage the catalyst. This problem is particularly acute in vehicular diesel applications where significant quantities of hydrocarbon can be adsorbed on the catalyst during cold-start; and Beta and ZSM-5 zeolites are also prone to coking by hydrocarbons.
  • Cu-based zeolite catalysts are less thermally durable, and produce higher levels OfN 2 O than Fe-based zeolite catalysts. However, they have a desirable advantage in that they slip less ammonia in. use compared with a corresponding Fe-zeolite catalyst.
  • aluminophosphate zeolites that contain transition metals demonstrate enhanced catalytic activity and superior thermal stability than aluminosilicate zeolite catalysts for SCR OfNO x with hydrocarbons (also known as lean NO x catalysis or "DeNOx catalysts" (e.g. Ishihara et ah, Journal of Catalysis, 169 (1997) 93)).
  • DeNOx catalysts also known as lean NO x catalysis or "DeNOx catalysts” (e.g. Ishihara et ah, Journal of Catalysis, 169 (1997) 93).
  • 2006/064805 discloses an electrical processing technology for treating diesel engine exhaust gas which utilizes corona discharge.
  • a combination of a device for adding a NO x reducer (hydrocarbon or fuel) and a Cu-SAPO-34 NO x reducing catalyst can be disposed downstream of the electrical processing apparatus.
  • NO x reducer hydrocarbon or fuel
  • Cu-SAPO-34 NO x reducing catalyst can be disposed downstream of the electrical processing apparatus.
  • WO 00/72965 discloses iron (Fe) exchanged zeolites for the selective catalytic reduction of nitrogen monoxide by ammonia for controlling NO x emissions from fossil-fuel power plants and engines.
  • the Fe-exchanged, and optionally Fe-rare earth-exchanged, e.g. Fe-Ce-exchanged, zeolites suggested include: ZSM-5, mordenite, SAPO, clinoptilolite, chabazite, ZK-4 and ZK-5. No specific SAPO zeolites are identified and no experiment using SAPO zeolites is disclosed.
  • WO '965 teaches that the disclosure has application to zeolites with a range of pore sizes, i.e.
  • US patent no. 4,735,927 discloses an extruded-type NH 3 -SCR catalyst with stability to sulfur poisoning comprising a high surface area titania in the form of anatase and a natural or synthetic zeolite.
  • the zeolite must be either in the acid form or thermally convertible to the acid form in the catalytic product.
  • suitable zeolites include mordenite, natural clinoptilolite, erionite, heulandite, ferrierite, natural faujasite or its synthetic counterpart zeolite Y, chabazite and gmelinite.
  • a preferred zeolite is natural clinoptilolite, which may be mixed with another acid stable zeolite such as chabazite.
  • the catalyst may optionally include small amounts (at least 0.1% by elemental weight) of a promoter in the form of precursors of vanadium oxide, copper oxide, molybdenum oxide or combinations thereof (0.2 wt% Cu and up to 1.6 wt% V are exemplified).
  • a promoter in the form of precursors of vanadium oxide, copper oxide, molybdenum oxide or combinations thereof (0.2 wt% Cu and up to 1.6 wt% V are exemplified).
  • Extruded-type catalysts are generally less durable, have lower chemical strength, require more catalyst material to achieve the same activity and are more complicated to manufacture than catalyst coatings applied to inert monolith substrates.
  • US patent no. 5,417,949 also discloses an extruded-type NH 3 -SCR catalyst comprising a zeolite having a constraint index of up to 12 and a titania binder. Intentionally, no transition metal promoter is present.
  • Constraint Index is a test to determine shape-selective catalytic behaviour in zeolites. It compares the reaction rates for the cracking of n-hexane and its isomer 3-methylpentane under competitive conditions (see VJ. Frillette et al., J Catal. 67 (1991) 218)).
  • US patent no. 5,589,147 discloses an ammonia SCR catalyst comprising a molecular sieve and a metal, which catalyst can be coated on a substrate monolith.
  • the molecular sieve ⁇ useful in the invention is not limited to any particular molecular sieve material and, in general, includes all metallosilicates, metallophosphates, silicoaluminophosphates and layered and pillared layered materials.
  • the metal is typically selected from at least one of the metals of Groups of the Periodic Table IIIA, IB, IIB, VA, VIA, VILA, VIIIA and combinations thereof.
  • Examples of these metals include at least one of copper, zinc, vanadium, chromium, manganese, cobalt, iron, nickel, rhodium, palladium, platinum, molybdenum, tungsten, cerium and mixtures thereof.
  • intermediate pore size zeolites are preferred because they provide constrained access to and egress from the intracrystalline free space: "The intermediate pore size zeolites...have an effective pore size such as to freely sorb normal hexane...if the only pore windows in a crystal are formed by 8- membered rings of oxygen atoms, then access to molecules of larger cross-section than normal hexane is excluded and the zeolite is not an intermediate pore size material.” Only extruded Fe- ZSM-5 is exemplified.
  • WO 2004/002611 discloses an NH 3 -SCR catalyst comprising a ceria-doped aluminosilicate zeolite.
  • US 6,514,470 discloses a process for catalytically reducing NO x in an exhaust gas stream containing nitrogen oxides and a reductant material.
  • the catalyst comprises an aluminium- silicate material and a metal in an amount of up to about 0.1 weight percent based on'the total weight of catalyst. All of the examples use ferrierite.
  • US patent no. 4,961,917 discloses an NH 3 -SCR catalyst comprising a zeolite having a silica-to-alumina ratio of at least about 10, and a pore structure which is interconnected in all three crystallographic dimensions by pores having an average kinetic pore diameter of at least about 7 Angstroms and a Cu or Fe promoter.
  • the catalysts are said to have high activity, reduced NH 3 oxidation and reduced sulphur poisoning.
  • Zeolite Beta and zeolite Y are two zeolites that meet the required definition.
  • US patent no. 3,895,094 discloses an NH 3 -SCR process using zeolite catalysts of at least 6 Angstrom intercrystalline.pore size. No mention is made of exchanging the zeolites with transition metals.
  • Angstrom pore size zeolites of Na or H form Angstrom pore size zeolites of Na or H form.
  • WO 02/41991 discloses metal promoted zeolite Beta for NH 3 -SCR, wherein the zeolite is pre-treated so as to provide it with improved hydrothermal stability.
  • the invention provides a method of converting nitrogen oxides in a gas to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a zeolite catalyst containing at least one transition metal, wherein the zeolite is a small pore zeolite containing a maximum ring size of eight tetrahedral atoms, wherein the at least one transition metal is selected from the group consisting of Cr, Mn, Fe 5 Co, Ce, Ni, Cu 5 Zn, Ga, Mo, Ru, Rh, Pd 5 Ag 5 In, Sn 5 Re 5 Ir and Pt.
  • zeolite catalyst containing at least one transition metal herein we mean a zeolite structure to which has been added by ion exchange, impregnation or isomorphous substitution etc. one or more metals.
  • Transition metal-containing zeolite catalyst and “zeolite catalyst containing at least one transition metal” and similar terms are used interchangeably herein.
  • zeolites by their Framework Type Codes we intend to include the "Type Material” and any and all isotypic framework materials.
  • the "Type Material” is the species first used to establish the framework type).
  • Table 1 lists a range of illustrative zeolite zeotype framework materials for use in the present invention.
  • chabazite is to the zeolite material per se (in this example the naturally occurring type material chabazite) and not to any other material designated by the Framework Type Code to which the individual zeolite may belong, e.g. some other isotypic framework material.
  • zeolite type materials such as naturally occurring (i.e. mineral) chabazite
  • isotypes within the same Framework Type Code is not merely arbitrary, but reflects differences in the properties between the materials, which may in turn lead to differences in activity in the method of the present invention.
  • chabazite naturally occurring (i.e. mineral) chabazite
  • isotypes within the same Framework Type Code is not merely arbitrary, but reflects differences in the properties between the materials, which may in turn lead to differences in activity in the method of the present invention.
  • the naturally occurring chabazite has a lower silica-to-alumina ratio than aluminosilicate isotypes such as SSZ-13, the naturally occurring chabazite has lower acidity than aluminosilicate isotypes such as SSZ-13 and the activity of the material in the method of the present invention is relatively low (see the comparison of Cu/naturally occurring chabazite with Cu/SAPO-34 in Example 13).
  • the zeolite catalysts for use in the present invention can be coated on a suitable substrate monolith or can be formed as extruded-type catalysts, but are preferably used in a catalyst coating.
  • a suitable substrate monolith can be formed as extruded-type catalysts, but are preferably used in a catalyst coating.
  • the prior art does mention a few small pore zeolites containing at least one transition metal for converting nitrogen oxides in a gas to nitrogen with a nitrogenous reducing agent
  • the prior art suggests using large, medium and small pore zeolites containing at least one transition metal, without distinction. Accordingly, we seek to exclude any specific small pore zeolites containing at least one transition metal that have been mentioned only in this context.
  • the zeolite catalyst is not one of Co, Ga, Mn, In or Zn or any combination of two or more thereof/epistilbite (see US patent no. 6,514,470).
  • the transition metal-containing small pore zeolite is not Cu/chabazite, Mo/chabazite, Cu-Mo/chabazite, Cu/erionite, Mo/erionite or Cu-Mo/erionite (see US patent no. 4,735,927).
  • the transition metal-containing small pore zeolite is not Ce/erionite (see WO 2004/002611).
  • the transition metal-containing small pore zeolite is not Fe/chabazite, Fe/ZK-5, Fe/ZK-4, Fe-rare-earth/chabazite, Fe-rare-earth/ZK-5 or Fe-rare- earth/ZK-4 (see WO 00/72965).
  • WO 00/72965 discloses the use of Ce/SAPO zeolites and Ce-rare-earth/SAPO zeolites in general, it does not disclose any particular small pore SAPO zeolites with application in the present invention, such as SAPO- 17, SAPO- 18, SAPO-34, SAPO-35, SAPO-39, SAPO-43 and SAPO-56.
  • the transition metal-containing small pore zeolite is not Fe/chabazite, (see Long et al. Journal of Catalysis 207 (2002) 274-285). Whilst, for the reasons given hereinabove, we do not believe that US patent no.
  • the zeolite catalyst is not any one of copper, zinc, chromium, manganese, cobalt, iron, nickel, rhodium, palladium, platinum, molybdenum, cerium or mixtures thereof/any one of aluminosilicate chabazite, aluminosilicate erionite, aluminosilicate ZSM-34 and SAPO-34.
  • the transition metal-containing zeolite catalyst is not LTA or Fe/CHA.
  • chabazite is a small pore zeolite according to the definition adopted herein and that the Long et al. paper mentioned above reports that Fe/chabazite has the poorest activity of any of the catalysts tested. Without wishing to be bound by any theory, we believe that the poor performance of the Fe/chabazite in this study is due to two principal reasons. Firstly, natural chabazite can contain basic metal cations including potassium, sodium, strontium and calcium. To obtain an active material the basic metal cations need to be exchanged for e.g. iron cations because basic metals are a known poison of zeolite acid sites.
  • iron ions can form metal complexes (coordination compounds) with suitable ligands in the ionic exchange medium.
  • coordination compounds metal complexes
  • suitable ligands in the ionic exchange medium.
  • Long et al. use an aqueous FeCl 2 solution for ion exchange. Since the zeolite pores are relatively small, it is possible that a bulky co-ordination compound may not be able to gain access to the active sites located in the pores.
  • Suitable substituent metals include one or more of, without limitation, As, B, Be, Co, Fe, Ga, Ge, Li, Mg, Mn, Zn and Zr.
  • the small pore zeolites for use in the present invention can be selected from the group consisting of aluminosilicate zeolites, metal-substituted aluminosilicate zeolites and aluminophosphate zeolites.
  • Aluminophosphate zeolites with application in the present invention include aluminophosphate (AlPO) zeolites, metal substituted zeolites (MeAh 0 O) zeolites, silico- aluminophosphate (SAPO) zeolites and metal substituted silico-aluminophosphate (MeAPSO) zeolites.
  • AlPO aluminophosphate
  • MeAh 0 O metal substituted zeolites
  • SAPO silico- aluminophosphate
  • MeAPSO metal substituted silico-aluminophosphate
  • the invention extends to catalyst coatings and extruded-type substrate monoliths comprising both transition metal-containing small pore zeolites according to the invention and non-small pore zeolites (whether metallised or not) such as medium-, large- and meso-pore zeolites (whether containing transition metal(s) or not) because such a combination also obtains the advantages of using small pore zeolites per se.
  • the catalyst coatings and extruded-type substrate monoliths for use in the invention can comprise combinations of two or more transition metal-containing small pore zeolites.
  • each small pore zeolite in such a combination can contain one or more transition metals, each being • selected from the group defined hereinabove, e.g. a first small pore zeolite can contain both Cu and Fe and a second small pore zeolite in combination with the first small pore zeolite can contain Ce.
  • transition metal-containing small pore zeolites are advantageous catalysts for SCR ofNO x with NH 3 .
  • transition metal-containing small pore zeolite catalysts demonstrate significantly improved NO x reduction activity, especially at low temperatures. They also exhibit high selectivity to N 2 (e.g. low N 2 O formation) and good hydrothermal stability.
  • small pore zeolites containing at least one transition metal. are more resistant to hydrocarbon inhibition than larger pore zeolites, e.g.
  • a medium pore zeolite such as ZSM-5
  • a large pore zeolite a zeolite having a maximum ring size of 12
  • Beta a medium pore zeolite
  • Small pore aluminophosphate zeolites for use in the present invention include SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-39, SAPO-43 and SAPO-56.
  • the small pore zeolite is selected from the group of Framework Type Codes consisting of: ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG and ZON.
  • Framework Type Codes consisting of: ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON,
  • Zeolites with application in the present invention can include those that have been treated to improve hydrothermal stability.
  • Illustrative methods of improving hydrothermal stability include: ' (i) Dealumination by: steaming and acid extraction using an acid or complexing agent e.g. (EDTA - ethylenediaminetetracetic acid); treatment with acid and/or complexing agent; treatment with a gaseous stream of SiCl 4 (replaces Al in the zeolite framework with Si);
  • small pore zeolites may minimise the detrimental effect of hydrocarbons by means of a molecular sieving effect, whereby the small pore zeolite allows NO and NH 3 to diffuse to the active sites inside the pores but that the diffusion of hydrocarbon molecules is restricted.
  • the kinetic diameter of both NO (3.16A) and NH 3 (2.6A) is smaller than those of the typical hydrocarbons (C 3 H 6 ⁇ 4.5A, H-C 8 H 18 -4.30A and C 7 H 8 ⁇ 6.0A) present in, for example, diesel engine exhaust.
  • the small pore zeolite catalysts for use in the present invention have a pore size in at least one dimension of less than 4.3 A.
  • Illustrative examples of suitable small pore zeolites are set out in Table 1.
  • Small pore zeolites with particular application for treating NO x in exhaust gases of lean- burn internal combustion engines, e.g. vehicular exhaust gases are set out in Table 2.
  • Table 2 Preferred small pore zeolites for use in treating exhaust gases of lean-burn internal combustion engines.
  • Small pore aluminosilicate zeolites for use in the present invention can have a silica-to- alumina ratio (SAR) of from 2 to 300, optionally 4 to 200 and preferably 8 to 150. It will be appreciated that higher SAR ratios are preferred to improve thermal stability but this may negatively affect transition metal exchange. Therefore, in selecting preferred materials consideration can be given to SAR so that a balance may be struck between these two properties.
  • SAR silica-to- alumina ratio
  • the gas containing the nitrogen oxides can. contact the zeolite catalyst at a gas hourly space velocity of from 5,000 hr "1 to 500,000 hr '1 , optionally from 10,000 hr "1 to 200,000 hr "1 .
  • the small pore zeolites for use in the present invention do not include aluminophosphate zeolites as defined herein.
  • the small pore zeolites (as defined herein) for use in the present invention are restricted to aluminophosphate zeolites (as defined herein).
  • small pore zeolites for use in the present invention are aluminosilicate zeolites and metal substituted aluminosilicate zeolites (and not aluminophosphate zeolites as defined herein).
  • Small pore zeolites for use in the invention can have three-dimensional dimensionality, i.e. a pore structure which is interconnected in all three crystallographic dimensions, or two- dimensional dimensionality, hi one embodiment, the small pore zeolites for use in the present invention consist of zeolites having three-dimensional dimensionality. In another embodiment, the small pore zeolites for use in the present invention consist of zeolites having two- dimensional dimensionality.
  • the at least one transition metal is selected from the group consisting of Cr, Ce, Mn, Fe, Co, Ni and Cu. In a preferred embodiment, the at least one transition metal is selected from the group consisting of Cu, Fe and Ce. In a particular embodiment, the at least one transition metal consists of Cu. In another particular embodiment, the at least one transition metal consists of Fe. In a further particular embodiment, the at least one transition metal is Cu and/or Fe.
  • the total of the at least one transition metal that can be included in the at least one transition metal-containing zeolite can be from 0.01 to 20 wt%, based on the total weight of the zeolite catalyst containing at least one transition metal. In one embodiment, the total of the at least one transition metal that can be included can be from 0.1 tol 0wt%. In a particular embodiment, the total of the at least one transition metal that can be included is from 0.5 to 5wt%.
  • a preferred transition metal-containing two dimensional small pore zeolite for use in the present invention consists of Cu/LEV, such as Cu/Nu-3, whereas a preferred transition metal- containing three dimensional small pore zeolite/aluminophosphate zeolite for use in the present invention consists of Cu/CHA, such as Cu/SAPO-34 or Cu/SSZ-13.
  • Fe-containing zeolite catalysts are preferred, such as Fe-CHA, e.g. Fe/SAPO-34 or Fe/SSZ-13.
  • the at least one transition metal can be included in the zeolite by any feasible method. For example, it can be added after the zeolite has been synthesised, e.g. by incipient wetness or exchange process; or the at least one metal can be added during zeolite synthesis.
  • the zeolite catalyst for use in the present invention can be coated, e.g. as a washcoat component, on a suitable monolith substrate, such as a metal or ceramic flow through monolith substrate or a filtering substrate, such as a wall-flow filter or sintered metal or partial filter (such as is disclosed in WO 01/80978 or EP 1057519, the latter document describing a substrate comprising convoluted flow paths that at least slows the passage of soot therethrough).
  • a suitable monolith substrate such as a metal or ceramic flow through monolith substrate or a filtering substrate, such as a wall-flow filter or sintered metal or partial filter (such as is disclosed in WO 01/80978 or EP 1057519, the latter document describing a substrate comprising convoluted flow paths that at least slows the passage of soot therethrough).
  • the zeolites for use in the present invention can be synthesized directly onto the substrate.
  • the zeolite catalysts according to the invention can be formed into an extruded-type flow through catalyst.
  • washcoat compositions containing the zeolites for use in the present invention for coating onto the monolith substrate for manufacturing extruded type substrate monoliths can comprise a binder selected from the group consisting of alumina, silica, (non zeolite) silica-alumina, naturally occurring clays, TiO 2 , ZrO 2 , and SnO 2 .
  • the nitrogen oxides are reduced with the reducing agent at a temperature of at least 100°C. In another embodiment, the nitrogen oxides are reduced with the reducing agent at a temperature from about 150°C to 750°C.
  • the latter embodiment is particularly useful for treating exhaust gases from heavy and light duty diesel engines, particularly engines comprising exhaust systems comprising (optionally catalysed) diesel particulate filters which are regenerated actively, e.g. by injecting hydrocarbon into the exhaust system upstream of the filter, wherein the zeolite catalyst for use in the present invention is located downstream of the filter.
  • the temperature range is from 175 to 550°C. hi another embodiment, the temperature range is from 175 to 400°C.
  • the nitrogen oxides reduction is carried out in the presence of oxygen. In an alternative embodiment, the nitrogen oxides reduction is carried out in the absence of oxygen.
  • Zeolites for use in the present application include natural and synthetic zeolites, preferably synthetic zeolites because the zeolites can have a more uniform: silica-to-alumina ratio (SAR), crystallite, size, crystallite morphology, and the absence of impurities (e.g. alkaline earth metals).
  • SAR silica-to-alumina ratio
  • crystallite size, crystallite morphology, and the absence of impurities (e.g. alkaline earth metals).
  • the source of nitrogenous reductant can be ammor ⁇ aper se, hydrazine or any suitable ammonia precursor, such as urea ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate.
  • the method can be performed on a gas derived from a combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine and coal or oil fired power plants.
  • a gas derived from a combustion process such as from an internal combustion engine (whether mobile or stationary), a gas turbine and coal or oil fired power plants.
  • the method may also be used to treat gas from industrial processes such as refining, from refinery heaters and boilers, furnaces, the chemical processing industry, coke ovens, municipal waste plants and incinerators, coffee roasting plants etc.
  • the method is used for treating exhaust gas from a vehicular lean burn internal combustion engine, such as a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.
  • a vehicular lean burn internal combustion engine such as a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.
  • the invention provides an exhaust system for a vehicular lean burn internal combustion engine, which system comprising a conduit for carrying a flowing exhaust gas, a source of nitrogenous reductant, a zeolite catalyst containing at least one transition metal ⁇ disposed in a flow path of the exhaust gas and means for metering nitrogenous reductant into a flowing exhaust gas upstream of the zeolite catalyst, wherein the zeolite catalyst is a small pore zeolite containing a maximum ring size of eight tetrahedral atoms, wherein the at least one transition metal is selected from the group consisting of Cr, Mn, Fe 3 Co, Ce, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir and Pt.
  • the small pore transition metal-containing zeolites for use in the exhaust system aspect of the present invention include any for use in the method according to the invention as described hereinabove.
  • the zeolite catalyst is coated on a flow-through monolith substrate (i.e. a honeycomb monolithic catalyst support structure with many small, parallel channels running axially through the entire part) or filter monolith substrate such as a wall-flow filter etc., as described hereinabove.
  • a flow-through monolith substrate i.e. a honeycomb monolithic catalyst support structure with many small, parallel channels running axially through the entire part
  • filter monolith substrate such as a wall-flow filter etc., as described hereinabove.
  • the zeolite catalyst is formed into an extruded-type catalyst.
  • the system can include means, when in use, for controlling the metering means so that nitrogenous reductant is metered into the flowing exhaust gas only when it is determined that the zeolite catalyst is capable of catalysing NO x reduction at or above a desired efficiency, such as at above 100°C, above 15O 0 C or above 175°C.
  • the determination by the control means can be assisted by one or more suitable sensor inputs indicative of a condition of the engine selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, mass flow of exhaust gas in the system, manifold vacuum, ignition timing, engine speed, lambda value of the exhaust gas, the quantity of fuel injected in the engine, the position of the exhaust gas recirculation (EGR) valve and thereby the amount of EGR and boost pressure.
  • suitable sensor inputs indicative of a condition of the engine selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, mass flow of exhaust gas in the system, manifold vacuum, ignition timing, engine speed, lambda value of the exhaust gas, the quantity of fuel injected in the engine, the position of the exhaust gas recirculation (EGR) valve and thereby the amount of EGR and boost pressure.
  • metering is controlled in response to the quantity of nitrogen oxides in the exhaust gas determined either directly (using a suitable NO x sensor) or indirectly, such as using pre-correlated look-up tables or maps - stored in the control means - correlating any one or more of the abovementioned inputs indicative of a condition of the engine with predicted NO x content of the exhaust gas.
  • the control means can comprise a pre-programmed processor such as an electronic control unit (ECU).
  • the metering of the nitrogenous reductant can be arranged such that 60% to 200% of theoretical ammonia is present in exhaust gas entering the SCR catalyst calculated at 1 :1 NH 3 /NO and 4:3 NH 3 /NO 2;
  • an oxidation catalyst for oxidising nitrogen monoxide in the exhaust gas to nitrogen dioxide can be located upstream of a point of metering the nitrogenous reductant into the exhaust gas.
  • the oxidation catalyst is adapted to yield a gas stream entering the SCR zeolite catalyst having a ratio of NO to NO 2 of from about 4:1 to about 1 :3 by volume, e.g. at an exhaust gas temperature at oxidation catalyst inlet of 250°C to 45O 0 C.
  • the oxidation catalyst can include at least one platinum group metal (or some combination of these), such as platinum, palladium, or rhodium, coated on a flow-through monolith substrate.
  • the at least one platinum group metal is platinum, palladium or a combination of both platinum and palladium.
  • the platinum group metal can be supported on a high surface area washcoat component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, non-zeolite silica alumina, ceria, zirconia, titania or a mixed or composite oxide containing both ceria and zirconia.
  • a suitable filter substrate is located between the oxidation catalyst and the zeolite catalyst.
  • Filter substrates can be selected from any of those mentioned above, e.g. wall flow filters.
  • the filter is catalysed, e.g. with an oxidation catalyst of the kind discussed above, preferably the point of metering nitrogenous reductant is located between the filter and the zeolite catalyst.
  • the means for metering nitrogenous reductant can be located between the oxidation catalyst and the filter. It will be appreciated that this arrangement is disclosed in WO 99/39809.
  • the zeolite catalyst for use in the present invention is coated on a filter located downstream of the oxidation catalyst.
  • the filter includes the zeolite catalyst for use in the present invention
  • the point of metering the nitrogenous reductant is preferably located between the oxidation catalyst and the filter.
  • control means meters nitrogenous reductant into the flowing exhaust gas . only when the exhaust gas temperature is at least 100°C, for example only when the exhaust gas temperature is from 150°C to 75O 0 C.
  • a vehicular lean-burn engine comprising an exhaust system according to the present invention.
  • the vehicular lean burn internal combustion engine can be a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.
  • Figure 1 is a graph showing NO x conversion (at a gas hourly space velocity of 30,000 hr " l ) comparing transition metal-containing aluminosilicate catalysts with a transition metal- containing aluminophosphate/small pore zeolite catalyst after relatively moderate lean hydrothermal ageing performed on a laboratory reactor;
  • Figure 2 is a graph showing N 2 O formation in the test shown in Figure 1;
  • Figure 3 is a graph showing NO x conversion (at a gas hourly space velocity of 100,000 hr '1 ) comparing Cu/Beta zeolite and Cu/SAPO-34 catalysts with a transition metal-containing aluminophosphate/small pore zeolite catalyst after relatively moderate lean hydrothermal ageing performed on a laboratory reactor;
  • Figure 4 is a graph showing NO x conversion (at a gas hourly space velocity of 30,000 hr " l ) comparing transition metal-containing aluminosilicate catalysts with a transition metal- containing aluminophosphate/small pore zeolite catalyst after relatively severe lean hydrothermal ageing performed on a laboratory reactor;
  • Figure 5 is a graph showing NO x conversion for fresh Cu/Zeolite catalysts;
  • Figure 6 is a graph showing NO x conversion for aged Cu/Zeolite catalysts
  • Figure 7 is a graph showing N 2 O formation for fresh Cu/Zeolite catalysts of Figure 5;
  • Figure 8 is a graph showing N 2 O formation for aged Cu/Zeolite catalysts of Figure 6;
  • Figure 9 is a graph showing the effect of adding HC species to Cu/zeolite catalysts during NH 3 SCR at 300°C; . ⁇
  • Figure 10 is a graph showing hydrocarbon breakthrough following addition of hydrocarbon species to Cu/zeolite catalysts during NH 3 SCR at 30O 0 C;
  • Figure 11 is a graph showing the adsorption profiles of n-octane at 150 0 C flowing through the Cu zeolite catalysts;
  • Figure 12 is a graph of the temperature programmed desorption (TPD) of HC species to Cu/zeolite catalysts after HC adsorption at 150 0 C;
  • Figure 13 is a graph similar to Figure 6 comparing NO x conversion activity for aged Cu/Sigma-1, Cu-SAPO-34, Cu/SSZ-13 and Cu/Beta;
  • Figure 14 is a graph similar to Figure 8 comparing N 2 O formation for the aged Cu/zeolite catalysts of Figure 13;
  • Figure 15 is a graph similar to Figure 13 comparing NO x conversion activity for aged Cu/ZSM-34, Cu/SAPO-34, Cu/SSZ-13 and Cu/Beta catalysts;
  • Figure 16 is a graph comparing the NO x conversion activity of fresh and aged Cu-SAPO-
  • Figure 17 is a graph comparing the NO x conversion activity of fresh samples of Cu/SAPO-34 with a Cu/naturally occurring chabazite type material
  • Figure 18 is a bar chart comparing the NO x conversion activity of fresh Cu/SAPO-34 with that of two fresh Cu/naturally occurring chabazite type materials at two temperature data points;
  • Figure 19 is a bar chart comparing the NO x conversion activity of aged Cu/Beta, Cu/SAPO-34, Fe/SAPO-34 and Fe/SSZ-13 catalysts at two temperature data points;
  • Figure 20 is a bar chart comparing the hydrocarbon inhibition effect of introducing n- octane into a feed gas for fresh Fe/Beta and Fe/SSZ-13 catalysts;
  • Figure 21 is a graph showing hydrocarbon breakthrough following the introduction of n- octane in the experiment of Figure 20;
  • Figure 22 is a bar chart comparing the effect on NO x conversion activity for a fresh
  • Figure 23 is a schematic diagram of an embodiment of an exhaust system according to the present invention.
  • FIG 23 is a schematic diagram of an embodiment of an exhaust system according to the present invention, wherein diesel engine 12 comprises an exhaust system 10 according to the present invention comprising an exhaust line 14 for conveying an exhaust gas from the engine to atmosphere via tailpipe 15.
  • an exhaust line 14 for conveying an exhaust gas from the engine to atmosphere via tailpipe 15.
  • a platinum or platinum/palladium NO oxidation catalyst 16 coated on a ceramic flow-through substrate monolith.
  • a ceramic wall- flow filter 18 Located downstream of oxidation catalyst 16 in the exhaust system is a ceramic wall- flow filter 18.
  • An iron/small pore zeolite SCR catalyst 20 also coated on a ceramic flow-through substrate monolith is disposed downstream of the wall-flow filter 18.
  • An NH 3 oxidation cleanup or slip catalyst 21 is coated on a downstream end of the SCR catalyst monolith substrate.
  • the NH 3 slip catalyst can be coated on a separate substrate located downstream of the SCR catalyst.
  • Means (injector 22) is provided for introducing nitrogenous reductant fluid (urea 26) from reservoir 24 into exhaust gas carried in the exhaust line 14. Injector 22 is controlled using valve 28, which valve is in turn controlled by electronic control unit 30 (valve control represented by dotted line).
  • Electronic control unit 30 receives closed loop feedback control input from a NO x sensor 32 located downstream of the SCR catalyst-
  • the oxidation catalyst 16 passively oxidises NO to NO 2 , particulate matter is trapped on filter 18 and is combusted in NO 2.
  • NO x emitted from the filter is reduced on the SCR catalyst 20 in the presence of ammonia derived from urea injected via injector 22. It is also understood that mixtures of NO and NO 2 in the total NO x content of the exhaust gas entering the SCR catalyst (about 1 :1) are desirable for NO x reduction on a SCR catalyst as they are more readily reduced to N 2 .
  • the NH 3 slip catalyst 21 oxidises NH 3 that would otherwise be exhausted to atmosphere. A similar arrangement is described in WO 99/39809.
  • Example 1 Method of making fresh 5wt% Fe/BetaBeta or SAPO-34 or 3wt% SSZ-13 zeolite catalyst
  • Beta zeolite, SAPO-34 or SSZ-13 was NH 4 + ion exchanged in a solution of NH 4 NO 3 , then filtered. The resulting material was added to an aqueous solution of Fe(NOs) 3 with stirring. The slurry was filtered, then washed and dried. The procedure can be repeated to achieve a desired metal loading. The final product was calcined.
  • SAPO-34, SSZ-13, Sigma-1, ZSM-34, Nu-3, ZSM-5 and Beta zeolites were NH 4 + ion exchanged in a solution of NH 4 NO 3 , then filtered. The resulting materials were added to an aqueous solution of Cu(NO 3 ) 2 with stirring. The slurry was filtered, then washed and dried. The procedure can be repeated to achieve a desired metal loading. The final product was calcined.
  • Example 4 Severe Lean Hydrothermal Ageing
  • the catalysts obtained by means of Examples 1 and 2 were severely lean hydrothermally ⁇ 5 aged at 900°C for 1 hour in 4.5% H 2 O/air mixture.
  • the catalysts obtained by means of Examples 1 and 2 were severely lean hydrothermally 10 aged at 900°C for a period of 3 hours in 4.5% H 2 O/air mixture.
  • Example 8 Results for experiments shown in Figures 1 to 4 inclusive
  • Figure 1 compares the NO x reduction efficiencies of a Cu/SAPO-34 catalyst against a series of aluminosilicate zeolite supported transition metal catalysts (Cu/ZSM-5, Cu/Beta and Fe/Beta) after a mild aging.
  • Cu/SAPO-34 has improved low temperature activity for SCR OfNO x with NH 3 .
  • Figure 2 compares the N 2 O formation over the catalysts. It is clear that the Cu/SAPO-34 catalyst produced lower levels OfN 2 O compared to the other two Cu-containing catalysts.
  • the Fe- containing catalyst also exhibits low N 2 O formation, but as shown in Figure 1 , the Fe catalyst is less active at lower temperatures.
  • Figure 3 compares the NO x reduction efficiencies of a Cu/SAPO-34 catalyst against a Cu/Beta catalyst tested at a higher gas hourly space velocity.
  • the Cu/SAPO-34 catalyst is significantly more active than the Cu-Beta catalyst at low reaction temperatures.
  • Figure 4 shows the NO x reduction efficiencies of a Cu/SAPO-34 catalyst and a series of aluminosilicate zeolite supported transition metal catalysts (Cu/ZSM-5, Cu/Beta, and Fe/Beta) after severe lean hydrothermal aging.
  • Cu/SAPO-34 catalyst has superior hydrothermal stability.
  • N 2 O formation measured for the fresh and aged catalysts is shown in Figures 7 and 8, respectively.
  • Figure 9 compares the effect of HC on Cu/zeolite catalysts where SAPO-34 and Nu-3 are used as examples of small pore zeolite materials.
  • ZSM-5 and Beta zeolite are used as examples of a medium and large pore zeolite, respectively.
  • Samples were exposed to different HC species (propene, n-octane and toluene) during NH 3 SCR reaction at 300°C.
  • Figure 10 shows the corresponding HC breakthrough following HC addition.
  • Figure 11 shows the adsorption profiles of n-octane at 150°C flowing through different
  • Cu/SSZ-13, Cu/SAPO-34, Cu/Sigma-1 and Cu/Beta prepared according to Example 2 were aged in the manner described in Example 4 and tested according to Example 6.
  • the results are shown in Figure 13, from which it can be seen that the NO x conversion activity of each of the severely lean hydrothermally aged Cu/SSZ-13, Cu/SAPO-34 and Cu/Sigma-1 samples is significantly better than that of the corresponding large-pore zeolite, Cu/Beta.
  • Figure 14 it can be seen that Cu/Beta generates significantly more N 2 O than the Cu/small-pore zeolite catalysts.
  • Cu/ZSM-34, Cu/SAPO-34, Cu/SSZ-13 and Cu/Beta prepared according to Example 2 were aged in the manner described in Example 3 and tested according to Example 6. The results are shown in Figure 15, from which it can be seen that the NO x conversion activity of each of the lean hydrothermally aged Cu/SSZ-13, Cu/SAPO-34 and Cu/ZSM-34 samples is significantly better than that of the corresponding large-pore zeolite, Cu/Beta.
  • Cu/SAPO-34 and a Cu/naturally occurring chabazite type material having a SAR of about 4 were prepared according to Example 2 and the fresh materials were tested according to Example 6. The results are shown in Figure 17, from which it can be seen that the NO x conversion activity of the naturally occurring Cu/chabazite is significantly lower than Cu/SAPO- 34.
  • Figure 18 is a bar chart comparing the NO x conversion activity of two fresh Cu/naturally occurring chabazite type materials prepared according to Example 2 at two temperature data points (200 0 C and 30O 0 C) 3 a first chabazite material having a SAR of about 4 and a second chabazite material of SAR about 7.
  • Cu/SAPO-34 and Cu/Beta were prepared according to Example 2.
  • Fe/SAPO-34 and Fe/SSZ-13 were prepared according to Example 1. The samples were aged according to
  • Example 4 and the aged samples were tested according to Example 6.
  • the NO x activity at the 350 0 C and 450°C data points is shown in Figure 19, from which it can be seen that the Cu/SAPO-34, Fe/SAPO-34 and Fe/SSZ-13 samples exhibit comparable or better performance than the Cu/Beta reference.
  • Fe/SSZ-13 and Fe/Beta prepared according to Example 1 were tested fresh as described in Example 7, wherein n-octane (to replicate the effects of unburned diesel fuel in a,exhaust gas) was introduced at 8 minutes into the test.
  • the results shown in Figure 20 compare the NOx conversion activity at 8 minutes into the test* but before n-octane was introduced into the feed gas (HC-) and 8 minutes after n-octane was introduced into the feed gas (HC+). It can be seen that the Fe/Beta activity dramatically reduces following n-octane introduction compared with Fe/SSZ-13. We believe that this effect results from coking of the catalyst.
  • Fe/SSZ-13 prepared according to Example 1 was tested fresh, i.e. without ageing, in the manner described in Example 6. The test was then repeated using identical conditions, except in that the 350ppm NO was replaced with a mixture of 175ppm NO and 175ppm NO 2 , i.e. 350ppm total NO x . The results from both tests are shown in Figure 22, from which the significant improvement obtainable from increasing the NO 2 content OfNO x in the feed gas to 1 : 1 can be seen.
  • the NOrNO 2 ratio can be adjusted by oxidising NO in an exhaust gas, e.g. of a diesel engine, using a suitable oxidation catalyst located upstream of the NH 3 -SCR catalyst.

Abstract

A method of converting nitrogen oxides in a gas to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the' presence of a zeolite catalyst containing at least one transition metal, wherein the zeolite is a small pore zeolite containing a maximum ring size of eight tetrahedral atoms, wherein the at least one transition metal is selected from the group consisting of Cr, Mn, Fe, Co, Ce, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir and Pt.

Description

TRANSITION METAL/ZEOLITE SCR CATALYSTS
The present invention relates to a method of converting nitrogen oxides in a gas, such as an exhaust gas of a vehicular lean-burn internal combustion engine, to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a transition metal-containing zeolite catalyst.
Selective catalytic reduction (SCR) OfNOx by nitrogenous compounds, such as ammonia or urea, was first developed for treating industrial stationary applications. SCR technology was first used in thermal power plants in Japan in the late 1970s, and has seen widespread application in Europe since the mid-1980s. In the USA, SCR systems were introduced for gas turbines in the 1990s and have been used more recently in coal-fired powerplants. In addition to coal-fired cogeneration plants and gas turbines, SCR applications include plant and refinery heaters and boilers in the chemical processing industry, furnaces, coke ovens, municipal waste plants and incinerators. More recently, NOx reduction systems based on SCR technology are being developed for a number of vehicular (mobile) applications in Europe, Japan, and the USA, e.g. for treating diesel exhaust gas.
Several chemical reactions occur in an NH3 SCR system, all of which represent desirable reactions that reduce NOx to nitrogen. The dominant reaction is represented by reaction (1).
4NO + 4NH3 + O2 → 4N2 + 6H2O (1)
Competing, non-selective reactions with oxygen can produce secondary emissions or may unproductively consume ammonia. One such non-selective reaction is the complete oxidation of ammonia, shown in reaction (2).
4NH3 + 5O2 → 4NO + 6H2O (2)
Also, side reactions may lead to undesirable products such as N2O, as represented by reaction (3).
4NH3 + 5NO + 3O2 → 4N2O + 6H2O (3) Aluminosilicate zeolites are used as catalysts for SCR of NOx with NH3. One application is to control NOx emissions from vehicular diesel engines, with the reductant obtainable from an ammonia precursor such as urea or by injecting aramorήaper se. To promote the catalytic activity, transition metals are incorporated into the aluminosilicate zeolites. The most commonly tested transition metal zeolites are Cu/ZSM-5, Cu/Beta, Fe/ZSM-5 and Fe/Beta because they have a relatively wide temperature activity window. In general, Cu-based zeolite catalysts show better low temperature NOx reduction activity than Fe-based zeolite catalysts.
However, in use, ZSM-5 and Beta zeolites have a number of drawbacks. They are susceptible to dealumination during high temperature hydrotheπήal ageing resulting in a loss of acidity, especially with Cu/Beta and Cu/ZSM-5 catalysts. Both Beta- and ZSM-5-based catalysts are also affected by hydrocarbons which become adsorbed on the catalysts at relatively low temperatures and ar,e oxidised as the temperature of the catalytic system is raised generating a significant exotherm, which can thermally damage the catalyst. This problem is particularly acute in vehicular diesel applications where significant quantities of hydrocarbon can be adsorbed on the catalyst during cold-start; and Beta and ZSM-5 zeolites are also prone to coking by hydrocarbons.
In general, Cu-based zeolite catalysts are less thermally durable, and produce higher levels OfN2O than Fe-based zeolite catalysts. However, they have a desirable advantage in that they slip less ammonia in. use compared with a corresponding Fe-zeolite catalyst.
It has been reported that aluminophosphate zeolites that contain transition metals demonstrate enhanced catalytic activity and superior thermal stability than aluminosilicate zeolite catalysts for SCR OfNOx with hydrocarbons (also known as lean NOx catalysis or "DeNOx catalysts" (e.g. Ishihara et ah, Journal of Catalysis, 169 (1997) 93)). In a similar vein, WO
2006/064805 discloses an electrical processing technology for treating diesel engine exhaust gas which utilizes corona discharge. A combination of a device for adding a NOx reducer (hydrocarbon or fuel) and a Cu-SAPO-34 NOx reducing catalyst can be disposed downstream of the electrical processing apparatus. However, to our knowledge, there has been no investigation of transition metal-containing aluminophosphate zeolites for SCR of NOx with NH3 (or urea) reported in any literature to date. •
WO 00/72965 discloses iron (Fe) exchanged zeolites for the selective catalytic reduction of nitrogen monoxide by ammonia for controlling NOx emissions from fossil-fuel power plants and engines. The Fe-exchanged, and optionally Fe-rare earth-exchanged, e.g. Fe-Ce-exchanged, zeolites suggested include: ZSM-5, mordenite, SAPO, clinoptilolite, chabazite, ZK-4 and ZK-5. No specific SAPO zeolites are identified and no experiment using SAPO zeolites is disclosed. Moreover, WO '965 teaches that the disclosure has application to zeolites with a range of pore sizes, i.e. large (mordenite), medium (ZSM-5, clinoptilolite) and small (chabazite, ZK-4, ZK-5) pore zeolites, with Fe-ZSM-5 preferred. There is no teaching or suggestion of any advantage in the use of small pore zeolites compared with medium and large pore zeolites. Moreover, ZK-4 zeolite is potentially hydrothermally unstable.
US patent no. 4,735,927 discloses an extruded-type NH3-SCR catalyst with stability to sulfur poisoning comprising a high surface area titania in the form of anatase and a natural or synthetic zeolite. The zeolite must be either in the acid form or thermally convertible to the acid form in the catalytic product. Examples of suitable zeolites include mordenite, natural clinoptilolite, erionite, heulandite, ferrierite, natural faujasite or its synthetic counterpart zeolite Y, chabazite and gmelinite. A preferred zeolite is natural clinoptilolite, which may be mixed with another acid stable zeolite such as chabazite. The catalyst may optionally include small amounts (at least 0.1% by elemental weight) of a promoter in the form of precursors of vanadium oxide, copper oxide, molybdenum oxide or combinations thereof (0.2 wt% Cu and up to 1.6 wt% V are exemplified). Extruded-type catalysts are generally less durable, have lower chemical strength, require more catalyst material to achieve the same activity and are more complicated to manufacture than catalyst coatings applied to inert monolith substrates.
US patent no. 5,417,949 also discloses an extruded-type NH3-SCR catalyst comprising a zeolite having a constraint index of up to 12 and a titania binder. Intentionally, no transition metal promoter is present. ("Constraint Index" is a test to determine shape-selective catalytic behaviour in zeolites. It compares the reaction rates for the cracking of n-hexane and its isomer 3-methylpentane under competitive conditions (see VJ. Frillette et al., J Catal. 67 (1991) 218)).
US patent no. 5,589,147 discloses an ammonia SCR catalyst comprising a molecular sieve and a metal, which catalyst can be coated on a substrate monolith. The molecular sieve ■ useful in the invention is not limited to any particular molecular sieve material and, in general, includes all metallosilicates, metallophosphates, silicoaluminophosphates and layered and pillared layered materials. The metal is typically selected from at least one of the metals of Groups of the Periodic Table IIIA, IB, IIB, VA, VIA, VILA, VIIIA and combinations thereof. Examples of these metals include at least one of copper, zinc, vanadium, chromium, manganese, cobalt, iron, nickel, rhodium, palladium, platinum, molybdenum, tungsten, cerium and mixtures thereof.
The disclosure of US 5,589,147 is ambiguous about whether small pore zeolites (as defined herein) have any application in the process of the invention. For example, on the one hand, certain small pore zeolites are mentioned as possible zeolites for use in the invention, i.e. erionite and chabazite, while, among others, the molecular sieve SAPO-34 was "contemplated". On the other hand a table is presented listing Constraint Index (CI) values for some typical zeolites "including some which are suitable as catalysts in the process of this invention". , The vast majority of the CI values in the table are well below 10, of which erionite (38 at 316°C) and ZSM-34 (50 at 3710C) are notable exceptions. However, what is clear is that intermediate pore size zeolites, e.g. those having pore sizes of from about 5 to less than 7 Angstroms, are preferred in the process of the invention. In particular, the disclosure explains that intermediate pore size zeolites are preferred because they provide constrained access to and egress from the intracrystalline free space: "The intermediate pore size zeolites...have an effective pore size such as to freely sorb normal hexane...if the only pore windows in a crystal are formed by 8- membered rings of oxygen atoms, then access to molecules of larger cross-section than normal hexane is excluded and the zeolite is not an intermediate pore size material." Only extruded Fe- ZSM-5 is exemplified.
WO 2004/002611 discloses an NH3-SCR catalyst comprising a ceria-doped aluminosilicate zeolite.
US 6,514,470 discloses a process for catalytically reducing NOx in an exhaust gas stream containing nitrogen oxides and a reductant material. The catalyst comprises an aluminium- silicate material and a metal in an amount of up to about 0.1 weight percent based on'the total weight of catalyst. All of the examples use ferrierite.
Long et al Journal of Catalysis 207 (2002) 274-285 reports on studies of Fe3+-exchanged zeolites for selective catalytic reduction of NO with ammonia. The zeolites investigated were mordenite, clinoptilolite, Beta, ferrierite and chabazite. It was found that in the conditions studied that the SCR activity decreases in the following order: Fe-mordenite > Fe-clinoptilolite > Fe-feπierite > Fe-Beta > Fe-chabazite. The chabazite used for making the Fe-chabazite was a naturally occurring mineral.
US patent no. 4,961,917 discloses an NH3-SCR catalyst comprising a zeolite having a silica-to-alumina ratio of at least about 10, and a pore structure which is interconnected in all three crystallographic dimensions by pores having an average kinetic pore diameter of at least about 7 Angstroms and a Cu or Fe promoter. The catalysts are said to have high activity, reduced NH3 oxidation and reduced sulphur poisoning. Zeolite Beta and zeolite Y are two zeolites that meet the required definition.
US patent no. 3,895,094 discloses an NH3-SCR process using zeolite catalysts of at least 6 Angstrom intercrystalline.pore size. No mention is made of exchanging the zeolites with transition metals.
US patent no. 4,220,632 also discloses an NH3-SCR process, this time using 3-10
Angstrom pore size zeolites of Na or H form.
WO 02/41991 discloses metal promoted zeolite Beta for NH3-SCR, wherein the zeolite is pre-treated so as to provide it with improved hydrothermal stability.
There is a need in the art for SCR catalysts that have relatively good low temperature SCR activity, that have relatively high selectivity to N2 - in particular low N2O formation, that have relatively good thermal durability and are relatively resistant to hydrocarbon inhibition. We have now discovered a family of transition metal-containing zeolites that meet or contribute to this need.
According to one aspect, the invention provides a method of converting nitrogen oxides in a gas to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a zeolite catalyst containing at least one transition metal, wherein the zeolite is a small pore zeolite containing a maximum ring size of eight tetrahedral atoms, wherein the at least one transition metal is selected from the group consisting of Cr, Mn, Fe5 Co, Ce, Ni, Cu5 Zn, Ga, Mo, Ru, Rh, Pd5 Ag5 In, Sn5 Re5 Ir and Pt. By "zeolite catalyst containing at least one transition metal" herein we mean a zeolite structure to which has been added by ion exchange, impregnation or isomorphous substitution etc. one or more metals. "Transition metal-containing zeolite catalyst" and "zeolite catalyst containing at least one transition metal" and similar terms are used interchangeably herein.
It will be appreciated that by defining the zeolites by their Framework Type Codes we intend to include the "Type Material" and any and all isotypic framework materials. (The "Type Material" is the species first used to establish the framework type). Reference is made to Table 1, which lists a range of illustrative zeolite zeotype framework materials for use in the present invention. For the avoidance of doubt, unless otherwise made clear, reference herein to a zeolite by name, e.g. "chabazite", is to the zeolite material per se (in this example the naturally occurring type material chabazite) and not to any other material designated by the Framework Type Code to which the individual zeolite may belong, e.g. some other isotypic framework material. So for example, where the attached claims disclaim a zeolite catalyst, this disclaimer should be interpreted narrowly, so that "wherein the transition metal-containing small pore zeolite is not Cu/chabazite" is intended to exclude the type material and not any isotypic framework materials such as SAPO-34 or SSZ-13. Equally, use of a FTC herein is intended to refer to the Type Material and all isotypic framework materials defined by that FTC. For further information, we direct the reader to the website of the International Zeolite Association at www.iza-online.org.
The distinction between zeolite type materials, such as naturally occurring (i.e. mineral) chabazite, and isotypes within the same Framework Type Code is not merely arbitrary, but reflects differences in the properties between the materials, which may in turn lead to differences in activity in the method of the present invention. For example, in addition to the comments made hereinbelow with reference to Long et al. Journal of Catalysis 207 (2002) 274-285, the naturally occurring chabazite has a lower silica-to-alumina ratio than aluminosilicate isotypes such as SSZ-13, the naturally occurring chabazite has lower acidity than aluminosilicate isotypes such as SSZ-13 and the activity of the material in the method of the present invention is relatively low (see the comparison of Cu/naturally occurring chabazite with Cu/SAPO-34 in Example 13).
The zeolite catalysts for use in the present invention can be coated on a suitable substrate monolith or can be formed as extruded-type catalysts, but are preferably used in a catalyst coating. Whilst the prior art (such as the documents discussed in the background section hereinabove) does mention a few small pore zeolites containing at least one transition metal for converting nitrogen oxides in a gas to nitrogen with a nitrogenous reducing agent, there is no appreciation in the prior art that we can find of the particular advantages of using small pore zeolites containing at least one transition metal for this purpose. Thus, the prior art suggests using large, medium and small pore zeolites containing at least one transition metal, without distinction. Accordingly, we seek to exclude any specific small pore zeolites containing at least one transition metal that have been mentioned only in this context.
hi this regard, in one embodiment, the zeolite catalyst is not one of Co, Ga, Mn, In or Zn or any combination of two or more thereof/epistilbite (see US patent no. 6,514,470). In another embodiment, the transition metal-containing small pore zeolite is not Cu/chabazite, Mo/chabazite, Cu-Mo/chabazite, Cu/erionite, Mo/erionite or Cu-Mo/erionite (see US patent no. 4,735,927). In a further embodiment^ the transition metal-containing small pore zeolite is not Ce/erionite (see WO 2004/002611). hi a further embodiment, the transition metal-containing small pore zeolite is not Fe/chabazite, Fe/ZK-5, Fe/ZK-4, Fe-rare-earth/chabazite, Fe-rare-earth/ZK-5 or Fe-rare- earth/ZK-4 (see WO 00/72965). Furthermore, although WO 00/72965 discloses the use of Ce/SAPO zeolites and Ce-rare-earth/SAPO zeolites in general, it does not disclose any particular small pore SAPO zeolites with application in the present invention, such as SAPO- 17, SAPO- 18, SAPO-34, SAPO-35, SAPO-39, SAPO-43 and SAPO-56. hi yet a further embodiment, the transition metal-containing small pore zeolite is not Fe/chabazite, (see Long et al. Journal of Catalysis 207 (2002) 274-285). Whilst, for the reasons given hereinabove, we do not believe that US patent no. 5,589,147 discloses the use of small pore zeolites containing at least one transition metal according the method of the present invention, for safety, according to another embodiment, the zeolite catalyst is not any one of copper, zinc, chromium, manganese, cobalt, iron, nickel, rhodium, palladium, platinum, molybdenum, cerium or mixtures thereof/any one of aluminosilicate chabazite, aluminosilicate erionite, aluminosilicate ZSM-34 and SAPO-34. hi another embodiment, the transition metal-containing zeolite catalyst is not LTA or Fe/CHA.
It will be appreciated that chabazite is a small pore zeolite according to the definition adopted herein and that the Long et al. paper mentioned above reports that Fe/chabazite has the poorest activity of any of the catalysts tested. Without wishing to be bound by any theory, we believe that the poor performance of the Fe/chabazite in this study is due to two principal reasons. Firstly, natural chabazite can contain basic metal cations including potassium, sodium, strontium and calcium. To obtain an active material the basic metal cations need to be exchanged for e.g. iron cations because basic metals are a known poison of zeolite acid sites. In the reported study the natural mineral is first treated with NH4Cl solution in an attempt to "flush out" the existing cations. However, we believe that one explanation for the poor reported activity is that the acidic sites in the chabazite of this study remain poisoned by basic metal cations.
Secondly, iron ions can form metal complexes (coordination compounds) with suitable ligands in the ionic exchange medium. In this regard we note .that Long et al. use an aqueous FeCl2 solution for ion exchange. Since the zeolite pores are relatively small, it is possible that a bulky co-ordination compound may not be able to gain access to the active sites located in the pores.
It will be appreciated, e.g. from Table 1 hereinbelow that by "MeAPSO" and "MeAlPO" we intend zeotypes substituted with one or more metals. . Suitable substituent metals include one or more of, without limitation, As, B, Be, Co, Fe, Ga, Ge, Li, Mg, Mn, Zn and Zr.
In a particular embodiment, the small pore zeolites for use in the present invention can be selected from the group consisting of aluminosilicate zeolites, metal-substituted aluminosilicate zeolites and aluminophosphate zeolites.
Aluminophosphate zeolites with application in the present invention include aluminophosphate (AlPO) zeolites, metal substituted zeolites (MeAh0O) zeolites, silico- aluminophosphate (SAPO) zeolites and metal substituted silico-aluminophosphate (MeAPSO) zeolites.
It will be appreciated that the invention extends to catalyst coatings and extruded-type substrate monoliths comprising both transition metal-containing small pore zeolites according to the invention and non-small pore zeolites (whether metallised or not) such as medium-, large- and meso-pore zeolites (whether containing transition metal(s) or not) because such a combination also obtains the advantages of using small pore zeolites per se. It should also be understood that the catalyst coatings and extruded-type substrate monoliths for use in the invention can comprise combinations of two or more transition metal-containing small pore zeolites. Furthermore, each small pore zeolite in such a combination can contain one or more transition metals, each being • selected from the group defined hereinabove, e.g. a first small pore zeolite can contain both Cu and Fe and a second small pore zeolite in combination with the first small pore zeolite can contain Ce.
In this invention, we have discovered that transition metal-containing small pore zeolites are advantageous catalysts for SCR ofNOx with NH3. Compared to transition metal-containing medium, large or meso-pore zeolite catalysts, transition metal-containing small pore zeolite catalysts demonstrate significantly improved NOx reduction activity, especially at low temperatures. They also exhibit high selectivity to N2 (e.g. low N2O formation) and good hydrothermal stability. Furthermore, small pore zeolites containing at least one transition metal. are more resistant to hydrocarbon inhibition than larger pore zeolites, e.g. a medium pore zeolite (a zeolite containing a maximum ring size of 10) such as ZSM-5 or a large pore zeolite (a zeolite having a maximum ring size of 12), such as Beta. Small pore aluminophosphate zeolites for use in the present invention include SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-39, SAPO-43 and SAPO-56.
In one embodiment, the small pore zeolite is selected from the group of Framework Type Codes consisting of: ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG and ZON.
Zeolites with application in the present invention can include those that have been treated to improve hydrothermal stability. Illustrative methods of improving hydrothermal stability include: ' (i) Dealumination by: steaming and acid extraction using an acid or complexing agent e.g. (EDTA - ethylenediaminetetracetic acid); treatment with acid and/or complexing agent; treatment with a gaseous stream of SiCl4 (replaces Al in the zeolite framework with Si);
(ii) Cation exchange - use of multi-valent cations such as La; and
(iii) Use of phosphorous containing compounds (see e.g. US patent no. 5,958,818).
We believe that small pore zeolites may minimise the detrimental effect of hydrocarbons by means of a molecular sieving effect, whereby the small pore zeolite allows NO and NH3 to diffuse to the active sites inside the pores but that the diffusion of hydrocarbon molecules is restricted. In this regard, the kinetic diameter of both NO (3.16A) and NH3 (2.6A) is smaller than those of the typical hydrocarbons (C3H6 ~ 4.5A, H-C8H18 -4.30A and C7H8 ~ 6.0A) present in, for example, diesel engine exhaust. Accordingly, in one embodiment the small pore zeolite catalysts for use in the present invention have a pore size in at least one dimension of less than 4.3 A. Illustrative examples of suitable small pore zeolites are set out in Table 1.
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Small pore zeolites with particular application for treating NOx in exhaust gases of lean- burn internal combustion engines, e.g. vehicular exhaust gases are set out in Table 2.
Table 2: Preferred small pore zeolites for use in treating exhaust gases of lean-burn internal combustion engines.
Figure imgf000019_0001
Small pore aluminosilicate zeolites for use in the present invention can have a silica-to- alumina ratio (SAR) of from 2 to 300, optionally 4 to 200 and preferably 8 to 150. It will be appreciated that higher SAR ratios are preferred to improve thermal stability but this may negatively affect transition metal exchange. Therefore, in selecting preferred materials consideration can be given to SAR so that a balance may be struck between these two properties.
The gas containing the nitrogen oxides can. contact the zeolite catalyst at a gas hourly space velocity of from 5,000 hr"1 to 500,000 hr'1, optionally from 10,000 hr"1 to 200,000 hr"1.
In one embodiment, the small pore zeolites for use in the present invention do not include aluminophosphate zeolites as defined herein. In a further embodiment, the small pore zeolites (as defined herein) for use in the present invention are restricted to aluminophosphate zeolites (as defined herein). In a further embodiment, small pore zeolites for use in the present invention are aluminosilicate zeolites and metal substituted aluminosilicate zeolites (and not aluminophosphate zeolites as defined herein).
Small pore zeolites for use in the invention can have three-dimensional dimensionality, i.e. a pore structure which is interconnected in all three crystallographic dimensions, or two- dimensional dimensionality, hi one embodiment, the small pore zeolites for use in the present invention consist of zeolites having three-dimensional dimensionality. In another embodiment, the small pore zeolites for use in the present invention consist of zeolites having two- dimensional dimensionality.
In one embodiment, the at least one transition metal is selected from the group consisting of Cr, Ce, Mn, Fe, Co, Ni and Cu. In a preferred embodiment, the at least one transition metal is selected from the group consisting of Cu, Fe and Ce. In a particular embodiment, the at least one transition metal consists of Cu. In another particular embodiment, the at least one transition metal consists of Fe. In a further particular embodiment, the at least one transition metal is Cu and/or Fe.
The total of the at least one transition metal that can be included in the at least one transition metal-containing zeolite can be from 0.01 to 20 wt%, based on the total weight of the zeolite catalyst containing at least one transition metal. In one embodiment, the total of the at least one transition metal that can be included can be from 0.1 tol 0wt%. In a particular embodiment, the total of the at least one transition metal that can be included is from 0.5 to 5wt%. A preferred transition metal-containing two dimensional small pore zeolite for use in the present invention consists of Cu/LEV, such as Cu/Nu-3, whereas a preferred transition metal- containing three dimensional small pore zeolite/aluminophosphate zeolite for use in the present invention consists of Cu/CHA, such as Cu/SAPO-34 or Cu/SSZ-13. In another embodiment, particularly where a ratio of NO/NO2 is adjusted, e.g. by using a suitable oxidation catalyst (see hereinbelow) to about 1:1, Fe-containing zeolite catalysts are preferred, such as Fe-CHA, e.g. Fe/SAPO-34 or Fe/SSZ-13. Preliminary analysis indicates that Cu/SSZ-13 and Cu/Nu-3 are more resistant than the equivalent Cu/SAPO-34 to extended severe high temperature lean hydrothermal ageing (900°C for 3 hours in 4.5% H2O/air mixture cf. Example 4).
The at least one transition metal can be included in the zeolite by any feasible method. For example, it can be added after the zeolite has been synthesised, e.g. by incipient wetness or exchange process; or the at least one metal can be added during zeolite synthesis.
The zeolite catalyst for use in the present invention can be coated, e.g. as a washcoat component, on a suitable monolith substrate, such as a metal or ceramic flow through monolith substrate or a filtering substrate, such as a wall-flow filter or sintered metal or partial filter (such as is disclosed in WO 01/80978 or EP 1057519, the latter document describing a substrate comprising convoluted flow paths that at least slows the passage of soot therethrough).
Alternatively, the zeolites for use in the present invention can be synthesized directly onto the substrate. Alternatively, the zeolite catalysts according to the invention can be formed into an extruded-type flow through catalyst.
The small pore zeolite catalyst containing at least one transition metal for use in the present invention is coated on a suitable monolith substrate. Washcoat compositions containing the zeolites for use in the present invention for coating onto the monolith substrate for manufacturing extruded type substrate monoliths can comprise a binder selected from the group consisting of alumina, silica, (non zeolite) silica-alumina, naturally occurring clays, TiO2, ZrO2, and SnO2.
In one embodiment, the nitrogen oxides are reduced with the reducing agent at a temperature of at least 100°C. In another embodiment, the nitrogen oxides are reduced with the reducing agent at a temperature from about 150°C to 750°C. The latter embodiment is particularly useful for treating exhaust gases from heavy and light duty diesel engines, particularly engines comprising exhaust systems comprising (optionally catalysed) diesel particulate filters which are regenerated actively, e.g. by injecting hydrocarbon into the exhaust system upstream of the filter, wherein the zeolite catalyst for use in the present invention is located downstream of the filter.
In a particular embodiment, the temperature range is from 175 to 550°C. hi another embodiment, the temperature range is from 175 to 400°C.
In another embodiment, the nitrogen oxides reduction is carried out in the presence of oxygen. In an alternative embodiment, the nitrogen oxides reduction is carried out in the absence of oxygen.
Zeolites for use in the present application include natural and synthetic zeolites, preferably synthetic zeolites because the zeolites can have a more uniform: silica-to-alumina ratio (SAR), crystallite, size, crystallite morphology, and the absence of impurities (e.g. alkaline earth metals).
The source of nitrogenous reductant can be ammorήaper se, hydrazine or any suitable ammonia precursor, such as urea
Figure imgf000022_0001
ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate.
The method can be performed on a gas derived from a combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine and coal or oil fired power plants. The method may also be used to treat gas from industrial processes such as refining, from refinery heaters and boilers, furnaces, the chemical processing industry, coke ovens, municipal waste plants and incinerators, coffee roasting plants etc.
In a particular embodiment, the method is used for treating exhaust gas from a vehicular lean burn internal combustion engine, such as a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.
According to a further aspect, the invention provides an exhaust system for a vehicular lean burn internal combustion engine, which system comprising a conduit for carrying a flowing exhaust gas, a source of nitrogenous reductant, a zeolite catalyst containing at least one transition metal ■ disposed in a flow path of the exhaust gas and means for metering nitrogenous reductant into a flowing exhaust gas upstream of the zeolite catalyst, wherein the zeolite catalyst is a small pore zeolite containing a maximum ring size of eight tetrahedral atoms, wherein the at least one transition metal is selected from the group consisting of Cr, Mn, Fe3 Co, Ce, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir and Pt.
For the avoidance of doubt, the small pore transition metal-containing zeolites for use in the exhaust system aspect of the present invention include any for use in the method according to the invention as described hereinabove.
In one embodiment, the zeolite catalyst is coated on a flow-through monolith substrate (i.e. a honeycomb monolithic catalyst support structure with many small, parallel channels running axially through the entire part) or filter monolith substrate such as a wall-flow filter etc., as described hereinabove. In another embodiment, the zeolite catalyst is formed into an extruded-type catalyst.
The system can include means, when in use, for controlling the metering means so that nitrogenous reductant is metered into the flowing exhaust gas only when it is determined that the zeolite catalyst is capable of catalysing NOx reduction at or above a desired efficiency, such as at above 100°C, above 15O0C or above 175°C. The determination by the control means can be assisted by one or more suitable sensor inputs indicative of a condition of the engine selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, mass flow of exhaust gas in the system, manifold vacuum, ignition timing, engine speed, lambda value of the exhaust gas, the quantity of fuel injected in the engine, the position of the exhaust gas recirculation (EGR) valve and thereby the amount of EGR and boost pressure.
hi a particular embodiment, metering is controlled in response to the quantity of nitrogen oxides in the exhaust gas determined either directly (using a suitable NOx sensor) or indirectly, such as using pre-correlated look-up tables or maps - stored in the control means - correlating any one or more of the abovementioned inputs indicative of a condition of the engine with predicted NOx content of the exhaust gas. The control means can comprise a pre-programmed processor such as an electronic control unit (ECU).
The metering of the nitrogenous reductant can be arranged such that 60% to 200% of theoretical ammonia is present in exhaust gas entering the SCR catalyst calculated at 1 :1 NH3/NO and 4:3 NH3/NO2;
In a further embodiment, an oxidation catalyst for oxidising nitrogen monoxide in the exhaust gas to nitrogen dioxide can be located upstream of a point of metering the nitrogenous reductant into the exhaust gas. In one embodiment, the oxidation catalyst is adapted to yield a gas stream entering the SCR zeolite catalyst having a ratio of NO to NO2 of from about 4:1 to about 1 :3 by volume, e.g. at an exhaust gas temperature at oxidation catalyst inlet of 250°C to 45O0C. This concept is disclosed in S. Kasaoka et al. "Effect of Inlet NO/NO2 Molar Ratio and Contribution of Oxygen in the Catalytic Reduction of Nitrogen Oxides with Ammonia", Nippon Kagaku Kaishi, 1978, No. 6, pp. 874-881 and WO 99/39809.
The oxidation catalyst can include at least one platinum group metal (or some combination of these), such as platinum, palladium, or rhodium, coated on a flow-through monolith substrate. In one embodiment, the at least one platinum group metal is platinum, palladium or a combination of both platinum and palladium. The platinum group metal can be supported on a high surface area washcoat component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, non-zeolite silica alumina, ceria, zirconia, titania or a mixed or composite oxide containing both ceria and zirconia.
In a further embodiment, a suitable filter substrate is located between the oxidation catalyst and the zeolite catalyst. Filter substrates can be selected from any of those mentioned above, e.g. wall flow filters. Where the filter is catalysed, e.g. with an oxidation catalyst of the kind discussed above, preferably the point of metering nitrogenous reductant is located between the filter and the zeolite catalyst. Alternatively, if the filter is uncatalysed, the means for metering nitrogenous reductant can be located between the oxidation catalyst and the filter. It will be appreciated that this arrangement is disclosed in WO 99/39809.
In a further embodiment, the zeolite catalyst for use in the present invention is coated on a filter located downstream of the oxidation catalyst. Where the filter includes the zeolite catalyst for use in the present invention, the point of metering the nitrogenous reductant is preferably located between the oxidation catalyst and the filter.
In one embodiment, the control means meters nitrogenous reductant into the flowing exhaust gas. only when the exhaust gas temperature is at least 100°C, for example only when the exhaust gas temperature is from 150°C to 75O0C.
Li a further aspect, there is provided a vehicular lean-burn engine comprising an exhaust system according to the present invention.
The vehicular lean burn internal combustion engine can be a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.
hi order that the invention may be more fully understood, reference is made to the following Examples by way of illustration only and with reference to the accompanying drawings, in which:
Figure 1 is a graph showing NOx conversion (at a gas hourly space velocity of 30,000 hr" l) comparing transition metal-containing aluminosilicate catalysts with a transition metal- containing aluminophosphate/small pore zeolite catalyst after relatively moderate lean hydrothermal ageing performed on a laboratory reactor;
Figure 2 is a graph showing N2O formation in the test shown in Figure 1;
Figure 3 is a graph showing NOx conversion (at a gas hourly space velocity of 100,000 hr'1) comparing Cu/Beta zeolite and Cu/SAPO-34 catalysts with a transition metal-containing aluminophosphate/small pore zeolite catalyst after relatively moderate lean hydrothermal ageing performed on a laboratory reactor;
Figure 4 is a graph showing NOx conversion (at a gas hourly space velocity of 30,000 hr" l) comparing transition metal-containing aluminosilicate catalysts with a transition metal- containing aluminophosphate/small pore zeolite catalyst after relatively severe lean hydrothermal ageing performed on a laboratory reactor; Figure 5 is a graph showing NOx conversion for fresh Cu/Zeolite catalysts;
Figure 6 is a graph showing NOx conversion for aged Cu/Zeolite catalysts;
Figure 7 is a graph showing N2O formation for fresh Cu/Zeolite catalysts of Figure 5;
Figure 8 is a graph showing N2O formation for aged Cu/Zeolite catalysts of Figure 6;
Figure 9 is a graph showing the effect of adding HC species to Cu/zeolite catalysts during NH3 SCR at 300°C; . ■
Figure 10 is a graph showing hydrocarbon breakthrough following addition of hydrocarbon species to Cu/zeolite catalysts during NH3 SCR at 30O0C;
Figure 11 is a graph showing the adsorption profiles of n-octane at 1500C flowing through the Cu zeolite catalysts;
Figure 12 is a graph of the temperature programmed desorption (TPD) of HC species to Cu/zeolite catalysts after HC adsorption at 1500C;
Figure 13 is a graph similar to Figure 6 comparing NOx conversion activity for aged Cu/Sigma-1, Cu-SAPO-34, Cu/SSZ-13 and Cu/Beta;
Figure 14 is a graph similar to Figure 8 comparing N2O formation for the aged Cu/zeolite catalysts of Figure 13;
Figure 15 is a graph similar to Figure 13 comparing NOx conversion activity for aged Cu/ZSM-34, Cu/SAPO-34, Cu/SSZ-13 and Cu/Beta catalysts;
Figure 16 is a graph comparing the NOx conversion activity of fresh and aged Cu-SAPO-
34 and Cu/SSZ-13 catalysts;
Figure 17 is a graph comparing the NOx conversion activity of fresh samples of Cu/SAPO-34 with a Cu/naturally occurring chabazite type material; Figure 18 is a bar chart comparing the NOx conversion activity of fresh Cu/SAPO-34 with that of two fresh Cu/naturally occurring chabazite type materials at two temperature data points;
Figure 19 is a bar chart comparing the NOx conversion activity of aged Cu/Beta, Cu/SAPO-34, Fe/SAPO-34 and Fe/SSZ-13 catalysts at two temperature data points;
Figure 20 is a bar chart comparing the hydrocarbon inhibition effect of introducing n- octane into a feed gas for fresh Fe/Beta and Fe/SSZ-13 catalysts;
Figure 21 is a graph showing hydrocarbon breakthrough following the introduction of n- octane in the experiment of Figure 20;
Figure 22 is a bar chart comparing the effect on NOx conversion activity for a fresh
Fe/SSZ-13 catalyst of using 100% NO as a component of the feed gas with using 1:1 NO:NO2;
Figure 23 is a schematic diagram of an embodiment of an exhaust system according to the present invention.
Figure 23 is a schematic diagram of an embodiment of an exhaust system according to the present invention, wherein diesel engine 12 comprises an exhaust system 10 according to the present invention comprising an exhaust line 14 for conveying an exhaust gas from the engine to atmosphere via tailpipe 15. In the flow path of the exhaust gas is disposed a platinum or platinum/palladium NO oxidation catalyst 16 coated on a ceramic flow-through substrate monolith. Located downstream of oxidation catalyst 16 in the exhaust system is a ceramic wall- flow filter 18.
An iron/small pore zeolite SCR catalyst 20 also coated on a ceramic flow-through substrate monolith is disposed downstream of the wall-flow filter 18. An NH3 oxidation cleanup or slip catalyst 21 is coated on a downstream end of the SCR catalyst monolith substrate. Alternatively, the NH3 slip catalyst can be coated on a separate substrate located downstream of the SCR catalyst. Means (injector 22) is provided for introducing nitrogenous reductant fluid (urea 26) from reservoir 24 into exhaust gas carried in the exhaust line 14. Injector 22 is controlled using valve 28, which valve is in turn controlled by electronic control unit 30 (valve control represented by dotted line). Electronic control unit 30 receives closed loop feedback control input from a NOx sensor 32 located downstream of the SCR catalyst-
In use, the oxidation catalyst 16 passively oxidises NO to NO2, particulate matter is trapped on filter 18 and is combusted in NO2. NOx emitted from the filter is reduced on the SCR catalyst 20 in the presence of ammonia derived from urea injected via injector 22. It is also understood that mixtures of NO and NO2 in the total NOx content of the exhaust gas entering the SCR catalyst (about 1 :1) are desirable for NOx reduction on a SCR catalyst as they are more readily reduced to N2. The NH3 slip catalyst 21 oxidises NH3 that would otherwise be exhausted to atmosphere. A similar arrangement is described in WO 99/39809.
EXAMPLES
Example 1 - Method of making fresh 5wt% Fe/BetaBeta or SAPO-34 or 3wt% SSZ-13 zeolite catalyst
Commercially available Beta zeolite, SAPO-34 or SSZ-13 was NH4 + ion exchanged in a solution of NH4NO3, then filtered. The resulting material was added to an aqueous solution of Fe(NOs)3 with stirring. The slurry was filtered, then washed and dried. The procedure can be repeated to achieve a desired metal loading. The final product was calcined.
Example 2 — Method of making fresh 3wt% Cu/zeolites
Commercially available SAPO-34, SSZ-13, Sigma-1, ZSM-34, Nu-3, ZSM-5 and Beta zeolites were NH4 + ion exchanged in a solution of NH4NO3, then filtered. The resulting materials were added to an aqueous solution of Cu(NO3)2 with stirring. The slurry was filtered, then washed and dried. The procedure can be repeated to achieve a desired metal loading. The final product was calcined.
Example 3 - Lean Hydrothermal Ageing
The catalysts obtained by means of Examples 1 and 2 were lean hydrothermally aged at 75O0C for 24 hours in 4.5% H2O/air mixture. Example 4 - Severe Lean Hydrothermal Ageing
The catalysts obtained by means of Examples 1 and 2 were severely lean hydrothermally ■ 5 aged at 900°C for 1 hour in 4.5% H2O/air mixture.
Example 5 - Extended Severe Lean Hvdrothermal Ageing
The catalysts obtained by means of Examples 1 and 2 were severely lean hydrothermally 10 aged at 900°C for a period of 3 hours in 4.5% H2O/air mixture.
Example 6 -Test Conditions
Separate samples of Fe/BetaBeta prepared according to Example 1 and Cu/BetaBeta, 15 Cu/ZSM-5 and Cu/SAPO-34 prepared according to Example 2 were aged according to Examples
3 and 4 and tested in a laboratory apparatus using the following gas mixture: 350ppm NO, 350ppm NH3, 14%O2, 4.5% H2O5 4.5% CO2, N2 balance. The results are shown in Figures 1 to
4 inclusive.
20 Tests were also conducted on Cu/BetaBeta, Cu/ZSM-5, Cu/SAPO-34 and Cu/Nu-3 prepared according to Example 2 and aged according to Example 3 and tested in a laboratory apparatus using the same gas mixture as described above, except in that 12%O2 was used. The results are shown in Figures 5 to 8 inclusive. 5 Example 7 - n-Octane adsorption test conditions
With the catalyst loaded in a laboratory apparatus, lOOOppm (as Cl equivalents) propene, n-octane or toluene was injected during NH3 SCR at 3000C (350ppm NO, 350ppm NH3, 12%O2, 4.5%H20, 4.5%CO2, balance N2). Hydrocarbon desorption was measured by ramping the 0 temperature at 10°C/minute in 12%O2, 4.5%H2O, 4.5%CO2, balance N2.
Example 8 — Results for experiments shown in Figures 1 to 4 inclusive Figure 1 compares the NOx reduction efficiencies of a Cu/SAPO-34 catalyst against a series of aluminosilicate zeolite supported transition metal catalysts (Cu/ZSM-5, Cu/Beta and Fe/Beta) after a mild aging. The result clearly demonstrates that Cu/SAPO-34 has improved low temperature activity for SCR OfNOx with NH3.
Figure 2 compares the N2O formation over the catalysts. It is clear that the Cu/SAPO-34 catalyst produced lower levels OfN2O compared to the other two Cu-containing catalysts. The Fe- containing catalyst also exhibits low N2O formation, but as shown in Figure 1 , the Fe catalyst is less active at lower temperatures.
Figure 3 compares the NOx reduction efficiencies of a Cu/SAPO-34 catalyst against a Cu/Beta catalyst tested at a higher gas hourly space velocity. The Cu/SAPO-34 catalyst is significantly more active than the Cu-Beta catalyst at low reaction temperatures.
Figure 4 shows the NOx reduction efficiencies of a Cu/SAPO-34 catalyst and a series of aluminosilicate zeolite supported transition metal catalysts (Cu/ZSM-5, Cu/Beta, and Fe/Beta) after severe lean hydrothermal aging. The result clearly demonstrates that the Cu/SAPO-34 catalyst has superior hydrothermal stability.
Example 9 - Results for experiments shown in Figures 5 to 12 inclusive
NH3 SCR activity of fresh (i.e. un-aged) Cu supported on the small pore zeolites SAPθ-34 and Nu-3 was compared to that of Cu supported on larger pore zeolites in Figure 5. The corresponding activity for the same catalysts aged under severe lean hydrothermal conditions is shown in Figure 6. Comparison of the fresh and aged activity profiles demonstrates that hydrothermal stability is only achieved for aluminosilicate zeolites when the Cu is supported on a • small pore zeolite.
The N2O formation measured for the fresh and aged catalysts is shown in Figures 7 and 8, respectively. The results clearly show that N2O formation is significantly reduced by means of • supporting Cu on zeolites that do not have large pores.
Figure 9 compares the effect of HC on Cu/zeolite catalysts where SAPO-34 and Nu-3 are used as examples of small pore zeolite materials. For comparison, ZSM-5 and Beta zeolite are used as examples of a medium and large pore zeolite, respectively. Samples were exposed to different HC species (propene, n-octane and toluene) during NH3 SCR reaction at 300°C. Figure 10 shows the corresponding HC breakthrough following HC addition.
Figure 11 shows the adsorption profiles of n-octane at 150°C flowing through different
Cu/zeolite catalysts. HC breakthrough is observed almost immediately with Cu supported on the small pore zeolites SAPO-34 and Nu-3, whereas significant HC uptake is observed with Cu on Beta zeolite and ZSM-5. Figure 12 shows the subsequent HC desorption profile as a function of increasing temperature and confirms that large amounts of HC are stored when Cu is supported on the larger pore zeolites, whereas very little HC is stored when small pore zeolites are employed.
Example 10 - Results for experiments shown in Figures 13 and 14
Cu/SSZ-13, Cu/SAPO-34, Cu/Sigma-1 and Cu/Beta prepared according to Example 2 were aged in the manner described in Example 4 and tested according to Example 6. The results are shown in Figure 13, from which it can be seen that the NOx conversion activity of each of the severely lean hydrothermally aged Cu/SSZ-13, Cu/SAPO-34 and Cu/Sigma-1 samples is significantly better than that of the corresponding large-pore zeolite, Cu/Beta. Moreover, from Figure 14 it can be seen that Cu/Beta generates significantly more N2O than the Cu/small-pore zeolite catalysts.
Example 11 - Results for experiments shown in Figure 15
Cu/ZSM-34, Cu/SAPO-34, Cu/SSZ-13 and Cu/Beta prepared according to Example 2 were aged in the manner described in Example 3 and tested according to Example 6. The results are shown in Figure 15, from which it can be seen that the NOx conversion activity of each of the lean hydrothermally aged Cu/SSZ-13, Cu/SAPO-34 and Cu/ZSM-34 samples is significantly better than that of the corresponding large-pore zeolite, Cu/Beta.
Example 12 - Results for experiments shown in Figure 16
Fresh samples of Cu/SSZ-13 and Cu/SAPO-34 were prepared according to Example 2, samples of which were aged in the manner described in Example 5. Fresh (i.e. un-aged) and aged samples were tested according to Example 6 and the results are shown in Figure 16, from .
which it can be seen that the NOx conversion activity of Cu/SSZ-13 is maintained even after extended severe lean hydrothermal ageing.
Example 13 - Results for experiments shown in Figures 17 and 18 ' • . •
Cu/SAPO-34 and a Cu/naturally occurring chabazite type material having a SAR of about 4 were prepared according to Example 2 and the fresh materials were tested according to Example 6. The results are shown in Figure 17, from which it can be seen that the NOx conversion activity of the naturally occurring Cu/chabazite is significantly lower than Cu/SAPO- 34. Figure 18 is a bar chart comparing the NOx conversion activity of two fresh Cu/naturally occurring chabazite type materials prepared according to Example 2 at two temperature data points (2000C and 30O0C)3 a first chabazite material having a SAR of about 4 and a second chabazite material of SAR about 7. It can be seen that whilst the NOx conversion activity for the SAR 7 chabazite is better than for the SAR 4 chabazite material, the activity of the SAR 7 chabazite material is still significantly lower than the fresh Cu/SAPO-34.
Example 14 - Results for experiments shown in Figure 19
Cu/SAPO-34 and Cu/Beta were prepared according to Example 2. Fe/SAPO-34 and Fe/SSZ-13 were prepared according to Example 1. The samples were aged according to
Example 4 and the aged samples were tested according to Example 6. The NOx activity at the 3500C and 450°C data points is shown in Figure 19, from which it can be seen that the Cu/SAPO-34, Fe/SAPO-34 and Fe/SSZ-13 samples exhibit comparable or better performance than the Cu/Beta reference.
Example 15 - Results for experiments shown in Figures 20 and 21
Fe/SSZ-13 and Fe/Beta prepared according to Example 1 were tested fresh as described in Example 7, wherein n-octane (to replicate the effects of unburned diesel fuel in a,exhaust gas) was introduced at 8 minutes into the test. The results shown in Figure 20 compare the NOx conversion activity at 8 minutes into the test* but before n-octane was introduced into the feed gas (HC-) and 8 minutes after n-octane was introduced into the feed gas (HC+). It can be seen that the Fe/Beta activity dramatically reduces following n-octane introduction compared with Fe/SSZ-13. We believe that this effect results from coking of the catalyst. The hypothesis that coking ot the Fe/Beta catalyst is responsible for the dramatic reduction of NOx conversion activity is reinforced by the results shown in Figure 21, wherein Cl hydrocarbon is detected downstream of the Fe/SSZ-13 catalyst almost immediately after n- octane is introduced into the feed gas at 8 minutes. By comparison, a significantly lower quantity of Cl hydrocarbon is observed in the effluent for the Fe/Beta sample. Since there is significantly less Cl hydrocarbon present in the effluent for the Fe/Beta sample, and the n-octane must have gone somewhere, the results suggest that it has become coked on the Fe/Beta catalyst, contributing to the loss in NOx conversion activity.
Example 16 - Results for experiments shown in Figure 22
Fe/SSZ-13 prepared according to Example 1 was tested fresh, i.e. without ageing, in the manner described in Example 6. The test was then repeated using identical conditions, except in that the 350ppm NO was replaced with a mixture of 175ppm NO and 175ppm NO2, i.e. 350ppm total NOx. The results from both tests are shown in Figure 22, from which the significant improvement obtainable from increasing the NO2 content OfNOx in the feed gas to 1 : 1 can be seen. In practice, the NOrNO2 ratio can be adjusted by oxidising NO in an exhaust gas, e.g. of a diesel engine, using a suitable oxidation catalyst located upstream of the NH3-SCR catalyst.
For the avoidance of any doubt, the entire contents of any and all prior art documents cited herein is incorporated herein by reference.

Claims

CLAIMS:
1. A method of converting nitrogen oxides in a gas to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a zeolite catalyst containing at least one transition metal, wherein the zeolite is a small pore zeolite containing a maximum ring size of eight tetrahedral atoms, wherein the at least one transition metal is selected from the group consisting of Cr, Mn, Fe3 Co, Ce, Ni, Cu5 Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir and Pt.
2. A method according to claim 1 , wherein the zeolite is an isotype containing one or more sύbstituent framework metal. .
3. A method according to claim 2, wherein the or each substituent framework metal is selected from the group consisting of As, B, Be, Co, Fe, Ga, Ge, Li5 Mg, Mn, Zn and Zr.
4. A method according to claim 1 , 2 or 3, wherein the small pore zeolite is not a framework type material or any isotype zeolite thereof with the Framework Type Code LTA.
5. A method according to any preceding claim, wherein the transition metal-containing small pore zeolite is not Ce/erionite.
6. A method according to any preceding claim, wherein the transition metal-containing small pore zeolite is not Cu/ chabazite, Mo/chabazite, Cu-Mo/chabazite, Cu/erionite, Mo/erionite or Cu-Mo/erionite.
7. A method according to any preceding claim, wherein the transition metal-containing small pore zeolite is not Fe/chabazite, Fe/ZK-5, Fe/ZK-4, Fe-rare-earth/chabazite, Fe-rare-earth/ZK-5 or Fe-rare-earth/ZK-4.
.8. A method according to any preceding claim, wherein the transition metal-containing small pore zeolite is not Fe/chabazite.
9. A method according to any preceding claim, wherein the small pore zeolite is selected from the group consisting of aluminosilicate zeolites, metal-substituted aluminosilicate zeolites and aluminophosphate zeolites.
10. A method according to claim 9, wherein the or each aluminophosphate zeolite is selected from the group consisting of AlPO zeolites, MeAlPO zeolites, SAPO zeolites and MeAPSO zeolites.
11. A method according to any preceding claim, wherein the small pore zeolite is selected from the group of Framework Type Codes consisting of: ACO, AEI, AEN5 AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG and ZON.
12. A method according to claim 11 , wherein the small pore zeolite containing a maximum ring size of eight tetrahedral atoms is selected from the group of Framework Type Codes consisting of CHA, LEV, ERI and DDR.
13. A method according to claim 12, wherein the CHA Framework Type Code zeolite is SAPO-34 or SSZ-13.
14. A method according to, claim 12, wherein the LEV Framework Type Code zeolite is Nu-3.
15. A method according to claim 12, wherein the ERI Framework Type Code zeolite is ZSM- 34.
16. A method according to claim 12, wherein the DDR Framework Type Code zeolite is Sigma- 1.
17. A method according to any preceding claim, wherein the zeolite has been treated to improve hydrothermal stability.
18. A method according to any preceding claim, wherein the pore size of the zeolite in at least one dimension is less than 4.3 A.
19. A method according to any preceding claim, wherein the zeolite has three-dimensional dimensionality. 451
20. A method according to any of claims 1 to 18, wherein the zeolite has two-dimensional dimensionality.
21. A method according to any preceding- claim, wherein the at least one transition metal is selected from the group consisting of Cr, Ce, Mn, Fe, Co, Ni and Cu.
22. A method according to any preceding claim, wherein the at least one transition metal is selected from the group consisting of Fe, Ce and Cu.
23. A method according to any preceding claim, wherein the at least one transition metal is Fe and/or Cu.
24. A method according to any preceding claim, wherein the total at least one transition metal present in the catalyst is from 0.01 to 20 wt%, based on the total weight of the zeolite catalyst.
25. A method according to any preceding claim, wherein the total at least one transition metal present in the catalyst is from 0.1 to 10 wt%, based on the total weight of the zeolite catalyst.
26. A method according to claim 25, wherein the total at least one transition metal present in the catalyst is from 0.5 to 5 wt%, based on the total weight of the zeolite catalyst.
27. A method according to any preceding claim, wherein the zeolite catalyst consists of Fe/CHA, particularly Fe/SAPO-34 or Fe/SSZ-13.
28. A method according to any of claims 1 to 26, wherein the zeolite catalyst consists of Cu/CHA, particularly Cu/SAPO-34 or Cu/SSZ-13.
29. A method according to any preceding claim, wherein the nitrogen oxides are reduced with the reducing agent at a temperature of at least 100°C.
30. A method according to claim 29, wherein the temperature is from about 1500C to 750°C.
31. A method according to any preceding claim, wherein the nitrogen oxides reduction is performed in the presence of oxygen.
32. A method according to any preceding claim,, wherein addition of nitrogenous reductant is controlled so that NH3 at the zeolite catalyst inlet is controlled to be 60% to 200% of theoretical ammonia calculated at 1:1 NH3/NO and 4:3 NH3/NO2.
33. A method according to any preceding claim, wherein nitrogen monoxide in the gas is oxidised to nitrogen dioxide using an oxidation catalyst located upstream of the zeolite catalyst and the resulting gas is then mixed with nitrogenous reductant before the mixture is fed into the zeolite catalyst, wherein the oxidation catalyst is adapted to yield a gas stream entering the zeolite catalyst having a ratio of NO to NO2 of from about 4:1 to about 1 :3 by volume.
34. A method according to any preceding claim, wherein the zeolite is a synthetic zeolite.
35. A method according to any preceding claim, wherein the nitrogenous reductant is ammonia per se, hydrazine or an ammonia precursor selected from the group consisting of urea ((NH2)2CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate and ammonium formate.
36. A method according to any preceding claim, wherein the gas containing nitrogen oxides is derived from a combustion process.
37. A method according to claim 36, wherein the combustion process is the combustion of fuel in a vehicular lean burn internal combustion engine.
38. An exhaust system for a vehicular lean burn internal combustion engine, which system comprising a conduit for carrying a flowing exhaust gas, a source of nitrogenous reductant, a zeolite catalyst containing at least one transition metal disposed in a flow path of the exhaust gas and means for metering nitrogenous reductant into a flowing exhaust gas upstream of the zeolite catalyst, wherein the zeolite catalyst is a small pore zeolite containing a maximum ring size of eight tetrahedral atoms, wherein the at least one transition metal is selected from the group consisting of Cr, Mn, Fe, Co, Ce5 Ni, Cu, Zn5 Ga, Mo5 Ru, Rh, Pd5 Ag, In, Sn, Re, Ir and Pt.
39. An exhaust system according to claim 38, wherein the zeolite catalyst is coated on a flow-through substrate. '
40. An exhaust system according to claim 38 or 39, comprising means, when in use, for controlling the metering means so that nitrogenous reductant is metered into the flowing exhaust gas only when it is determined that the zeolite catalyst is capable of catalysing NOx reduction at or above a desired efficiency. .
41. . An exhaust system according to claim 40, wherein the control means, when in use, is arranged to respond to received inputs indicative of a condition of the engine selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, mass flow of exhaust gas in the system, manifold vacuum, ignition timing, engine speed, lambda value of the exhaμst gas, the quantity of fuel injected in the engine and the position of the exhaust gas' recirculation (EGR) valve and thereby the amount of EGR and boost pressure.
42. An exhaust system according to claim 41, wherein the control means, when in use, controls the metering of nitrogenous reductant in response to the quantity of nitrogen oxides in the exhaust gas determined.
43. An exhaust gas according to claim 40, 41 or 42, wherein the control means is adapted, when in use, to meter nitrogenous reductant into the exhaust gas such that 60% to 200% of theoretical ammonia is present in exhaust gas entering the zeolite catalyst calculated at 1 :1 NH3/NO and.4:3 NH3/NO2.
44. An exhaust system according to claim 40, 41, 42 or 43, wherein the control means comprises a pre-programmed processor.
45. An exhaust system according to any of claims 38 to 44, wherein an oxidation catalyst for oxidising nitrogen monoxide to nitrogen dioxide is located upstream of the means for metering nitrogenous reductant into a flowing exhaust gas.
46. An exhaust system according to claim 45, wherein the oxidation catalyst comprises at least one platinum group metal, preferably comprising platinum.
47. An exhaust system according to claim 45 or 46, wherein the catalyst, when in use, is adapted to yield a ratio of NO to NO2 of from about 4: 1 to about 1 :3 by volume at an exhaust gas temperature at oxidation catalyst inlet of 150°C to 750°C.
48. An exhaust system according to any of claims 38 to 47, wherein a filter substrate is located between the oxidation catalyst and the zeolite catalyst.
49. An apparatus comprising vehicular lean-burn engine and an exhaust system according to any of claims 38 to 48.
50. An apparatus according to claim 49, wherein the engine is a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.
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CN2008800217622A CN101730575B (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts
EP19206118.2A EP3626329B1 (en) 2007-04-26 2008-04-24 Exhaust system comprising copper/zsm-34 zeolite scr catalyst and method of converting nitrogen oxides
EP08762186.8A EP2150328B1 (en) 2007-04-26 2008-04-24 SCR METHOD AND SYSTEM USING Cu/SAPO-34 ZEOLITE CATALYST
EP17200920.1A EP3300791B1 (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts
RU2009143682/05A RU2506989C2 (en) 2007-04-26 2008-04-24 Scr catalysts: transition metal/zeolite
EP12177705.6A EP2517778B2 (en) 2007-04-26 2008-04-24 Transition metal/aei-zeolite scr catalyst
JP2010504833A JP5777339B2 (en) 2007-04-26 2008-04-24 Transition metal / zeolite SCR catalyst
CA2685009A CA2685009C (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts
US12/597,707 US20100290963A1 (en) 2007-04-26 2008-04-24 Transition metal / zeolite scr catalysts
EP12177604.1A EP2517773B2 (en) 2007-04-26 2008-04-24 Copper/LEV-zeolite SCR catalyst
KR1020157010306A KR20150052335A (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts
KR1020167033642A KR101965943B1 (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts
MX2009011443A MX2009011443A (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts.
EP21204033.1A EP3981502A1 (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts
DK08762186.8T DK2150328T5 (en) 2007-04-26 2008-04-24 SCR method and system with Cu / SAPO-34 zeolite catalyst
BRPI0810133-7A BRPI0810133B1 (en) 2007-04-26 2008-04-24 METHOD FOR CONVERTING NITROGEN OXIDES FROM A GAS TO NITROGEN, EXHAUST SYSTEM FOR A VEHICLE LOW-BURNING INTERNAL COMBUSTION ENGINE, AND APPARATUS
KR1020187011116A KR20180043406A (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts
KR1020197000095A KR102089480B1 (en) 2007-04-26 2008-04-24 Transition metal/zeolite scr catalysts
EP12177690.0A EP2517776B2 (en) 2007-04-26 2008-04-24 Transition metal/kfi-zeolite scr catalyst
US13/164,150 US8603432B2 (en) 2007-04-26 2011-06-20 Transition metal/zeolite SCR catalysts
US13/567,705 US8906820B2 (en) 2007-04-26 2012-08-06 Transition metal/zeolite SCR catalysts
US13/567,698 US20120301379A1 (en) 2007-04-26 2012-08-06 Transition metal/zeolite scr catalysts
US13/567,703 US20120301380A1 (en) 2007-04-26 2012-08-06 Transition metal/zeolite scr catalysts
US13/567,692 US20120301378A1 (en) 2007-04-26 2012-08-06 Transition metal/zeolite scr catalysts
US14/552,161 US20150078968A1 (en) 2007-04-26 2014-11-24 Transition metal/zeolite scr catalysts
US14/587,613 US20150118114A1 (en) 2007-04-26 2014-12-31 Transition metal/zeolite scr catalysts
US14/587,653 US20150118121A1 (en) 2007-04-26 2014-12-31 Transition metal/zeolite scr catalysts
US14/587,793 US20150110682A1 (en) 2007-04-26 2014-12-31 Transition metal/zeolite scr catalysts
US14/587,709 US20150118115A1 (en) 2007-04-26 2014-12-31 Transition metal/zeolite scr catalysts
US15/252,376 US20160367939A1 (en) 2007-04-26 2016-08-31 Transition metal/zeolite scr catalysts
US15/991,565 US11478748B2 (en) 2007-04-26 2018-05-29 Transition metal/zeolite SCR catalysts

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Cited By (144)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009099937A1 (en) * 2008-01-31 2009-08-13 Basf Catalysts Llc Catalysts, systems and methods utilizing non-zeolitic metal-containing molecular sieves having the cha crystal structure
US7601662B2 (en) 2007-02-27 2009-10-13 Basf Catalysts Llc Copper CHA zeolite catalysts
WO2009135588A1 (en) * 2008-05-07 2009-11-12 Umicore Ag & Co. Kg Method for decreasing nitrogen oxides in hydrocarbon-containing exhaust gases using an scr catalyst based on a molecular sieve
WO2009141324A1 (en) * 2008-05-21 2009-11-26 Basf Se Process for the direct synthesis of cu containing zeolites having cha structure
WO2010043891A1 (en) 2008-10-15 2010-04-22 Johnson Matthey Public Limited Company Transition metal-containing aluminosilicate zeolite
WO2010097634A1 (en) 2009-02-26 2010-09-02 Johnson Matthey Public Limited Company Filter for filtering particulate matter from exhaust gas emitted from a positive ignition engine
WO2010121257A1 (en) 2009-04-17 2010-10-21 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
EP2269733A1 (en) 2009-06-08 2011-01-05 Basf Se Process for the direct synthesis of cu containing silicoaluminophosphate (cu-sapo-34)
US20110011067A1 (en) * 2009-07-14 2011-01-20 Gm Global Technology Operations, Inc. Ash Filter, Exhaust Gas Treatment System Incorporating the Same and Method of Using the Same
DE102010027883A1 (en) 2009-04-17 2011-03-31 Johnson Matthey Public Ltd., Co. Process for using a catalyst with copper and a small pore molecular sieve in a chemical process
JP2011067814A (en) * 2009-08-27 2011-04-07 Tosoh Corp Highly heat-resistant aqueous scr catalyst and manufacturing method thereof
WO2011045252A1 (en) 2009-10-14 2011-04-21 Basf Se Copper containing levyne molecular sieve for selective reduction of nox
EP2325143A2 (en) 2009-11-24 2011-05-25 Basf Se Process for the preparation of zeolites having B-CHA structure
WO2011064186A1 (en) 2009-11-24 2011-06-03 Basf Se Process for the preparation of zeolites having cha structure
WO2011064666A2 (en) 2009-11-30 2011-06-03 Johnson Matthey Public Limited Company Catalysts for treating transient nox emissions
WO2011073390A2 (en) 2009-12-18 2011-06-23 Basf Corporation Process for preparation of copper containing molecular sieves with the cha structure, catalysts, systems and methods
WO2011073398A2 (en) 2009-12-18 2011-06-23 Basf Corporation Process of direct copper exchange into na+-form of chabazite molecular sieve, and catalysts, systems and methods
WO2011077168A1 (en) 2009-12-24 2011-06-30 Johnson Matthey Plc Exhaust system for a vehicular positive ignition internal combustion engine
JP2011125852A (en) * 2009-11-19 2011-06-30 Ibiden Co Ltd Honeycomb structure and exhaust gas cleaning apparatus
JP2011125846A (en) * 2009-11-19 2011-06-30 Ibiden Co Ltd Honeycomb structure and apparatus for cleaning exhaust gas
WO2011092521A1 (en) * 2010-02-01 2011-08-04 Johnson Matthey Plc Extruded scr filter
DE102010007626A1 (en) 2010-02-11 2011-08-11 Süd-Chemie AG, 80333 Copper-containing zeolite of the KFI type and use in SCR catalysis
US7998423B2 (en) 2007-02-27 2011-08-16 Basf Corporation SCR on low thermal mass filter substrates
WO2011110919A1 (en) 2010-03-08 2011-09-15 Johnson Matthey Public Limited Company Improvements in control of emissions
WO2011073123A3 (en) * 2009-12-18 2011-10-20 Basf Se Ferrous zeolite, method for producing ferrous zeolites, and method for catalytically reducing nitrous oxides
EP2377613A3 (en) * 2009-12-18 2011-11-02 JGC Catalysts and Chemicals Ltd. Metal-supported crystalline silica aluminophosphate catalyst and process for producing the same
WO2011151711A1 (en) 2010-06-02 2011-12-08 Johnson Matthey Public Limited Company Diesel particulate filter
US20110305614A1 (en) * 2010-04-08 2011-12-15 Basf Corporation Cu-CHA/Fe-MFI Mixed Zeolite Catalyst And Process For The Treatment Of NOx In Gas Streams
US20120014866A1 (en) * 2010-07-15 2012-01-19 Ivor Bull Copper Containing ZSM-34, OFF And/Or ERI Zeolitic Material For Selective Reduction Of NOx
WO2012007873A1 (en) * 2010-07-15 2012-01-19 Basf Se Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
WO2012007874A1 (en) * 2010-07-15 2012-01-19 Basf Se Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
US20120014867A1 (en) * 2010-07-15 2012-01-19 Basf Se Copper Containing ZSM-34, OFF And/Or ERI Zeolitic Material For Selective Reduction Of NOx
US20120014865A1 (en) * 2010-07-15 2012-01-19 Basf Se Copper Containing ZSM-34, OFF And/Or ERI Zeolitic Material For Selective Reduction Of NOx
US20120020875A1 (en) * 2009-01-22 2012-01-26 Mitsubishi Plastics, Inc. Catalyst for reducing nitrogen oxides and method for producing the same
KR20120008521A (en) * 2009-04-03 2012-01-30 바스프 코포레이션 Emissions treatment system with ammonia-generating and scr catalysts
US20120039759A1 (en) * 2010-08-13 2012-02-16 Ut-Battelle, Llc Zeolite-based scr catalysts and their use in diesel engine emission treatment
EP2463028A1 (en) 2010-12-11 2012-06-13 Umicore Ag & Co. Kg Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic removal of nitrogen oxides
DE102011089371A1 (en) 2010-12-21 2012-06-21 Johnson Matthey Plc Oxidation catalyst for a lean-burn internal combustion engine
WO2012090922A1 (en) 2010-12-27 2012-07-05 三菱樹脂株式会社 Catalyst for nitrogen oxide removal
DE102012203461A1 (en) 2011-03-04 2012-09-06 Johnson Matthey Public Ltd. Co. CATALYST AND METHOD OF MANUFACTURE
CN102671691A (en) * 2012-05-28 2012-09-19 四川君和环保工程有限公司 Low-temperature SCR (Selective Catalytic Reduction) denitrification catalyst, as well as preparation method and application thereof
US20120251422A1 (en) * 2011-04-04 2012-10-04 Pq Corporation Fe-SAPO-34 CATALYST AND METHODS OF MAKING AND USING THE SAME
WO2012158239A1 (en) 2011-02-28 2012-11-22 Johnson Matthey Public Limited Company High-temperature scr catalyst
EP2555866A1 (en) * 2010-04-08 2013-02-13 Basf Se Cu-cha/fe-mfi mixed zeolite catalyst and process for treating nox in gas streams using the same
JP2013506787A (en) * 2009-10-02 2013-02-28 ビー・エイ・エス・エフ、コーポレーション Catalyst used for four-cycle diesel and method of using the same
WO2013030584A1 (en) 2011-08-31 2013-03-07 Johnson Matthey Public Limited Company Method and system using a filter for treating exhaust gas having particulate matter
WO2013050784A2 (en) 2011-10-06 2013-04-11 Johnson Matthey Public Limited Company Oxidation catalyst for internal combustion engine exhaust gas treatment
WO2013050964A1 (en) * 2011-10-05 2013-04-11 Basf Se Cu-CHA/Fe-BEA MIXED ZEOLITE CATALYST AND PROCESS FOR THE TREATMENT OF NOX IN GAS STREAMS
US20130089483A1 (en) * 2011-10-05 2013-04-11 Basf Se Cu-CHA/Fe-BEA Mixed Zeolite Catalyst And Process For The Treatment Of NOx In Gas Streams
WO2013088133A1 (en) 2011-12-12 2013-06-20 Johnson Matthey Public Limited Company Catalysed substrate monolith
WO2013088132A1 (en) 2011-12-12 2013-06-20 Johnson Matthey Public Limited Company Exhaust system for a lean-burn ic engine comprising a pgm component and a scr catalyst
WO2013088129A2 (en) 2011-12-12 2013-06-20 Johnson Matthey Public Limited Company Substrate monolith comprising scr catalyst
WO2013088128A1 (en) 2011-12-12 2013-06-20 Johnson Matthey Public Limited Company Exhaust system for a lean-burn internal combustion engine including scr catalyst
WO2013114172A1 (en) * 2012-01-31 2013-08-08 Johnson Matthey Public Limited Company Catalyst blends
WO2013126619A1 (en) * 2012-02-24 2013-08-29 Ut-Battelle, Llc Hydrothermally stable, low-temperature nox reduction nh3-scr catalyst
WO2013159828A1 (en) 2012-04-27 2013-10-31 Haldor Topsøe A/S Process for the direct synthesis of cu-sapo-34
US8603432B2 (en) 2007-04-26 2013-12-10 Paul Joseph Andersen Transition metal/zeolite SCR catalysts
US8617502B2 (en) 2011-02-07 2013-12-31 Cristal Usa Inc. Ce containing, V-free mobile denox catalyst
RU2506999C2 (en) * 2009-09-05 2014-02-20 Джонсон Мэтти Каталистс (Джермани) Гмбх Method of obtaining scr-active zeolite catalyst and scr-active zeolite catalyst
DE102013223845A1 (en) 2012-11-21 2014-05-22 Johnson Matthey Public Limited Company Oxidation catalyst for the treatment of exhaust gas of an internal combustion engine
US8809217B2 (en) 2010-03-11 2014-08-19 Johnson Matthey Public Limited Company Disordered molecular sieve supports for the selective catalytic reduction of NOx
WO2014141200A1 (en) * 2013-03-15 2014-09-18 Johnson Matthey Public Limited Company Catalyst for treating exhaust gas
DE102013005749A1 (en) 2013-04-05 2014-10-09 Umicore Ag & Co. Kg CuCHA material for SCR catalysis
DE102014105736A1 (en) 2013-04-24 2014-10-30 Johnson Matthey Public Limited Company A spark-ignition engine and exhaust system comprising a catalyzed zoned filter substrate
DE102014106943A1 (en) 2013-05-17 2014-11-20 Johnson Matthey Public Limited Company OXIDATION CATALYST FOR A COMPRESSION IGNITION ENGINE
WO2014199945A1 (en) 2013-06-14 2014-12-18 東ソー株式会社 Lev-type zeolite and production method therefor
WO2015018815A1 (en) * 2013-08-09 2015-02-12 Basf Se Process for the oxygen free conversion of methane to ethylene on zeolite catalysts
US8956992B2 (en) 2011-10-27 2015-02-17 GM Global Technology Operations LLC SCR catalysts preparation methods
US8992869B2 (en) 2012-12-20 2015-03-31 Caterpillar Inc. Ammonia oxidation catalyst system
CN104520548A (en) * 2012-04-27 2015-04-15 赫多特普索化工设备公司 Method and system for the purification of exhaust gas from an internal combustion engine
DE102014117672A1 (en) 2013-12-02 2015-06-03 Johnson Matthey Public Limited Company WALL CURRENT FILTER CONTAINING A CATALYTIC WASHCOAT
WO2015084834A1 (en) * 2013-12-02 2015-06-11 Johnson Matthey Public Limited Company Synthesis of aei zeolite
GB2522977A (en) * 2013-12-06 2015-08-12 Johnson Matthey Plc Passive NOx adsorber
US20150231617A1 (en) * 2014-02-19 2015-08-20 Ford Global Technologies, Llc Fe-SAPO-34 CATALYST FOR USE IN NOX REDUCTION AND METHOD OF MAKING
US20150231620A1 (en) * 2014-02-19 2015-08-20 Ford Global Technologies, Llc IRON-ZEOLITE CHABAZITE CATALYST FOR USE IN NOx REDUCTION AND METHOD OF MAKING
US9138731B2 (en) 2011-08-03 2015-09-22 Johnson Matthey Public Limited Company Extruded honeycomb catalyst
US20150290632A1 (en) * 2014-04-09 2015-10-15 Ford Global Technologies, Llc IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION
EP2593212B1 (en) * 2010-07-15 2015-12-16 Basf Se Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
GB2527398A (en) * 2014-03-27 2015-12-23 Johnson Matthey Plc SCR method for reducing oxides of nitrogen and method for producing a catalyst for such method
EP2985068A1 (en) 2014-08-13 2016-02-17 Umicore AG & Co. KG Catalyst system for the reduction of nitrogen oxides
US9327239B2 (en) 2013-04-05 2016-05-03 Johnson Matthey Public Limited Company Filter substrate comprising three-way catalyst
RU2584748C2 (en) * 2010-09-13 2016-05-20 Умикоре Аг Унд Ко. Кг Catalyst for removing nitrogen oxides from exhaust gases of diesel engines
US9352279B2 (en) 2012-04-24 2016-05-31 Johnson Matthey Public Limited Company Filter substrate comprising three-way catalyst
US9403157B2 (en) 2013-04-29 2016-08-02 Ford Global Technologies, Llc Three-way catalyst comprising mixture of nickel and copper
DE102016102527A1 (en) 2015-02-16 2016-08-18 Johnson Matthey Public Limited Company Catalyst with stable nitrogen monoxide (NO) oxidation performance
GB2538877A (en) * 2014-12-08 2016-11-30 Johnson Matthey Plc Passive NOx adsorber
DE102016111766A1 (en) 2015-06-28 2016-12-29 Johnson Matthey Public Limited Company CATALYTIC WALL CURRENT FILTER WITH A MEMBRANE
RU2608616C2 (en) * 2011-10-24 2017-01-23 Хальдор Топсеэ А/С Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides
US9630146B2 (en) 2013-06-03 2017-04-25 Ford Global Technologies, Llc Particulate filter containing a nickel-copper catalyst
US9802182B2 (en) 2013-03-13 2017-10-31 Basf Corporation Stabilized metal-exchanged SAPO material
US20170333883A1 (en) * 2014-10-30 2017-11-23 Basf Corporation Mixed metal large crystal molecular sieve catalyst compositions, catalytic articles, systems and methods
WO2017207969A1 (en) * 2016-05-31 2017-12-07 Johnson Matthey Public Limited Company Method and exhaust system for treating nox in exhaust gas from stationary emission sources
EP3281698A1 (en) 2016-08-11 2018-02-14 Umicore AG & Co. KG Scr active material
WO2018029329A1 (en) 2016-08-11 2018-02-15 Umicore Ag & Co. Kg Scr-active material having enhanced thermal stability
WO2018054929A1 (en) 2016-09-20 2018-03-29 Umicore Ag & Co. Kg Diesel particle filter
WO2018069199A1 (en) 2016-10-10 2018-04-19 Umicore Ag & Co. Kg Catalytic converter arrangement
DE102017125192A1 (en) 2016-10-28 2018-05-03 Johnson Matthey Public Limited Company Catalytic wall-flow filter with partial surface coating
WO2018081682A1 (en) * 2016-10-31 2018-05-03 Johnson Matthey Public Limited Company Lta catalysts having extra-framework iron and/or manganese for treating exhaust gas
WO2018100368A1 (en) * 2016-12-01 2018-06-07 Johnson Matthey Public Limited Company METHOD OF EXTENDING THE USEFUL LIFE OF AN AGED SCR CATALYST BED IN AN EXHAUST SYSTEM OF A STATIONARY SOURCE OF NOx
US10001053B2 (en) 2008-06-27 2018-06-19 Umicore Ag & Co. Kg Method and device for the purification of diesel exhaust gases
EP2352912B1 (en) 2008-11-03 2018-07-04 BASF Corporation Integrated scr and amox catalyst systems
EP3357558A1 (en) 2017-02-03 2018-08-08 Umicore Ag & Co. Kg Catalyst for cleaning diesel engine exhaust gases
DE102018204690A1 (en) 2017-03-31 2018-10-04 Johnson Matthey Catalysts (Germany) Gmbh Selective catalytic reduction catalyst
DE102018204802A1 (en) 2017-03-31 2018-10-04 Friedrich-Alexander-Universität Erlangen-Nürnberg Catalyst composition for selective catalytic reduction
US10092897B2 (en) * 2016-04-20 2018-10-09 Ford Global Technologies, Llc Catalyst trap
US10105691B2 (en) 2016-03-31 2018-10-23 Ford Global Technologies, Llc Multiple zeolite hydrocarbon traps
CN109250729A (en) * 2017-07-12 2019-01-22 中国科学院大连化学物理研究所 The molecular sieve and application of Cu-SAPO-34 Zeolite synthesis method and synthesis
EP3450015A1 (en) 2017-08-31 2019-03-06 Umicore Ag & Co. Kg Palladium-zeolite-based passive nitrogen oxide adsorber catalyst for exhaust gas treatment
EP3449999A1 (en) 2017-08-31 2019-03-06 Umicore Ag & Co. Kg Passive nitric oxide adsorber
EP3450016A1 (en) 2017-08-31 2019-03-06 Umicore Ag & Co. Kg Palladium-zeolite-based passive nitrogen oxide adsorber catalyst for exhaust gas treatment
WO2019042883A1 (en) 2017-08-31 2019-03-07 Umicore Ag & Co. Kg Palladium/zeolite-based passive nitrogen oxide adsorber catalyst for purifying exhaust gas
DE102018121503A1 (en) 2017-09-05 2019-03-07 Umicore Ag & Co. Kg Exhaust gas purification with NO oxidation catalyst and SCR-active particle filter
WO2019042884A1 (en) 2017-08-31 2019-03-07 Umicore Ag & Co. Kg Use of a palladium/platinum/zeolite-based catalyst as passive nitrogen oxide adsorber for purifying exhaust gas
US10226762B1 (en) * 2011-06-17 2019-03-12 Johnson Matthey Public Limited Company Alumina binders for SCR catalysts
WO2019077111A1 (en) 2017-10-20 2019-04-25 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber catalyst
WO2019134958A1 (en) 2018-01-05 2019-07-11 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber
DE102018100833A1 (en) 2018-01-16 2019-07-18 Umicore Ag & Co. Kg Process for producing an SCR catalyst
DE102018100834A1 (en) 2018-01-16 2019-07-18 Umicore Ag & Co. Kg Process for producing an SCR catalyst
WO2019145198A1 (en) 2018-01-23 2019-08-01 Umicore Ag & Co. Kg Scr catalyst and exhaust gas cleaning system
EP3411145A4 (en) * 2016-02-03 2019-10-02 BASF Corporation Copper and iron co-exchanged chabazite catalyst
US10456746B2 (en) 2018-02-12 2019-10-29 GM Global Technology Operations LLC Selective catalytic reduction filter for reducing nitrous oxide formation and methods of using the same
RU2704617C2 (en) * 2012-10-19 2019-10-30 Басф Корпорейшн 8-ring molecular sieve with small pores as high-temperature scr catalyst
EP3613503A1 (en) 2018-08-22 2020-02-26 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber
EP3616792A1 (en) 2018-08-28 2020-03-04 Umicore Ag & Co. Kg Nitrogen oxide storage catalyst
US10583424B2 (en) 2008-11-06 2020-03-10 Basf Corporation Chabazite zeolite catalysts having low silica to alumina ratios
WO2020089043A1 (en) 2018-11-02 2020-05-07 Basf Corporation Exhaust treatment system for a lean burn engine
WO2020099253A1 (en) 2018-11-16 2020-05-22 Umicore Ag & Co. Kg Low temperature nitrogen oxide adsorber
WO2020109810A1 (en) 2018-11-30 2020-06-04 Johnson Matthey Public Limited Company Enhanced introduction of extra-frame work metal into aluminosilicate zeolites
WO2020144195A1 (en) 2019-01-08 2020-07-16 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber having oxidation-catalytically active function
WO2020148186A1 (en) 2019-01-14 2020-07-23 Friedrich-Alexander-Universität Erlangen-Nürnberg Iron-loaded small pore aluminosilicate cha zeolites and method of making metal loaded small pore aluminosilicate cha zeolites
EP3695902A1 (en) 2019-02-18 2020-08-19 Umicore Ag & Co. Kg Catalyst for reducing nitrogen oxides
EP3753626A1 (en) 2013-04-24 2020-12-23 Johnson Matthey Public Limited Company Filter substrate comprising zone-coated catalyst washcoat
EP3791955A1 (en) 2019-09-10 2021-03-17 Umicore Ag & Co. Kg Scr-catalytic material containing copper-zeolite and copper/alumina, exhaust gas treatment process with said material and method for producing said material
EP3812034A1 (en) 2019-10-24 2021-04-28 Dinex A/S Durable copper-scr catalyst
US11014077B2 (en) 2016-05-03 2021-05-25 Umicore Ag & Co. Kg Active SCR catalyst
EP3824988A1 (en) 2019-11-20 2021-05-26 UMICORE AG & Co. KG Catalyst for reducing nitrogen oxides
EP3307434B1 (en) 2015-04-09 2021-06-09 PQ Corporation Stabilized microporous crystalline material, the method of making the same, and the use for selective catalytic reduction of nox
EP3885040A1 (en) 2020-03-24 2021-09-29 UMICORE AG & Co. KG Ammonia oxidation catalyst
EP3978100A1 (en) 2020-09-30 2022-04-06 UMICORE AG & Co. KG Bismuth-containing zoned diesel oxidation catalyst
WO2022069465A1 (en) 2020-09-30 2022-04-07 Umicore Ag & Co. Kg Bismut containing dieseloxidation catalyst
WO2022079141A1 (en) 2020-10-14 2022-04-21 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber
RU2771714C2 (en) * 2013-03-15 2022-05-11 Джонсон Мэтти Паблик Лимитед Компани Catalyst for exhaust gas processing
EP4063003A1 (en) 2021-03-23 2022-09-28 UMICORE AG & Co. KG Filter for the aftertreatment of exhaust gases of internal combustion engines
WO2023067134A1 (en) 2021-10-22 2023-04-27 Johnson Matthey Catalysts (Germany) Gmbh Method and catalyst article

Families Citing this family (131)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5549839B2 (en) * 2008-08-19 2014-07-16 東ソー株式会社 High heat-resistant β-type zeolite and SCR catalyst using the same
WO2011042990A1 (en) * 2009-10-09 2011-04-14 イビデン株式会社 Honeycomb filter
WO2011061839A1 (en) * 2009-11-19 2011-05-26 イビデン株式会社 Honeycomb structure and exhaust gas purification apparatus
WO2011061841A1 (en) 2009-11-19 2011-05-26 イビデン株式会社 Honeycomb structure and exhaust gas purification apparatus
CN102666430B (en) * 2009-11-19 2015-04-29 揖斐电株式会社 Honeycomb structure and exhaust gas purification apparatus
JP5573453B2 (en) * 2010-07-21 2014-08-20 三菱樹脂株式会社 Nitrogen oxide purification catalyst and method for producing the same
JP5756714B2 (en) * 2010-09-02 2015-07-29 イビデン株式会社 Silicoaluminophosphate, honeycomb structure and exhaust gas purification device
US8568677B2 (en) 2010-10-12 2013-10-29 Basf Se P/S-TM-comprising zeolites for decomposition of N2O
KR20130141519A (en) * 2010-10-12 2013-12-26 바스프 에스이 P/s-tm-comprising zeolites for decomposition of n2o
CN102451749A (en) * 2010-10-27 2012-05-16 中国科学院大连化学物理研究所 Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof
JP6450521B2 (en) * 2010-12-02 2019-01-09 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Metal-containing zeolite catalyst
EP2465606A1 (en) * 2010-12-16 2012-06-20 Umicore Ag & Co. Kg Zeolith-based catalytic converter with improved catalytic activity for reducing nitrogen oxides
US9074530B2 (en) * 2011-01-13 2015-07-07 General Electric Company Stoichiometric exhaust gas recirculation and related combustion control
EP2495032A1 (en) 2011-03-03 2012-09-05 Umicore Ag & Co. Kg SCR catalyst with improved hydrocarbon resistance
WO2012117042A2 (en) * 2011-03-03 2012-09-07 Umicore Ag & Co. Kg Catalytically active material and catalytic converter for the selective catalytic reduction of nitrogen oxides
JP2012215166A (en) * 2011-03-29 2012-11-08 Ibiden Co Ltd Exhaust emission control system and method
US8101146B2 (en) * 2011-04-08 2012-01-24 Johnson Matthey Public Limited Company Catalysts for the reduction of ammonia emission from rich-burn exhaust
EP2590730B1 (en) 2011-05-31 2014-06-25 Johnson Matthey Public Limited Company Dual function catalytic filter
US9174849B2 (en) * 2011-08-25 2015-11-03 Basf Corporation Molecular sieve precursors and synthesis of molecular sieves
GB2493987B (en) * 2011-08-26 2014-03-19 Jc Bamford Excavators Ltd An engine system
IN2014CN04885A (en) * 2011-12-01 2015-09-18 Johnson Matthey Plc
US9981256B2 (en) * 2011-12-02 2018-05-29 Pq Corporation Stabilized microporous crystalline material, the method of making the same, and the use for selective catalytic reduction of NOx
BR112014012846B1 (en) * 2011-12-02 2021-10-26 Pq Corporation CRYSTALLINE ALUMINOSILICATE MATERIAL, THE METHOD OF MANUFACTURING IT, AND SELECTIVE CATALYTIC REDUCTION METHOD OF NITROGEN OXIDES IN EXHAUST GAS
US9101877B2 (en) * 2012-02-13 2015-08-11 Siemens Energy, Inc. Selective catalytic reduction system and process for control of NOx emissions in a sulfur-containing gas stream
JP6163715B2 (en) * 2012-03-30 2017-07-19 三菱ケミカル株式会社 Zeolite membrane composite
RU2634899C2 (en) * 2012-04-11 2017-11-08 Джонсон Мэтти Паблик Лимитед Компани Zeolite catalysts containing metals
RU2670760C9 (en) * 2012-08-17 2018-12-17 Джонсон Мэтти Паблик Лимитед Компани Zeolite promoted v/ti/w catalysts
MX2015002165A (en) 2012-08-24 2015-05-11 Cristal Usa Inc Catalyst support materials, catalysts, methods of making them and uses thereof.
DE102012018629A1 (en) * 2012-09-21 2014-03-27 Clariant International Ltd. Process for purifying exhaust gas and regenerating an oxidation catalyst
EP2900372B1 (en) * 2012-09-28 2018-01-10 Pacific Industrial Development Corporation An alumina silicate zeolite-type material for use as a catalyst in selective catalytic reduction and process of making thereof
RU2509599C1 (en) * 2012-10-01 2014-03-20 Федеральное государственное унитарное предприятие "Государственный научный центр "Научно-исследовательский институт органических полупродуктов и красителей" (ФГУП "ГНЦ "НИОПИК") Method of removing nitrogen oxides from air
US20150273446A1 (en) * 2012-10-03 2015-10-01 Ibiden Co., Ltd. Honeycomb structure
KR102149735B1 (en) * 2012-10-18 2020-08-31 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Close-coupled scr system
CN104736241B (en) * 2012-10-19 2020-05-19 巴斯夫公司 8-ring small pore molecular sieve with promoter to improve low temperature performance
EP2908947B1 (en) * 2012-10-19 2021-09-29 BASF Corporation Mixed metal 8-ring small pore molecular sieve catalytic articles and methods
EP2969195A1 (en) * 2013-03-14 2016-01-20 BASF Corporation Selective catalytic reduction catalyst system
RU2662821C2 (en) 2013-03-14 2018-07-31 Джонсон Мэтти Паблик Лимитед Компани Aluminosilicate or silicoaluminophosphate molecular sieve/manganese octahedral molecular sieve as catalysts for treating exhaust gas
CN105073687B (en) * 2013-03-29 2017-04-12 日本碍子株式会社 Aluminophosphate-metal oxide joined body and production method for same
BR112015029656A2 (en) * 2013-05-31 2017-07-25 Johnson Matthey Plc diesel particulate filter, system for treating a poor burning exhaust gas, and method for reducing soot in a poor burning exhaust gas
BR112015029664A2 (en) * 2013-05-31 2017-07-25 Johnson Matthey Plc diesel particulate filter, system for treating a poor burning exhaust gas, and method for reducing soot in a poor burning exhaust gas
KR102227267B1 (en) * 2013-07-30 2021-03-12 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Ammonia slip catalyst
JP6245895B2 (en) * 2013-08-27 2017-12-13 イビデン株式会社 Honeycomb catalyst and exhaust gas purification device
JP6204751B2 (en) * 2013-08-27 2017-09-27 イビデン株式会社 Honeycomb catalyst and exhaust gas purification device
KR20160048082A (en) 2013-08-30 2016-05-03 오츠카 가가쿠 가부시키가이샤 Exhaust gas purification filter and exhaust gas purification apparatus
US9782761B2 (en) 2013-10-03 2017-10-10 Ford Global Technologies, Llc Selective catalytic reduction catalyst
JP6513652B2 (en) 2013-10-31 2019-05-15 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Synthesis of AEI zeolite
US9283548B2 (en) 2013-11-19 2016-03-15 Toyota Motor Engineering & Manufacturing North America, Inc. Ceria-supported metal catalysts for the selective reduction of NOx
DE112015001008T5 (en) * 2014-02-28 2017-04-20 Johnson Matthey Public Limited Company Improved low temperature performance SCR catalysts and methods of making and using same
US9561469B2 (en) 2014-03-24 2017-02-07 Johnson Matthey Public Limited Company Catalyst for treating exhaust gas
GB2528737B (en) * 2014-03-24 2019-01-23 Johnson Matthey Plc Method for treating exhaust gas
WO2015146482A1 (en) * 2014-03-26 2015-10-01 三菱樹脂株式会社 Method for producing transition metal-containing zeolite, transition metal-containing zeolite obtained by said method, and exhaust gas purifying catalyst using said zeolite
JP6204238B2 (en) * 2014-03-26 2017-09-27 トヨタ自動車株式会社 Exhaust gas purification device for internal combustion engine
DE102014205760A1 (en) * 2014-03-27 2015-10-01 Johnson Matthey Public Limited Company Process for producing a catalyst and catalyst
JP6126141B2 (en) * 2014-05-30 2017-05-10 トヨタ自動車株式会社 Method for producing exhaust gas purification catalyst
US10850265B2 (en) 2014-06-18 2020-12-01 Basf Corporation Molecular sieve catalyst compositions, catalytic composites, systems, and methods
US9889437B2 (en) 2015-04-15 2018-02-13 Basf Corporation Isomorphously substituted catalyst
US9764313B2 (en) 2014-06-18 2017-09-19 Basf Corporation Molecular sieve catalyst compositions, catalyst composites, systems, and methods
ES2554648B1 (en) 2014-06-20 2016-09-08 Consejo Superior De Investigaciones Científicas (Csic) ITQ-55 material, preparation and use procedure
GB2533448B (en) * 2014-08-07 2017-06-28 Johnson Matthey Plc Zoned catalyst for treating exhaust gas
RU2698817C2 (en) * 2014-08-15 2019-08-30 Джонсон Мэтти Паблик Лимитед Компани Zoned catalyst for treating exhaust gas
CN104226361B (en) * 2014-09-01 2017-06-20 清华大学苏州汽车研究院（吴江） Iron-based SCR catalyst and preparation method thereof
EP3204157A1 (en) * 2014-10-07 2017-08-16 Johnson Matthey Public Limited Company Molecular sieve catalyst for treating exhaust gas
CN104475152B (en) * 2014-10-09 2017-12-22 南开大学 Catalyst and its application for the reduction of nitrogen oxides hydrogen selective catalysis
US10807082B2 (en) * 2014-10-13 2020-10-20 Johnson Matthey Public Limited Company Zeolite catalyst containing metals
EP3221032B1 (en) * 2014-11-19 2020-09-09 Johnson Matthey Public Limited Company Combining scr with pna for low temperature emission control
WO2016120840A1 (en) 2015-01-29 2016-08-04 Johnson Matthey Public Limited Company Direct incorporation of iron complexes into sapo-34 (cha) type materials
DE112016000534T5 (en) * 2015-01-30 2017-11-16 Ngk Insulators, Ltd. Separation membrane structure and nitrogen concentration reduction process
GB2540832B (en) * 2015-02-20 2019-04-17 Johnson Matthey Plc Bi-metal molecular sieve catalysts
MX2017010990A (en) 2015-02-27 2017-10-18 Basf Corp Exhaust gas treatment system.
CN104801335A (en) * 2015-04-11 2015-07-29 桂林理工大学 Zr-Ce-Mn/ZSM-5 complex oxide catalyst adopting NH3 to reduce NOx at low temperature as well as preparation method of Zr-Ce-Mn/ZSM-5 complex oxide catalyst
JP6292159B2 (en) * 2015-04-13 2018-03-14 トヨタ自動車株式会社 Exhaust gas purification catalyst
ES2586770B1 (en) 2015-04-16 2017-08-14 Consejo Superior De Investigaciones Científicas (Csic) DIRECT SYNTHESIS METHOD OF CU-SILICOALUMINATE MATERIAL WITH AEI ZEOLITHIC STRUCTURE, AND ITS CATALYTIC APPLICATIONS
RU2706923C2 (en) * 2015-05-19 2019-11-21 Басф Корпорейшн Catalysed particulate filter for use in passive selective catalytic reduction
EP3356019A1 (en) 2015-09-29 2018-08-08 Johnson Matthey Public Limited Company Catalytic filter having a soot catalyst and an scr catalyst
WO2017109705A1 (en) * 2015-12-22 2017-06-29 Basf Corporation Process for preparing iron(iii)-exchanged zeolite composition
JP6779498B2 (en) * 2016-01-22 2020-11-04 国立大学法人広島大学 Zeolites containing tin and methods for producing them
JP6951343B2 (en) * 2016-02-01 2021-10-20 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ Methods for Direct Synthesis of Iron-Containing AEI Zeolite Catalysts
US20190060885A1 (en) * 2016-04-13 2019-02-28 Umicore Ag & Co. Kg Particle filter having scr-active coating
CN109475855A (en) * 2016-05-11 2019-03-15 巴斯夫公司 The carbon monoxide-olefin polymeric containing magnetic material suitable for induction heating
GB201608643D0 (en) * 2016-05-17 2016-06-29 Thermo Fisher Scient Bremen Elemental analysis system and method
CN109475804A (en) * 2016-07-22 2019-03-15 庄信万丰股份有限公司 Exhaust gas catalyst and catalyst binder for filter substrate
KR101846914B1 (en) * 2016-10-21 2018-04-09 현대자동차 주식회사 Catalyst and manufacturing method of catalyst
EP3323785A1 (en) 2016-11-18 2018-05-23 Umicore AG & Co. KG Crystalline zeolites with eri/cha intergrowth framework type
US11104637B2 (en) * 2016-11-30 2021-08-31 Basf Se Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the MOR framework structure
KR101879695B1 (en) * 2016-12-02 2018-07-18 희성촉매 주식회사 Zeolite structures with specific Cu2+ (α)/ Cu2+ (β) ratio in NO DRIFTS spectrum, a method for preparing zeolite structures, and a catalyst composition comprising the zeolite structures
CN107497482A (en) * 2016-12-29 2017-12-22 廊坊市北辰创业树脂材料有限公司 A kind of preparation and application of new type low temperature composite catalyst
CN106799234B (en) * 2016-12-30 2019-07-05 包头稀土研究院 A kind of automobile-used rare-earth base SCR catalyst of diesel oil and preparation method
GB2562160B (en) 2017-03-20 2021-06-23 Johnson Matthey Plc Catalytic wall-flow filter with an ammonia slip catalyst
GB2560990A (en) * 2017-03-31 2018-10-03 Johnson Matthey Catalysts Germany Gmbh Composite material
US11179707B2 (en) 2017-03-31 2021-11-23 Johnson Matthey Catalysts (Germany) Gmbh Composite material
BR112019020841A2 (en) * 2017-04-04 2020-04-28 Basf Corp catalytic article of monolithic wall flow filter, vehicles, exhaust gas treatment systems and methods for treating an exhaust stream
CN108855079B (en) * 2017-05-11 2020-07-07 中国石油化工股份有限公司 Flue gas denitration catalyst, preparation method thereof and denitration process
CN107138174A (en) * 2017-06-23 2017-09-08 华娜 A kind of denitrating catalyst and preparation method thereof
EP3651900A1 (en) * 2017-07-11 2020-05-20 Shell Internationale Research Maatschappij B.V. A catalyst and method of use thereof
EP3651899A1 (en) 2017-07-11 2020-05-20 Shell Internationale Research Maatschappij B.V. Catalyst and method of use thereof in the conversion of nox and n2o
CN109422276B (en) * 2017-08-30 2022-10-18 中国科学院大连化学物理研究所 Transition metal doped molecular sieve and preparation method and application thereof
JP6964479B2 (en) 2017-10-03 2021-11-10 エヌ・イーケムキャット株式会社 Rare earth element skeleton-substituted zeolite and its production method, NOx adsorbent using them, selective reduction catalyst and automobile exhaust gas catalyst
CN107649175B (en) * 2017-10-23 2020-11-03 上海歌通实业有限公司 Preparation method of Ga-Ge-doped MnOx-SAPO molecular sieve catalyst
CN109794284B (en) * 2017-11-17 2020-06-09 中国科学院大连化学物理研究所 Molecular sieve material with metal enriched surface, preparation method and application thereof
JP7158141B2 (en) 2017-11-27 2022-10-21 エヌ・イーケムキャット株式会社 Slurry composition for catalyst, method for producing the same, method for producing catalyst using the same, and method for producing Cu-containing zeolite
CN109833905A (en) 2017-11-29 2019-06-04 中国科学院大连化学物理研究所 Molecular sieve catalyst and its preparation method and application
CN108187655A (en) * 2017-12-27 2018-06-22 龙岩紫荆创新研究院 A kind of SCR catalyst for denitrating flue gas, preparation method and applications system
EP3727685A4 (en) * 2018-01-03 2021-08-25 BASF Corporation Surface-treated silicoaluminophosphate molecular sieve
JP2019142753A (en) * 2018-02-22 2019-08-29 いすゞ自動車株式会社 SSZ-13 and method for producing SSZ-13
JP7091768B2 (en) * 2018-03-27 2022-06-28 三菱ケミカル株式会社 Zeolite powder
JP2021520995A (en) * 2018-04-11 2021-08-26 ビーエーエスエフ コーポレーション Mixed zeolite-containing SCR catalyst
KR101963082B1 (en) 2018-05-15 2019-03-27 경북대학교 산학협력단 Organic thermoelectric material including organic weak base and organic thermoelectric element thereof
US10850264B2 (en) * 2018-05-18 2020-12-01 Umicore Ag & Co. Kg Hydrocarbon trap catalyst
FR3081340B1 (en) * 2018-05-24 2020-06-26 IFP Energies Nouvelles CATALYST COMPRISING A MIXTURE OF AN AFX STRUCTURAL TYPE ZEOLITE AND A BEA STRUCTURAL TYPE ZEOLITE AND AT LEAST ONE TRANSITIONAL METAL FOR THE SELECTIVE NOX REDUCTION
CN114072222A (en) * 2018-08-31 2022-02-18 庄信万丰股份有限公司 Bimetallic Cu/Mn catalyst for selective catalytic reduction
CN109433256A (en) * 2018-11-06 2019-03-08 广东工业大学 A kind of Cu/Mn-SSZ-39 catalyst and its preparation method and application
WO2020116020A1 (en) 2018-12-06 2020-06-11 エヌ・イーケムキャット株式会社 Exhaust gas purging device
CN109794286B (en) * 2019-01-16 2021-12-28 山东国瓷功能材料股份有限公司 CHA/AEI composite denitration catalyst and preparation method and application thereof
US10703986B1 (en) 2019-01-30 2020-07-07 Exxonmobil Research And Engineering Company Selective oxidation using encapsulated catalytic metal
JP7194431B2 (en) * 2019-05-15 2022-12-22 株式会社 Acr Catalysts, catalyst products and methods for producing catalysts
CN110026182A (en) * 2019-05-20 2019-07-19 中国人民大学 Low-temperature denitration catalyst and its preparation and application in high sulfur resistive
CN110292944B (en) * 2019-07-31 2022-11-08 北京工业大学 SCR denitration catalyst with ultra-wide temperature window and preparation method thereof
KR20210029943A (en) 2019-09-09 2021-03-17 현대자동차주식회사 High-performance zeolites for reducing nitrogen oxide and a manufacturing method thereof and a catalyst using the same
WO2021065577A1 (en) 2019-10-03 2021-04-08 エヌ・イーケムキャット株式会社 Exhaust gas purification device
JP7367203B2 (en) * 2019-10-16 2023-10-23 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー Combined zone-coated dual-use ammonia (AMOX) and nitric oxide oxidation catalyst
WO2021080894A1 (en) * 2019-10-21 2021-04-29 Basf Corporation Low temperature nox adsorber with enhanced regeneration efficiency
CN111013648A (en) * 2019-12-14 2020-04-17 中触媒新材料股份有限公司 Symbiotic composite molecular sieve with CHA/KFI structure, preparation method thereof and SCR application thereof
CN111437875B (en) * 2020-03-24 2023-10-27 武汉科技大学 Cerium-iron molecular sieve based catalyst with wide temperature range and preparation method thereof
US20220314207A9 (en) * 2020-03-31 2022-10-06 Massachusetts Institute Of Technology Catalytic compositions for the oxidation of substrates
CN112169830B (en) * 2020-10-16 2022-11-08 万华化学集团股份有限公司 Preparation method of basic metal oxide @ ZSM-5 catalyst, catalyst prepared by preparation method and application of catalyst
KR20220069375A (en) * 2020-11-20 2022-05-27 현대자동차주식회사 Zeolite catalyst for hydrocarbon oxidation and method for preparing the same
CN112691700A (en) * 2020-12-28 2021-04-23 廊坊市北辰创业树脂材料股份有限公司 Preparation method and application of small-pore Cu-ZK-5 molecular sieve catalyst
CN112973777B (en) * 2021-02-23 2022-10-21 浙江浙能技术研究院有限公司 Low Ir-loaded catalyst for efficiently decomposing nitrous oxide and preparation method thereof
KR20230073794A (en) 2021-11-19 2023-05-26 한국세라믹기술원 DeNOx CATALYST LOADED WITH CRYSTALLINE ZEOLITES AND METHOD FOR PREPARATION OF THE SAME
CN114505079B (en) * 2022-04-20 2022-06-24 山东万达环保科技有限公司 Preparation method of low-temperature manganese-based SCR denitration catalyst and application of low-temperature manganese-based SCR denitration catalyst in flue gas denitration
CN114713243A (en) * 2022-04-29 2022-07-08 辽宁科隆精细化工股份有限公司 Low-temperature efficient high-sulfur-resistance long-time stable SCR denitration catalyst and preparation method thereof

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3895094A (en) 1974-01-28 1975-07-15 Gulf Oil Corp Process for selective reduction of oxides of nitrogen
US4220632A (en) 1974-09-10 1980-09-02 The United States Of America As Represented By The United States Department Of Energy Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia
US4961917A (en) 1989-04-20 1990-10-09 Engelhard Corporation Method for reduction of nitrogen oxides with ammonia using promoted zeolite catalysts
US5589147A (en) 1994-07-07 1996-12-31 Mobil Oil Corporation Catalytic system for the reducton of nitrogen oxides
WO1999039809A1 (en) 1998-02-06 1999-08-12 Johnson Matthey Public Limited Company SYSTEM FOR NOx REDUCTION IN EXHAUST GASES
US5958818A (en) 1997-04-14 1999-09-28 Bulldog Technologies U.S.A., Inc. Alkaline phosphate-activated clay/zeolite catalysts
EP1057519A1 (en) 1999-05-18 2000-12-06 Kemira Metalkat Oy Purification system for diesel engine exhaust gases
WO2000072965A1 (en) 1999-05-27 2000-12-07 The Regents Of The University Of Michigan Zeolite catalysts for selective catalytic reduction of nitric oxide by ammonia and method of making
WO2001080978A1 (en) 2000-04-25 2001-11-01 Emitec Gesellschaft Für Emissionstechnologie Mbh Method for removing soot particles from an exhaust gas and corresponding collecting element
WO2002041991A2 (en) 2000-11-15 2002-05-30 Engelhard Corporation HYDROTHERMALLY STABLE METAL PROMOTED ZEOLITE BETA FOR NOx REDUCTION
US6514470B1 (en) 1999-10-28 2003-02-04 The Regents Of The University Of California Catalysts for lean burn engine exhaust abatement
WO2004002611A1 (en) 2002-06-28 2004-01-08 Johnson Matthey Public Limited Company Doped ceria-containing zeolite-based nh3 scr catalyst
DE102004013164A1 (en) 2004-03-17 2005-10-13 Adam Opel Ag Catalyst for improving the efficiency of NOx reduction in motor vehicles
WO2006064805A1 (en) 2004-12-17 2006-06-22 Munekatsu Furugen Electric treating method for exhaust gas of diesel engine and its device
DE102005010221A1 (en) 2005-03-05 2006-09-07 S&B Industrial Minerals Gmbh Process for the preparation of a catalytically active mineral based on a framework silicate
WO2008106519A1 (en) 2007-02-27 2008-09-04 Basf Catalysts Llc Copper cha zeolite catalysts
WO2008118434A1 (en) 2007-03-26 2008-10-02 Pq Corporation Novel microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same

Family Cites Families (186)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US798813A (en) † 1904-06-13 1905-09-05 Samuel James Macfarren Steering-gear for automobiles.
US3459676A (en) † 1966-06-14 1969-08-05 Mobil Oil Corp Synthetic zeolite and method for preparing the same
JPS51147470A (en) * 1975-06-12 1976-12-17 Toa Nenryo Kogyo Kk A process for catalytic reduction of nitrogen oxides
US4086186A (en) * 1976-11-04 1978-04-25 Mobil Oil Corporation Crystalline zeolite ZSM-34 and method of preparing the same
US4187199A (en) * 1977-02-25 1980-02-05 Chevron Research Company Hydrocarbon conversion catalyst
US4210521A (en) * 1977-05-04 1980-07-01 Mobil Oil Corporation Catalytic upgrading of refractory hydrocarbon stocks
US4297328A (en) * 1979-09-28 1981-10-27 Union Carbide Corporation Three-way catalytic process for gaseous streams
US4471150A (en) * 1981-12-30 1984-09-11 Mobil Oil Corporation Catalysts for light olefin production
WO1984000071A1 (en) * 1982-06-16 1984-01-05 Boeing Co Autopilot flight director system
US4544538A (en) 1982-07-09 1985-10-01 Chevron Research Company Zeolite SSZ-13 and its method of preparation
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
EP0115031A1 (en) * 1982-12-23 1984-08-08 Union Carbide Corporation Ferrosilicate molecular sieve composition
US4567029A (en) * 1983-07-15 1986-01-28 Union Carbide Corporation Crystalline metal aluminophosphates
US4735927A (en) 1985-10-22 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
US4735930A (en) * 1986-02-18 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
EP0233642A3 (en) * 1986-02-18 1989-09-06 W.R. Grace & Co.-Conn. Process for hydrogenation of organic compounds
US4798813A (en) 1986-07-04 1989-01-17 Babcock-Hitachi Kabushiki Kaisha Catalyst for removing nitrogen oxide and process for producing the catalyst
JPH0611381B2 (en) * 1986-10-17 1994-02-16 株式会社豊田中央研究所 Exhaust gas purification method
US4912776A (en) 1987-03-23 1990-03-27 W. R. Grace & Co.-Conn. Process for removal of NOx from fluid streams
JPS63294950A (en) * 1987-05-27 1988-12-01 Cataler Kogyo Kk Catalyst for reducing nitrogen oxide
DE3723072A1 (en) * 1987-07-11 1989-01-19 Basf Ag METHOD FOR REMOVING NITROGEN OXIDES FROM EXHAUST GASES
US4861743A (en) * 1987-11-25 1989-08-29 Uop Process for the production of molecular sieves
US4867954A (en) † 1988-04-07 1989-09-19 Uop Catalytic reduction of nitrogen oxides
US4874590A (en) * 1988-04-07 1989-10-17 Uop Catalytic reduction of nitrogen oxides
JP2732614B2 (en) * 1988-10-18 1998-03-30 バブコツク日立株式会社 Exhaust gas purification catalyst and exhaust gas purification method
FR2645141B1 (en) 1989-03-31 1992-05-29 Elf France PROCESS FOR THE SYNTHESIS OF PRECURSORS OF MOLECULAR SIEVES OF THE SILICOALUMINOPHOSPHATE TYPE, PRECURSORS OBTAINED AND THEIR APPLICATION FOR OBTAINING SAID MOLECULAR SIEVES
US5024981A (en) † 1989-04-20 1991-06-18 Engelhard Corporation Staged metal-promoted zeolite catalysts and method for catalytic reduction of nitrogen oxides using the same
JP2533371B2 (en) 1989-05-01 1996-09-11 株式会社豊田中央研究所 Exhaust gas purification catalyst
US5477014A (en) 1989-07-28 1995-12-19 Uop Muffler device for internal combustion engines
JPH07106300B2 (en) * 1989-12-08 1995-11-15 財団法人産業創造研究所 Method for removing nitrogen oxides in combustion exhaust gas
US6063723A (en) * 1990-03-02 2000-05-16 Chevron U.S.A. Inc. Sulfur tolerant zeolite catalyst
JP2645614B2 (en) * 1991-01-08 1997-08-25 財団法人石油産業活性化センター Purification method of exhaust gas containing nitrogen oxides
EP0494388B1 (en) 1991-01-08 1995-12-06 Agency Of Industrial Science And Technology Process for removing nitrogen oxides from exhaust gases
GB9101456D0 (en) 1991-01-23 1991-03-06 Exxon Chemical Patents Inc Process for producing substantially binder-free zeolite
US5233117A (en) * 1991-02-28 1993-08-03 Uop Methanol conversion processes using syocatalysts
US5348643A (en) * 1991-03-12 1994-09-20 Mobil Oil Corp. Catalytic conversion with improved catalyst
JPH0557194A (en) 1991-07-06 1993-03-09 Toyota Motor Corp Production of catalyst for purifying exhaust gas
JP2887984B2 (en) 1991-09-20 1999-05-10 トヨタ自動車株式会社 Exhaust gas purification device for internal combustion engine
US5171553A (en) * 1991-11-08 1992-12-15 Air Products And Chemicals, Inc. Catalytic decomposition of N2 O
JP3303341B2 (en) 1992-07-30 2002-07-22 三菱化学株式会社 Method for producing beta zeolite
US5316753A (en) * 1992-10-09 1994-05-31 Chevron Research And Technology Company Zeolite SSZ-35
US6248684B1 (en) 1992-11-19 2001-06-19 Englehard Corporation Zeolite-containing oxidation catalyst and method of use
WO1994011623A2 (en) 1992-11-19 1994-05-26 Engelhard Corporation Method and apparatus for treating an engine exhaust gas stream
ATE191060T1 (en) 1992-11-19 2000-04-15 Engelhard Corp APPLICATION AND DEVICE FOR TREATING A MACHINE EXHAUST STREAM
US5346612A (en) * 1993-02-19 1994-09-13 Amoco Corporation Distillate hydrogenation utilizing a catalyst comprising platinum, palladium, and a beta zeolite support
DE69427932T2 (en) * 1993-05-10 2002-04-04 Sakai Chemical Industry Co Catalyst for the catalytic reduction of nitrogen oxides
JPH06320006A (en) * 1993-05-10 1994-11-22 Sekiyu Sangyo Kasseika Center Catalyst for catalytic reduction of nox
US5417949A (en) 1993-08-25 1995-05-23 Mobil Oil Corporation NOx abatement process
WO1995013128A1 (en) 1993-11-09 1995-05-18 Union Carbide Chemicals & Plastics Technology Corporation Absorption of mercaptans
KR960000008A (en) 1994-06-13 1996-01-25 전상정 How to prepare seedling mat
CA2193951A1 (en) * 1994-07-07 1996-01-25 Costandi Amin Audeh Catalytic system for the reduction of nitrogen oxides
US5482692A (en) * 1994-07-07 1996-01-09 Mobil Oil Corporation Selective catalytic reduction of nitrogen oxides using a ferrocene impregnated zeolite catalyst
US5520895A (en) * 1994-07-07 1996-05-28 Mobil Oil Corporation Method for the reduction of nitrogen oxides using iron impregnated zeolites
JPH0824656A (en) * 1994-07-22 1996-01-30 Mazda Motor Corp Catalyst for purifying exhaust gas
US6080377A (en) * 1995-04-27 2000-06-27 Engelhard Corporation Method of abating NOx and a catalytic material therefor
JP3375790B2 (en) 1995-06-23 2003-02-10 日本碍子株式会社 Exhaust gas purification system and exhaust gas purification method
US6471924B1 (en) * 1995-07-12 2002-10-29 Engelhard Corporation Method and apparatus for NOx abatement in lean gaseous streams
US6133185A (en) 1995-11-09 2000-10-17 Toyota Jidosha Kabushiki Kaisha Exhaust gas purifying catalyst
JPH10180041A (en) 1996-12-20 1998-07-07 Ngk Insulators Ltd Catalyst for purification of exhaust gas and exhaust gas purifying system
US5925800A (en) * 1996-12-31 1999-07-20 Exxon Chemical Patents Inc. Conversion of oxygenates to hydrocarbons with monolith supported non-zeolitic molecular sieve catalysts
US5897846A (en) 1997-01-27 1999-04-27 Asec Manufacturing Catalytic converter having a catalyst with noble metal on molecular sieve crystal surface and method of treating diesel engine exhaust gas with same
DE19723950A1 (en) * 1997-06-06 1998-12-10 Basf Ag Process for the oxidation of an organic compound having at least one C-C double bond
US6004527A (en) * 1997-09-29 1999-12-21 Abb Lummus Global Inc. Method for making molecular sieves and novel molecular sieve compositions
JPH11114413A (en) 1997-10-09 1999-04-27 Ngk Insulators Ltd Adsorbent for cleaning exhaust gas
US6162415A (en) 1997-10-14 2000-12-19 Exxon Chemical Patents Inc. Synthesis of SAPO-44
EP1044068A1 (en) * 1997-12-03 2000-10-18 Exxon Chemical Patents Inc. Catalyst comprising a zeolite partially coated with a second zeolite, its use for hydrocarbon conversion
US7033969B1 (en) 1997-12-10 2006-04-25 Volvo Car Corporation Porous material, method and arrangement for catalytic conversion of exhaust gases
US5958370A (en) † 1997-12-11 1999-09-28 Chevron U.S.A. Inc. Zeolite SSZ-39
US6346498B1 (en) * 1997-12-19 2002-02-12 Exxonmobil Oil Corporation Zeolite catalysts having stabilized hydrogenation-dehydrogenation function
GB9808876D0 (en) 1998-04-28 1998-06-24 Johnson Matthey Plc Combatting air pollution
AU3765299A (en) 1998-05-07 1999-11-23 Engelhard Corporation Catalyzed hydrocarbon trap and method using the same
US6576203B2 (en) 1998-06-29 2003-06-10 Ngk Insulators, Ltd. Reformer
US6143681A (en) * 1998-07-10 2000-11-07 Northwestern University NOx reduction catalyst
EP1105348B1 (en) * 1998-07-29 2003-04-02 ExxonMobil Chemical Patents Inc. Crystalline molecular sieves
US20020014071A1 (en) * 1998-10-01 2002-02-07 Mari Lou Balmer Catalytic plasma reduction of nox
EP1005904A3 (en) 1998-10-30 2000-06-14 The Boc Group, Inc. Adsorbents and adsorptive separation process
DE19854502A1 (en) 1998-11-25 2000-05-31 Siemens Ag Catalyst body and process for breaking down nitrogen oxides
KR100293531B1 (en) 1998-12-24 2001-10-26 윤덕용 Hybrid Catalysts for Hydrocarbon Generation from Carbon Dioxide
US6787023B1 (en) * 1999-05-20 2004-09-07 Exxonmobil Chemical Patents Inc. Metal-containing macrostructures of porous inorganic oxide, preparation thereof, and use
US6503863B2 (en) 1999-06-07 2003-01-07 Exxonmobil Chemical Patents, Inc. Heat treating a molecular sieve and catalyst
US6316683B1 (en) 1999-06-07 2001-11-13 Exxonmobil Chemical Patents Inc. Protecting catalytic activity of a SAPO molecular sieve
US6395674B1 (en) 1999-06-07 2002-05-28 Exxon Mobil Chemical Patents, Inc. Heat treating a molecular sieve and catalyst
JP4352516B2 (en) * 1999-08-03 2009-10-28 トヨタ自動車株式会社 Exhaust gas purification device for internal combustion engine
US7084087B2 (en) * 1999-09-07 2006-08-01 Abb Lummus Global Inc. Zeolite composite, method for making and catalytic application thereof
JP4380859B2 (en) * 1999-11-29 2009-12-09 三菱瓦斯化学株式会社 Catalyst molded body
RU2002118713A (en) * 1999-12-15 2004-02-27 Шеврон Ю.Эс.Эй. Инк. (Us) Zeolite SSZ-50
ES2250035T3 (en) 2000-03-01 2006-04-16 UMICORE AG & CO. KG CATALYST FOR PURIFICATION OF DIESEL ENGINE EXHAUST GASES AND PROCESS FOR PREPARATION.
US6606856B1 (en) 2000-03-03 2003-08-19 The Lubrizol Corporation Process for reducing pollutants from the exhaust of a diesel engine
JP2001280363A (en) 2000-03-29 2001-10-10 Toyota Autom Loom Works Ltd Power transmission mechanism
DE10036476A1 (en) * 2000-07-25 2002-02-07 Basf Ag Heterogeneous catalyzed gas phase decomposition of N2O uses fixed bed catalyst comprising two or more catalyst layers that are optionally separated by inert intermediate layers or gas chambers
AU2001252241A1 (en) * 2000-04-03 2001-10-15 Basf Aktiengesellschaft Catalyst system for the decomposition of n2o
DE10020100A1 (en) 2000-04-22 2001-10-31 Dmc2 Degussa Metals Catalysts Process and catalyst for the reduction of nitrogen oxides
US6448197B1 (en) * 2000-07-13 2002-09-10 Exxonmobil Chemical Patents Inc. Method for making a metal containing small pore molecular sieve catalyst
US6576796B1 (en) * 2000-06-28 2003-06-10 Basf Aktiengesellschaft Process for the preparation of alkylamines
DE10059520A1 (en) 2000-11-30 2001-05-17 Univ Karlsruhe Separation of zeolite crystals, useful as catalyst or adsorbent, involves adding water-soluble salt or precursor to aqueous sol or suspension before sedimentation, centrifugation or filtration
US20050096214A1 (en) 2001-03-01 2005-05-05 Janssen Marcel J. Silicoaluminophosphate molecular sieve
US6440894B1 (en) 2001-06-25 2002-08-27 Exxonmobil Chemical Patents, Inc. Methods of removing halogen from non-zeolitic molecular sieve catalysts
CN1239262C (en) 2001-06-25 2006-02-01 埃克森美孚化学专利公司 Molecular sieve catalyst composition, its making and use in conversion processes
US20030007901A1 (en) * 2001-07-03 2003-01-09 John Hoard Method and system for reduction of NOx in automotive vehicle exhaust systems
JP5189236B2 (en) 2001-07-25 2013-04-24 日本碍子株式会社 Exhaust gas purification honeycomb structure and exhaust gas purification honeycomb catalyst body
US6759358B2 (en) † 2001-08-21 2004-07-06 Sud-Chemie Inc. Method for washcoating a catalytic material onto a monolithic structure
US6709644B2 (en) 2001-08-30 2004-03-23 Chevron U.S.A. Inc. Small crystallite zeolite CHA
US6914026B2 (en) 2001-09-07 2005-07-05 Engelhard Corporation Hydrothermally stable metal promoted zeolite beta for NOx reduction
US6508860B1 (en) * 2001-09-21 2003-01-21 L'air Liquide - Societe Anonyme A'directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Gas separation membrane with organosilicon-treated molecular sieve
DE10150480B4 (en) * 2001-10-16 2019-11-28 Exxonmobil Chemical Patents Inc. Process for the preparation of an olefin-containing product stream
US6601385B2 (en) * 2001-10-17 2003-08-05 Fleetguard, Inc. Impactor for selective catalytic reduction system
US7014827B2 (en) 2001-10-23 2006-03-21 Machteld Maria Mertens Synthesis of silicoaluminophosphates
US6696032B2 (en) 2001-11-29 2004-02-24 Exxonmobil Chemical Patents Inc. Process for manufacturing a silicoaluminophosphate molecular sieve
US7264785B2 (en) 2001-12-20 2007-09-04 Johnson Matthey Public Limited Company Selective catalytic reduction
US6685905B2 (en) 2001-12-21 2004-02-03 Exxonmobil Chemical Patents Inc. Silicoaluminophosphate molecular sieves
EP1472202A4 (en) * 2002-01-03 2008-01-23 Exxonmobil Chem Patents Inc Stabilisation of acid catalysts
US6995111B2 (en) * 2002-02-28 2006-02-07 Exxonmobil Chemical Patents Inc. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes
DE10232406A1 (en) 2002-07-17 2004-01-29 Basf Ag Process for the preparation of a zeolite-containing solid
US20040064007A1 (en) * 2002-09-30 2004-04-01 Beech James H. Method and system for regenerating catalyst from a plurality of hydrocarbon conversion apparatuses
US6717025B1 (en) * 2002-11-15 2004-04-06 Exxonmobil Chemical Patents Inc Process for removing oxygenates from an olefinic stream
US6928806B2 (en) 2002-11-21 2005-08-16 Ford Global Technologies, Llc Exhaust gas aftertreatment systems
JP2004188388A (en) * 2002-12-13 2004-07-08 Babcock Hitachi Kk Filter for cleaning diesel exhaust gas and its production method
US7122492B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
WO2004074411A1 (en) * 2003-02-18 2004-09-02 Japan Gas Synthesize, Ltd. Method for producing liquefied petroleum gas
US7049261B2 (en) 2003-02-27 2006-05-23 General Motors Corporation Zeolite catalyst and preparation process for NOx reduction
DE10315593B4 (en) * 2003-04-05 2005-12-22 Daimlerchrysler Ag Exhaust gas aftertreatment device and method
JP4413520B2 (en) 2003-04-17 2010-02-10 株式会社アイシーティー Exhaust gas purification catalyst and exhaust gas purification method using the catalyst
US6897179B2 (en) * 2003-06-13 2005-05-24 Exxonmobil Chemical Patents Inc. Method of protecting SAPO molecular sieve from loss of catalytic activity
DE602004006415T2 (en) 2003-06-18 2008-01-10 Johnson Matthey Public Ltd., Co. PROCESS FOR CONTROLLING THE REDUCTION ADDITIVE
US20040262197A1 (en) * 2003-06-24 2004-12-30 Mcgregor Duane R. Reduction of NOx in low CO partial-burn operation using full burn regenerator additives
JP2005047721A (en) * 2003-07-29 2005-02-24 Mitsubishi Chemicals Corp Production method for aluminophosphate
US7229597B2 (en) 2003-08-05 2007-06-12 Basfd Catalysts Llc Catalyzed SCR filter and emission treatment system
US7253005B2 (en) * 2003-08-29 2007-08-07 Exxonmobil Chemical Patents Inc. Catalyst sampling system
JP4842143B2 (en) 2003-12-23 2011-12-21 エクソンモービル・ケミカル・パテンツ・インク Kabasite-containing molecular sieve, its synthesis and its use in the conversion of eusigenate to olefins
EA011395B1 (en) 2003-12-23 2009-02-27 Эксонмобил Кемикэл Пейтентс Инк. Aei-type zeolite, its synthesis and its use in the conversion of oxygenates to olefins
GB0405015D0 (en) * 2004-03-05 2004-04-07 Johnson Matthey Plc Method of loading a monolith with catalyst and/or washcoat
US7192987B2 (en) * 2004-03-05 2007-03-20 Exxonmobil Chemical Patents Inc. Processes for making methanol streams and uses for the streams
DE102004013165A1 (en) * 2004-03-17 2005-10-06 Adam Opel Ag Method for improving the effectiveness of NOx reduction in motor vehicles
NL1026207C2 (en) * 2004-05-17 2005-11-21 Stichting Energie Process for the decomposition of N2O, catalyst for it and preparation of this catalyst.
EP1787720B1 (en) * 2004-07-15 2016-11-02 Nikki-Universal Co., Ltd. Catalyst for purifying exhaust gas containing organic nitrogen compound and method for purifying such exhaust gas
CA2575338C (en) * 2004-07-27 2015-09-01 Los Alamos National Security, Llc Catalyst and method for reduction of nitrogen oxides
US20060035782A1 (en) * 2004-08-12 2006-02-16 Ford Global Technologies, Llc PROCESSING METHODS AND FORMULATIONS TO ENHANCE STABILITY OF LEAN-NOx-TRAP CATALYSTS BASED ON ALKALI- AND ALKALINE-EARTH-METAL COMPOUNDS
US7481983B2 (en) 2004-08-23 2009-01-27 Basf Catalysts Llc Zone coated catalyst to simultaneously reduce NOx and unreacted ammonia
JP4662334B2 (en) 2004-11-04 2011-03-30 三菱ふそうトラック・バス株式会社 Exhaust gas purification device for internal combustion engine
EP1824784B1 (en) * 2004-11-29 2019-08-21 Chevron U.S.A., Inc. High-silica molecular sieve cha
US20060115403A1 (en) 2004-11-29 2006-06-01 Chevron U.S.A. Inc. Reduction of oxides of nitrogen in a gas stream using high-silics molecular sieve CHA
JP2008521746A (en) * 2004-11-30 2008-06-26 シェブロン ユー．エス．エー． インコーポレイテッド Boron-containing molecular sieve CHA
MX2007011531A (en) * 2005-03-24 2007-11-16 Grace W R & Co Method for controlling nox emissions in the fccu.
US20090060809A1 (en) 2005-03-30 2009-03-05 Sued-Chemie Catalysts Japan, Inc. Ammonia Decomposition Catalyst and Process for Decomposition of Ammonia Using the Catalyst
JP5383184B2 (en) * 2005-04-27 2014-01-08 ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット Compositions and methods for reducing NOx emissions during fluid catalytic cracking
US7879295B2 (en) * 2005-06-30 2011-02-01 General Electric Company Conversion system for reducing NOx emissions
EP1904229A4 (en) 2005-07-06 2014-04-16 Heesung Catalysts Corp An oxidation catalyst for nh3 and an apparatus for treating slipped or scrippedd nh3
US20070012032A1 (en) * 2005-07-12 2007-01-18 Eaton Corporation Hybrid system comprising HC-SCR, NOx-trapping, and NH3-SCR for exhaust emission reduction
US8048402B2 (en) 2005-08-18 2011-11-01 Exxonmobil Chemical Patents Inc. Synthesis of molecular sieves having the chabazite framework type and their use in the conversion of oxygenates to olefins
JP4698359B2 (en) 2005-09-22 2011-06-08 Ｕｄトラックス株式会社 Exhaust purification device
JP2007100508A (en) 2005-09-30 2007-04-19 Bosch Corp Exhaust emission control device of internal combustion engine, and exhaust emission control method for internal combustion engine
US7678955B2 (en) 2005-10-13 2010-03-16 Exxonmobil Chemical Patents Inc Porous composite materials having micro and meso/macroporosity
US7807122B2 (en) * 2005-11-02 2010-10-05 Exxonmobil Chemical Patents Inc. Metalloaluminophosphate molecular sieves, their synthesis and use
RU2008128363A (en) * 2005-12-14 2010-01-20 Басф Каталистс Ллк (Us) ZEOLITE CATALYST WITH IMPROVED NOx REDUCTION IN SCR
US20070149385A1 (en) 2005-12-23 2007-06-28 Ke Liu Catalyst system for reducing nitrogen oxide emissions
WO2007104385A1 (en) * 2006-03-10 2007-09-20 Exxonmobil Chemical Patents Inc. Lowering nitrogen-containing lewis bases in molecular sieve oligomerisation
US8383079B2 (en) * 2006-04-17 2013-02-26 Exxonmobil Chemical Patents Inc. Molecular sieves having micro and mesoporosity, their synthesis and their use in the organic conversion reactions
DE102006020158B4 (en) * 2006-05-02 2009-04-09 Argillon Gmbh Extruded full catalyst and process for its preparation
US8383080B2 (en) 2006-06-09 2013-02-26 Exxonmobil Chemical Patents Inc. Treatment of CHA-type molecular sieves and their use in the conversion of oxygenates to olefins
US20080003909A1 (en) 2006-06-29 2008-01-03 Hien Nguyen Non-woven structures and methods of making the same
DE102006037314A1 (en) * 2006-08-08 2008-02-14 Süd-Chemie AG Use of a catalyst based on zeolites in the reaction of oxygenates to lower olefins and processes for this purpose
CN101121532A (en) 2006-08-08 2008-02-13 中国科学院大连化学物理研究所 Metal modifying method for pinhole phosphorus-silicon-aluminum molecular sieve
US7829751B2 (en) * 2006-10-27 2010-11-09 Exxonmobil Chemical Patents, Inc. Processes for converting oxygenates to olefins using aluminosilicate catalysts
US7815712B2 (en) * 2006-12-18 2010-10-19 Uop Llc Method of making high performance mixed matrix membranes using suspensions containing polymers and polymer stabilized molecular sieves
MY151327A (en) 2007-01-31 2014-05-15 Basf Catalysts Llc Gas catalysts comprising porous wall honeycombs
CA2679599C (en) 2007-02-27 2016-01-05 Basf Catalysts Llc Bifunctional catalysts for selective ammonia oxidation
US7998423B2 (en) * 2007-02-27 2011-08-16 Basf Corporation SCR on low thermal mass filter substrates
US10384162B2 (en) * 2007-03-26 2019-08-20 Pq Corporation High silica chabazite for selective catalytic reduction, methods of making and using same
JP5777339B2 (en) 2007-04-26 2015-09-09 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Transition metal / zeolite SCR catalyst
DE102007063604A1 (en) 2007-05-24 2008-12-04 Süd-Chemie AG Metal-doped zeolite and process for its preparation
DE102007030895A1 (en) 2007-07-03 2009-01-08 Süd-Chemie AG Catalytic converter for hydrochloric acid-containing exhaust gases
CN101827654B (en) 2007-08-13 2013-11-06 Pq公司 Novel iron-containing aluminosilicate zeolites and methods of making and using same
US20090056319A1 (en) * 2007-09-04 2009-03-05 Warner Jay V Exhaust Aftertreatment System with Pre-Catalysis
EP2234938B1 (en) 2007-11-30 2019-08-07 Corning Incorporated Zeolite-based honeycomb body
US20090196812A1 (en) * 2008-01-31 2009-08-06 Basf Catalysts Llc Catalysts, Systems and Methods Utilizing Non-Zeolitic Metal-Containing Molecular Sieves Having the CHA Crystal Structure
US8232550B2 (en) * 2008-06-11 2012-07-31 3M Innovative Properties Company Mixed solvent systems for deposition of organic semiconductors
US8225597B2 (en) * 2008-09-30 2012-07-24 Ford Global Technologies, Llc System for reducing NOx in exhaust
GB0903262D0 (en) 2009-02-26 2009-04-08 Johnson Matthey Plc Filter
WO2010121257A1 (en) 2009-04-17 2010-10-21 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
DE102010007626A1 (en) † 2010-02-11 2011-08-11 Süd-Chemie AG, 80333 Copper-containing zeolite of the KFI type and use in SCR catalysis
US8017097B1 (en) 2010-03-26 2011-09-13 Umicore Ag & Co. Kg ZrOx, Ce-ZrOx, Ce-Zr-REOx as host matrices for redox active cations for low temperature, hydrothermally durable and poison resistant SCR catalysts
US9221015B2 (en) 2010-07-15 2015-12-29 Basf Se Copper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx
US8956992B2 (en) * 2011-10-27 2015-02-17 GM Global Technology Operations LLC SCR catalysts preparation methods
EP2908947B1 (en) * 2012-10-19 2021-09-29 BASF Corporation Mixed metal 8-ring small pore molecular sieve catalytic articles and methods
US10018070B2 (en) * 2013-09-30 2018-07-10 Siemens Aktiengesellschaft Method for operating a turbomachine, wherein an efficiency characteristic value of a stage is determined, and turbomachine having a device for carrying out the method
US10711674B2 (en) * 2017-10-20 2020-07-14 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber catalyst

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3895094A (en) 1974-01-28 1975-07-15 Gulf Oil Corp Process for selective reduction of oxides of nitrogen
US4220632A (en) 1974-09-10 1980-09-02 The United States Of America As Represented By The United States Department Of Energy Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia
US4961917A (en) 1989-04-20 1990-10-09 Engelhard Corporation Method for reduction of nitrogen oxides with ammonia using promoted zeolite catalysts
US5589147A (en) 1994-07-07 1996-12-31 Mobil Oil Corporation Catalytic system for the reducton of nitrogen oxides
US5958818A (en) 1997-04-14 1999-09-28 Bulldog Technologies U.S.A., Inc. Alkaline phosphate-activated clay/zeolite catalysts
WO1999039809A1 (en) 1998-02-06 1999-08-12 Johnson Matthey Public Limited Company SYSTEM FOR NOx REDUCTION IN EXHAUST GASES
EP1057519A1 (en) 1999-05-18 2000-12-06 Kemira Metalkat Oy Purification system for diesel engine exhaust gases
WO2000072965A1 (en) 1999-05-27 2000-12-07 The Regents Of The University Of Michigan Zeolite catalysts for selective catalytic reduction of nitric oxide by ammonia and method of making
US6514470B1 (en) 1999-10-28 2003-02-04 The Regents Of The University Of California Catalysts for lean burn engine exhaust abatement
WO2001080978A1 (en) 2000-04-25 2001-11-01 Emitec Gesellschaft Für Emissionstechnologie Mbh Method for removing soot particles from an exhaust gas and corresponding collecting element
WO2002041991A2 (en) 2000-11-15 2002-05-30 Engelhard Corporation HYDROTHERMALLY STABLE METAL PROMOTED ZEOLITE BETA FOR NOx REDUCTION
WO2004002611A1 (en) 2002-06-28 2004-01-08 Johnson Matthey Public Limited Company Doped ceria-containing zeolite-based nh3 scr catalyst
DE102004013164A1 (en) 2004-03-17 2005-10-13 Adam Opel Ag Catalyst for improving the efficiency of NOx reduction in motor vehicles
WO2006064805A1 (en) 2004-12-17 2006-06-22 Munekatsu Furugen Electric treating method for exhaust gas of diesel engine and its device
DE102005010221A1 (en) 2005-03-05 2006-09-07 S&B Industrial Minerals Gmbh Process for the preparation of a catalytically active mineral based on a framework silicate
WO2008106519A1 (en) 2007-02-27 2008-09-04 Basf Catalysts Llc Copper cha zeolite catalysts
WO2008118434A1 (en) 2007-03-26 2008-10-02 Pq Corporation Novel microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ISHIHARA ET AL., JOURNAL OF CATALYSIS, vol. 169, 1997, pages 93
LONG ET AL., JOURNAL OF CATALYSIS, vol. 207, 2002, pages 274 - 285
S. KASAOKA ET AL.: "Effect of Inlet NO/N02 Molar Ratio and Contribution of Oxygen in the Catalytic Reduction of Nitrogen Oxides with Ammonia", NIPPON KAGAKU KAISHI, vol. 6, 1978, pages 874 - 881

Cited By (394)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10654031B2 (en) 2007-02-27 2020-05-19 Basf Corporation Copper CHA zeolite catalysts
US8119088B2 (en) 2007-02-27 2012-02-21 Basf Corporation SCR on low thermal mass filter substrates
US8735311B2 (en) 2007-02-27 2014-05-27 Basf Corporation Copper CHA zeolite catalysts
US7998423B2 (en) 2007-02-27 2011-08-16 Basf Corporation SCR on low thermal mass filter substrates
US11845067B2 (en) 2007-02-27 2023-12-19 Basf Corporation Copper CHA zeolite catalysts
US7601662B2 (en) 2007-02-27 2009-10-13 Basf Catalysts Llc Copper CHA zeolite catalysts
US11529619B2 (en) 2007-02-27 2022-12-20 Basf Corporation Copper CHA zeolite catalysts
US9162218B2 (en) 2007-02-27 2015-10-20 Basf Corporation Copper CHA zeolite catalysts
US8404203B2 (en) 2007-02-27 2013-03-26 Basf Corporation Processes for reducing nitrogen oxides using copper CHA zeolite catalysts
US9839905B2 (en) 2007-02-27 2017-12-12 Basf Corporation Copper CHA zeolite catalysts
EP2117707A1 (en) 2007-02-27 2009-11-18 Basf Catalysts Llc Copper cha zeolite catalysts
US9138732B2 (en) 2007-02-27 2015-09-22 Basf Corporation Copper CHA zeolite catalysts
US9656254B2 (en) 2007-02-27 2017-05-23 Basf Corporation Copper CHA zeolite catalysts
US8603432B2 (en) 2007-04-26 2013-12-10 Paul Joseph Andersen Transition metal/zeolite SCR catalysts
EP2517776B2 (en) † 2007-04-26 2019-08-07 Johnson Matthey Public Limited Company Transition metal/kfi-zeolite scr catalyst
US11478748B2 (en) 2007-04-26 2022-10-25 Johnson Matthey Public Limited Company Transition metal/zeolite SCR catalysts
WO2009099937A1 (en) * 2008-01-31 2009-08-13 Basf Catalysts Llc Catalysts, systems and methods utilizing non-zeolitic metal-containing molecular sieves having the cha crystal structure
US8617474B2 (en) 2008-01-31 2013-12-31 Basf Corporation Systems utilizing non-zeolitic metal-containing molecular sieves having the CHA crystal structure
US10105649B2 (en) 2008-01-31 2018-10-23 Basf Corporation Methods utilizing non-zeolitic metal-containing molecular sieves having the CHA crystal structure
EP2918329B1 (en) 2008-05-07 2017-08-02 Umicore Ag & Co. Kg Device and method for reducing nitrogen oxides in hydrocarbon-containing waste gas streams using an scr catalytic converter on the basis of a molecular filter
EP2918329A1 (en) * 2008-05-07 2015-09-16 Umicore Ag & Co. Kg Method for reducing nitrogen oxides in hydrocarbon containing waste gas streams using an scr catalytic converter on the basis of a molecular filter
WO2009135588A1 (en) * 2008-05-07 2009-11-12 Umicore Ag & Co. Kg Method for decreasing nitrogen oxides in hydrocarbon-containing exhaust gases using an scr catalyst based on a molecular sieve
EP2918330A1 (en) * 2008-05-07 2015-09-16 Umicore Ag & Co. Kg Method for reducing nitrogen oxides in hydrocarbon containing waste gas streams using an scr catalytic converter on the basis of a molecular filter
JP2011519722A (en) * 2008-05-07 2011-07-14 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト Method for reducing nitrogen oxides in exhaust gases containing hydrocarbons using SCR catalysts based on molecular sieves
EP2898941A1 (en) * 2008-05-07 2015-07-29 Umicore AG & Co. KG System for treating diesel engine exhaust gases containing nitrogen oxides and hydrocarbons
EP3195920A1 (en) * 2008-05-07 2017-07-26 Umicore Ag & Co. Kg Method for decreasing nitrogen oxides in hydrocarbon-containing exhaust gases using an scr catalyst based on a molecular sieve
WO2009141324A1 (en) * 2008-05-21 2009-11-26 Basf Se Process for the direct synthesis of cu containing zeolites having cha structure
US8715618B2 (en) 2008-05-21 2014-05-06 Basf Se Process for the direct synthesis of Cu containing zeolites having CHA structure
EP3778484A1 (en) * 2008-05-21 2021-02-17 Basf Se Process for the direct synthesis of cu containing zeolites having cha structure
US9272272B2 (en) 2008-05-21 2016-03-01 Basf Se Process for the direct synthesis of Cu containing zeolites having CHA structure
EP2551240A3 (en) * 2008-05-21 2016-04-20 Basf Se Process for the direct synthesis of Cu containing zeolites having CHA structure
US10316739B2 (en) 2008-06-27 2019-06-11 Umicore Ag & Co. Kg Method and device for the purification of diesel exhaust gases
US10001053B2 (en) 2008-06-27 2018-06-19 Umicore Ag & Co. Kg Method and device for the purification of diesel exhaust gases
EP2878361A1 (en) * 2008-10-15 2015-06-03 Johnson Matthey Public Limited Company Transition metal-containing aluminosilicate zeolite
WO2010043891A1 (en) 2008-10-15 2010-04-22 Johnson Matthey Public Limited Company Transition metal-containing aluminosilicate zeolite
DE202009018988U1 (en) 2008-10-15 2015-03-05 Johnson Matthey Public Ltd., Co. Copper-containing aluminosilicate zeolite catalyst
EP2352912B1 (en) 2008-11-03 2018-07-04 BASF Corporation Integrated scr and amox catalyst systems
US11660585B2 (en) 2008-11-06 2023-05-30 Basf Corporation Chabazite zeolite catalysts having low silica to alumina ratios
US10583424B2 (en) 2008-11-06 2020-03-10 Basf Corporation Chabazite zeolite catalysts having low silica to alumina ratios
US20120020875A1 (en) * 2009-01-22 2012-01-26 Mitsubishi Plastics, Inc. Catalyst for reducing nitrogen oxides and method for producing the same
DE102010002425B4 (en) * 2009-02-26 2016-03-31 Johnson Matthey Public Limited Company filter
EP2401056B1 (en) 2009-02-26 2016-04-13 Johnson Matthey Public Limited Company Filter for filtering particulate matter from exhaust gas emitted from a positive ignition engine
US8512657B2 (en) 2009-02-26 2013-08-20 Johnson Matthey Public Limited Company Method and system using a filter for treating exhaust gas having particulate matter
US8012439B2 (en) 2009-02-26 2011-09-06 Johnson Matthey Public Limited Company Filter
DE202010018079U1 (en) 2009-02-26 2014-02-04 Johnson Matthey Public Limited Company A spark-ignition engine comprising an exhaust system with a filter therefor
US9415344B2 (en) * 2009-02-26 2016-08-16 Johnson Matthey Public Limited Company Method and system using a filter for treating exhaust gas having particulate matter
US8919110B2 (en) * 2009-02-26 2014-12-30 Johnson Matthey Public Limited Company Method and system using a filter for treating exhaust gas having particulate matter
US8608820B2 (en) 2009-02-26 2013-12-17 Johnson Matthey Public Limited Company Filter for filtering particulate matter from exhaust gas emitted from a compression ignition engine
EP3777998A1 (en) 2009-02-26 2021-02-17 Johnson Matthey Public Limited Company Filter
DE102010002425A1 (en) 2009-02-26 2010-09-23 Johnson Matthey Public Limited Company filter
WO2010097638A1 (en) 2009-02-26 2010-09-02 Johnson Matthey Public Limited Company Filter for filtering particulate matter from exhaust gas emitted from a compression ignition engine
WO2010097634A1 (en) 2009-02-26 2010-09-02 Johnson Matthey Public Limited Company Filter for filtering particulate matter from exhaust gas emitted from a positive ignition engine
US8211393B2 (en) 2009-02-26 2012-07-03 Johnson Matthey Public Limited Company Exhaust system for a vehicular positive ignition internal combustion engine
DE202010018081U1 (en) 2009-02-26 2014-02-17 Johnson Matthey Public Limited Company filter
US9662611B2 (en) 2009-04-03 2017-05-30 Basf Corporation Emissions treatment system with ammonia-generating and SCR catalysts
JP2017225974A (en) * 2009-04-03 2017-12-28 ビーエーエスエフ コーポレーション Emissions treatment system with ammonia-generating and scr catalysts
EP2414081B1 (en) 2009-04-03 2018-06-06 BASF Corporation Emissions treatment system with ammonia-generating and scr catalysts
KR102031990B1 (en) * 2009-04-03 2019-10-14 바스프 코포레이션 Emissions treatment system with ammonia-generating and scr catalysts
KR20120008521A (en) * 2009-04-03 2012-01-30 바스프 코포레이션 Emissions treatment system with ammonia-generating and scr catalysts
US9358503B2 (en) 2009-04-03 2016-06-07 Basf Corporation Emissions treatment system with ammonia-generating and SCR catalysts
US9321009B2 (en) 2009-04-03 2016-04-26 Basf Corporation Emissions treatment system with ammonia-generating and SCR catalysts
JP2012522636A (en) * 2009-04-03 2012-09-27 ビーエーエスエフ コーポレーション Emission treatment system comprising an ammonia generation catalyst and an SCR catalyst
US10124292B2 (en) 2009-04-03 2018-11-13 Basf Corporation Emissions treatment system with ammonia-generating and SCR catalysts
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KR102268414B1 (en) * 2009-04-03 2021-06-23 바스프 코포레이션 Emissions treatment system with ammonia-generating and scr catalysts
US7998443B2 (en) 2009-04-17 2011-08-16 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
US9802156B2 (en) 2009-04-17 2017-10-31 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
JP2019000848A (en) * 2009-04-17 2019-01-10 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Small pore molecular sieve supported copper catalysts durable against lean/rich aging for reduction of nitrogen oxides
KR20170141263A (en) * 2009-04-17 2017-12-22 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
US8101147B2 (en) 2009-04-17 2012-01-24 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
DE102010027883A1 (en) 2009-04-17 2011-03-31 Johnson Matthey Public Ltd., Co. Process for using a catalyst with copper and a small pore molecular sieve in a chemical process
GB2482094A (en) * 2009-04-17 2012-01-18 Johnson Matthey Plc Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
CN105833717A (en) * 2009-04-17 2016-08-10 约翰逊马西有限公司 Small pore molecular sieve supported copper catalysts
EP3456413A3 (en) * 2009-04-17 2019-12-25 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalyst durable against lean/rich aging for the reduction of nitrogen oxides
JP2020116573A (en) * 2009-04-17 2020-08-06 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Small pore molecular sieve supported copper catalysts durable against lean/rich aging for reduction of nitrogen oxides
EP2698193A1 (en) 2009-04-17 2014-02-19 Johnson Matthey Public Limited Company Exhaust gas treatment with a small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
KR102180723B1 (en) * 2009-04-17 2020-11-20 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
EP2995367B1 (en) 2009-04-17 2017-12-20 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
GB2482094B (en) * 2009-04-17 2014-05-14 Johnson Matthey Plc Small pore molecular sieve supported copper catalysts durable against lean/rich ageing for the reduction of nitrogen oxides
CN105749747A (en) * 2009-04-17 2016-07-13 约翰逊马西有限公司 Small pore molecular sieve supported copper catalysts
CN102802791A (en) * 2009-04-17 2012-11-28 约翰逊马西有限公司 Small Pore Molecular Sieve Supported Copper Catalysts Durable Against Lean/rich Aging For The Reduction Of Nitrogen Oxides
JP2015164729A (en) * 2009-04-17 2015-09-17 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
EP4112168A1 (en) 2009-04-17 2023-01-04 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalyst durable against lean/rich aging for the reduction of nitrogen oxides
EP2698192A1 (en) 2009-04-17 2014-02-19 Johnson Matthey Public Limited Company Exhaust gas treatment with a small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
EP2995367A1 (en) 2009-04-17 2016-03-16 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
EP3456413A2 (en) 2009-04-17 2019-03-20 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalyst durable against lean/rich aging for the reduction of nitrogen oxides
WO2010121257A1 (en) 2009-04-17 2010-10-21 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
EP2269733A1 (en) 2009-06-08 2011-01-05 Basf Se Process for the direct synthesis of cu containing silicoaluminophosphate (cu-sapo-34)
US8887495B2 (en) * 2009-07-14 2014-11-18 GM Global Technology Operations LLC Ash filter, exhaust gas treatment system incorporating the same and method of using the same
US20110011067A1 (en) * 2009-07-14 2011-01-20 Gm Global Technology Operations, Inc. Ash Filter, Exhaust Gas Treatment System Incorporating the Same and Method of Using the Same
EP2471597A1 (en) * 2009-08-27 2012-07-04 Tosoh Corporation Highly heat-resistant aqueous scr catalyst and manufacturing method therefor
EP2471597A4 (en) * 2009-08-27 2013-02-27 Tosoh Corp Highly heat-resistant aqueous scr catalyst and manufacturing method therefor
CN102548658A (en) * 2009-08-27 2012-07-04 东曹株式会社 Highly heat-resistant aqueous SCR catalyst and manufacturing method therefor
US9138685B2 (en) 2009-08-27 2015-09-22 Tosoh Corporation Highly hydrothermal-resistant SCR catalyst and manufacturing method therefor
JP2011067814A (en) * 2009-08-27 2011-04-07 Tosoh Corp Highly heat-resistant aqueous scr catalyst and manufacturing method thereof
US9550182B2 (en) 2009-09-05 2017-01-24 Johnson Matthey Catalysts (Germany) Gmbh Method for the production of an SCR-active zeolite catalyst, and SCR-active zeolite catalyst
RU2506999C2 (en) * 2009-09-05 2014-02-20 Джонсон Мэтти Каталистс (Джермани) Гмбх Method of obtaining scr-active zeolite catalyst and scr-active zeolite catalyst
JP2013506787A (en) * 2009-10-02 2013-02-28 ビー・エイ・エス・エフ、コーポレーション Catalyst used for four-cycle diesel and method of using the same
US20160129431A1 (en) * 2009-10-14 2016-05-12 Basf Se Copper Containing Levyne Molecular Sieve For Selective Reduction Of NOx
WO2011045252A1 (en) 2009-10-14 2011-04-21 Basf Se Copper containing levyne molecular sieve for selective reduction of nox
JP2013507321A (en) * 2009-10-14 2013-03-04 ビーエーエスエフ ソシエタス・ヨーロピア Copper-containing levite molecular sieve for selective reduction of NOx
US9242241B2 (en) 2009-10-14 2016-01-26 Base Se Copper containing levyne molecular sieve for selective reduction of NOx
JP2011125846A (en) * 2009-11-19 2011-06-30 Ibiden Co Ltd Honeycomb structure and apparatus for cleaning exhaust gas
JP2011125852A (en) * 2009-11-19 2011-06-30 Ibiden Co Ltd Honeycomb structure and exhaust gas cleaning apparatus
US9895684B2 (en) 2009-11-24 2018-02-20 Basf Se Process for the preparation of zeolites having CHA structure
EP2325143A2 (en) 2009-11-24 2011-05-25 Basf Se Process for the preparation of zeolites having B-CHA structure
WO2011064186A1 (en) 2009-11-24 2011-06-03 Basf Se Process for the preparation of zeolites having cha structure
US8409546B2 (en) 2009-11-24 2013-04-02 Basf Se Process for the preparation of zeolites having B-CHA structure
US8883119B2 (en) 2009-11-24 2014-11-11 Basf Se Process for the preparation of zeolites having CHA structure
JP2013013894A (en) * 2009-11-30 2013-01-24 Johnson Matthey Plc Catalyst for treating transient nox emissions
KR101843388B1 (en) * 2009-11-30 2018-03-29 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Catalysts for treating transient nox emissions
US9815048B2 (en) * 2009-11-30 2017-11-14 Johnson Matthey Public Limited Company Catalysts for treating transient NOx emissions
JP2016175076A (en) * 2009-11-30 2016-10-06 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ CATALYSTS FOR TREATING TRANSIENT NOx EXHAUST GAS
EP2520365A2 (en) 2009-11-30 2012-11-07 Johnson Matthey Public Limited Company Catalysts for treating transient nox emissions
KR101985158B1 (en) * 2009-11-30 2019-05-31 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Catalysts for treating transient nox emissions
KR101969688B1 (en) 2009-11-30 2019-04-16 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Catalysts for treating transient nox emissions
JP2018183774A (en) * 2009-11-30 2018-11-22 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ CATALYSTS FOR TREATING TRANSIENT NOx EMISSIONS
CN104588092A (en) * 2009-11-30 2015-05-06 约翰逊马西有限公司 CATALYSTS FOR TREATING TRANSIENT NOx EMISSIONS
CN102821847A (en) * 2009-11-30 2012-12-12 约翰逊马西有限公司 Catalysts for treating transient NOX emissions
KR20180037298A (en) * 2009-11-30 2018-04-11 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Catalysts for treating transient nox emissions
WO2011064666A2 (en) 2009-11-30 2011-06-03 Johnson Matthey Public Limited Company Catalysts for treating transient nox emissions
CN105032477A (en) * 2009-11-30 2015-11-11 约翰逊马西有限公司 Catalysts for treating transient NOX emissions
GB2475740B (en) * 2009-11-30 2017-06-07 Johnson Matthey Plc Catalysts for treating transient NOx emissions
KR20180034714A (en) * 2009-11-30 2018-04-04 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Catalysts for treating transient nox emissions
US9616420B2 (en) 2009-11-30 2017-04-11 Johnson Matthey Public Limited Company Catalysts for treating transient NOx emissions
CN102946997A (en) * 2009-12-18 2013-02-27 巴斯夫公司 Process of direct copper exchange into na+-form of chabazite molecular sieve, and catalysts, systems and methods
US9517461B2 (en) 2009-12-18 2016-12-13 Basf Se Ferrous zeolite, method for producing ferrous zeolites, and method for catalytically reducing nitrous oxides
CN102655933A (en) * 2009-12-18 2012-09-05 巴斯夫欧洲公司 Ferrous zeolite, method for producing ferrous zeolites, and method for catalytically reducing nitrous oxides
WO2011073123A3 (en) * 2009-12-18 2011-10-20 Basf Se Ferrous zeolite, method for producing ferrous zeolites, and method for catalytically reducing nitrous oxides
WO2011073390A2 (en) 2009-12-18 2011-06-23 Basf Corporation Process for preparation of copper containing molecular sieves with the cha structure, catalysts, systems and methods
US8293199B2 (en) 2009-12-18 2012-10-23 Basf Corporation Process for preparation of copper containing molecular sieves with the CHA structure, catalysts, systems and methods
WO2011073398A3 (en) * 2009-12-18 2011-12-15 Basf Corporation Process of direct copper exchange into na+-form of chabazite molecular sieve, and catalysts, systems and methods
RU2587078C2 (en) * 2009-12-18 2016-06-10 Басф Се Iron-containing zeolite, method of producing iron-containing zeolites and method for catalytic reduction of nitrogen oxides
EP2965813A1 (en) 2009-12-18 2016-01-13 BASF Corporation Process for the preparation of copper containing molecular sieves with the cha structure
WO2011073398A2 (en) 2009-12-18 2011-06-23 Basf Corporation Process of direct copper exchange into na+-form of chabazite molecular sieve, and catalysts, systems and methods
US8293198B2 (en) 2009-12-18 2012-10-23 Basf Corporation Process of direct copper exchange into Na+-form of chabazite molecular sieve, and catalysts, systems and methods
EP2377613A3 (en) * 2009-12-18 2011-11-02 JGC Catalysts and Chemicals Ltd. Metal-supported crystalline silica aluminophosphate catalyst and process for producing the same
WO2011077168A1 (en) 2009-12-24 2011-06-30 Johnson Matthey Plc Exhaust system for a vehicular positive ignition internal combustion engine
DE102010056223A1 (en) 2009-12-24 2011-07-28 Johnson Matthey Public Limited Company Exhaust system for a vehicle engine with spark ignition
US8609047B2 (en) 2010-02-01 2013-12-17 Johnson Matthey Public Limited Company Extruded SCR filter
US8815190B2 (en) 2010-02-01 2014-08-26 Johnson Matthey Public Limited Company Extruded SCR filter
US8603423B2 (en) 2010-02-01 2013-12-10 Johnson Matthey Public Limited Co. Three way catalyst comprising extruded solid body
WO2011092521A1 (en) * 2010-02-01 2011-08-04 Johnson Matthey Plc Extruded scr filter
US8641993B2 (en) 2010-02-01 2014-02-04 Johnson Matthey Public Limited Co. NOx absorber catalysts
US9040003B2 (en) 2010-02-01 2015-05-26 Johnson Matthey Public Limited Company Three way catalyst comprising extruded solid body
US9283519B2 (en) 2010-02-01 2016-03-15 Johnson Matthey Public Limited Company Filter comprising combined soot oxidation and NH3-SCR catalyst
US8263032B2 (en) 2010-02-01 2012-09-11 Johnson Matthey Public Limited Company Oxidation catalyst
DE102010007626A1 (en) 2010-02-11 2011-08-11 Süd-Chemie AG, 80333 Copper-containing zeolite of the KFI type and use in SCR catalysis
WO2011098512A1 (en) 2010-02-11 2011-08-18 Süd-Chemie AG Kfi-type copper-containing zeolith and use in the scr-catalyst
CN102822462A (en) * 2010-03-08 2012-12-12 约翰逊马西有限公司 Improvements in control of emissions
WO2011110919A1 (en) 2010-03-08 2011-09-15 Johnson Matthey Public Limited Company Improvements in control of emissions
JP2013522517A (en) * 2010-03-08 2013-06-13 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー Improved exhaust gas control
KR101798030B1 (en) * 2010-03-08 2017-11-15 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Improvements in control of emissions
US9574474B2 (en) 2010-03-08 2017-02-21 Johnson Matthey Public Limited Company Control of emissions
US8809217B2 (en) 2010-03-11 2014-08-19 Johnson Matthey Public Limited Company Disordered molecular sieve supports for the selective catalytic reduction of NOx
US8932973B2 (en) 2010-03-11 2015-01-13 Johnson Matthey Public Limited Company Disordered molecular sieve supports for the selective catalytic reduction of NOx
EP2555866A4 (en) * 2010-04-08 2014-12-10 Basf Se Cu-cha/fe-mfi mixed zeolite catalyst and process for treating nox in gas streams using the same
EP2555866A1 (en) * 2010-04-08 2013-02-13 Basf Se Cu-cha/fe-mfi mixed zeolite catalyst and process for treating nox in gas streams using the same
KR101844089B1 (en) * 2010-04-08 2018-03-30 바스프 에스이 Cu-cha/fe-mfi mixed zeolite catalyst and process for treating nox in gas streams using the same
US20110305614A1 (en) * 2010-04-08 2011-12-15 Basf Corporation Cu-CHA/Fe-MFI Mixed Zeolite Catalyst And Process For The Treatment Of NOx In Gas Streams
US9352307B2 (en) * 2010-04-08 2016-05-31 Basf Corporation Cu-CHA/Fe-MFI mixed zeolite catalyst and process for the treatment of NOx in gas streams
US9352277B2 (en) 2010-06-02 2016-05-31 Johnson Matthey Plc Diesel particulate filter
WO2011151711A1 (en) 2010-06-02 2011-12-08 Johnson Matthey Public Limited Company Diesel particulate filter
US20120014866A1 (en) * 2010-07-15 2012-01-19 Ivor Bull Copper Containing ZSM-34, OFF And/Or ERI Zeolitic Material For Selective Reduction Of NOx
EP2593222B1 (en) * 2010-07-15 2015-12-16 Basf Se Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
WO2012007874A1 (en) * 2010-07-15 2012-01-19 Basf Se Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
US9221015B2 (en) 2010-07-15 2015-12-29 Basf Se Copper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx
US9289756B2 (en) 2010-07-15 2016-03-22 Basf Se Copper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx
CN103167907A (en) * 2010-07-15 2013-06-19 巴斯夫欧洲公司 Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
EP2593222A1 (en) 2010-07-15 2013-05-22 Basf Se Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
US20120014867A1 (en) * 2010-07-15 2012-01-19 Basf Se Copper Containing ZSM-34, OFF And/Or ERI Zeolitic Material For Selective Reduction Of NOx
US20120014865A1 (en) * 2010-07-15 2012-01-19 Basf Se Copper Containing ZSM-34, OFF And/Or ERI Zeolitic Material For Selective Reduction Of NOx
EP2593212B1 (en) * 2010-07-15 2015-12-16 Basf Se Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
WO2012007873A1 (en) * 2010-07-15 2012-01-19 Basf Se Copper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
US8987161B2 (en) * 2010-08-13 2015-03-24 Ut-Battelle, Llc Zeolite-based SCR catalysts and their use in diesel engine emission treatment
US9403156B2 (en) 2010-08-13 2016-08-02 Ut-Battelle, Llc Zeolite-based SCR catalysts and their use in diesel engine emission treatment
US20120039759A1 (en) * 2010-08-13 2012-02-16 Ut-Battelle, Llc Zeolite-based scr catalysts and their use in diesel engine emission treatment
RU2584748C2 (en) * 2010-09-13 2016-05-20 Умикоре Аг Унд Ко. Кг Catalyst for removing nitrogen oxides from exhaust gases of diesel engines
EP2463028A1 (en) 2010-12-11 2012-06-13 Umicore Ag & Co. Kg Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic removal of nitrogen oxides
WO2012076648A1 (en) 2010-12-11 2012-06-14 Umicore Ag & Co. Kg Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides
US8865120B2 (en) 2010-12-11 2014-10-21 Umicore Ag & Co., Kg Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides
EP3673978A1 (en) 2010-12-21 2020-07-01 Johnson Matthey Public Limited Company Oxidation catalyst for a lean burn internal combustion engine
DE102011089371A1 (en) 2010-12-21 2012-06-21 Johnson Matthey Plc Oxidation catalyst for a lean-burn internal combustion engine
WO2012085572A2 (en) 2010-12-21 2012-06-28 Johnson Matthey Public Limited Company Oxidation catalyst for a lean burn internal combustion engine
US9140167B2 (en) 2010-12-21 2015-09-22 Johnson Matthey Public Limited Company Oxidation catalyst for a lean burn internal combustion engine
WO2012090922A1 (en) 2010-12-27 2012-07-05 三菱樹脂株式会社 Catalyst for nitrogen oxide removal
US8617502B2 (en) 2011-02-07 2013-12-31 Cristal Usa Inc. Ce containing, V-free mobile denox catalyst
WO2012158239A1 (en) 2011-02-28 2012-11-22 Johnson Matthey Public Limited Company High-temperature scr catalyst
WO2012120292A1 (en) 2011-03-04 2012-09-13 Johnson Matthey Public Limited Company Alloy-comprising catalyst, method of preparation and uses
US9616409B2 (en) 2011-03-04 2017-04-11 Johnson Matthey Public Limited Company Catalyst and method of preparation
DE102012203461A1 (en) 2011-03-04 2012-09-06 Johnson Matthey Public Ltd. Co. CATALYST AND METHOD OF MANUFACTURE
US20120251422A1 (en) * 2011-04-04 2012-10-04 Pq Corporation Fe-SAPO-34 CATALYST AND METHODS OF MAKING AND USING THE SAME
WO2012138652A1 (en) 2011-04-04 2012-10-11 Pq Corporation Fe-sapo-34 catalyst and methods of making and using the same
US10226762B1 (en) * 2011-06-17 2019-03-12 Johnson Matthey Public Limited Company Alumina binders for SCR catalysts
US9138731B2 (en) 2011-08-03 2015-09-22 Johnson Matthey Public Limited Company Extruded honeycomb catalyst
WO2013030584A1 (en) 2011-08-31 2013-03-07 Johnson Matthey Public Limited Company Method and system using a filter for treating exhaust gas having particulate matter
US20130089483A1 (en) * 2011-10-05 2013-04-11 Basf Se Cu-CHA/Fe-BEA Mixed Zeolite Catalyst And Process For The Treatment Of NOx In Gas Streams
US9999877B2 (en) 2011-10-05 2018-06-19 Basf Se Cu-CHA/Fe-BEA mixed zeolite catalyst and process for the treatment of NOx in gas streams
WO2013050964A1 (en) * 2011-10-05 2013-04-11 Basf Se Cu-CHA/Fe-BEA MIXED ZEOLITE CATALYST AND PROCESS FOR THE TREATMENT OF NOX IN GAS STREAMS
WO2013050784A2 (en) 2011-10-06 2013-04-11 Johnson Matthey Public Limited Company Oxidation catalyst for internal combustion engine exhaust gas treatment
DE102012218254B4 (en) 2011-10-06 2022-11-17 Johnson Matthey Public Limited Company EXHAUST SYSTEM FOR AN INTERNAL COMBUSTION ENGINE
EP3363525A1 (en) 2011-10-06 2018-08-22 Johnson Matthey Public Limited Company Oxidation catalyst for internal combustion engine exhaust gas treatment
EP3363526A1 (en) 2011-10-06 2018-08-22 Johnson Matthey Public Limited Company Oxidation catalyst for internal combustion engine exhaust gas treatment
DE102012218254A1 (en) 2011-10-06 2013-04-11 Johnson Matthey Japan Godo Kaisha Oxidation catalyst for a treatment of exhaust gas of an internal combustion engine
US8652429B2 (en) 2011-10-06 2014-02-18 Johnson Matthey Public Limited Company Oxidation catalyst for internal combustion engine exhaust gas treatment
US9005559B2 (en) 2011-10-06 2015-04-14 Johnson Matthey Public Limited Company Oxidation catalyst for internal combustion engine exhaust gas treatment
US9868115B2 (en) 2011-10-06 2018-01-16 Johnson Matthey Public Limited Company Oxidation catalyst for internal combustion engine exhaust gas treatment
RU2608616C2 (en) * 2011-10-24 2017-01-23 Хальдор Топсеэ А/С Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides
US8956992B2 (en) 2011-10-27 2015-02-17 GM Global Technology Operations LLC SCR catalysts preparation methods
WO2013088132A1 (en) 2011-12-12 2013-06-20 Johnson Matthey Public Limited Company Exhaust system for a lean-burn ic engine comprising a pgm component and a scr catalyst
US8668891B2 (en) 2011-12-12 2014-03-11 Johnson Matthey Public Limited Company Exhaust system for a lean-burn IC engine comprising a PGM component and a SCR catalyst
WO2013088129A2 (en) 2011-12-12 2013-06-20 Johnson Matthey Public Limited Company Substrate monolith comprising scr catalyst
DE102012025751A1 (en) 2011-12-12 2015-07-30 Johnson Matthey Public Limited Company An exhaust system for a lean-burn internal combustion engine comprising a PGM component and an SCR catalyst
WO2013088133A1 (en) 2011-12-12 2013-06-20 Johnson Matthey Public Limited Company Catalysed substrate monolith
DE102012025746A1 (en) 2011-12-12 2015-06-25 Johnson Matthey Public Limited Company Catalyzed substrate monolith
US9046022B2 (en) 2011-12-12 2015-06-02 Johnson Matthey Public Limited Company Catalysed substrate monolith
WO2013088128A1 (en) 2011-12-12 2013-06-20 Johnson Matthey Public Limited Company Exhaust system for a lean-burn internal combustion engine including scr catalyst
DE102012222801A1 (en) 2011-12-12 2013-06-27 Johnson Matthey Public Limited Company Catalyzed substrate monolith
DE102012222806A1 (en) 2011-12-12 2013-06-27 Johnson Matthey Public Limited Company An exhaust system for a lean-burn internal combustion engine comprising a PGM component and an SCR catalyst
DE102012222807A1 (en) 2011-12-12 2013-06-27 Johnson Matthey Public Limited Company Exhaust system for a lean-burn internal combustion engine comprising an SCR catalyst
DE102012222801B4 (en) 2011-12-12 2020-06-04 Johnson Matthey Public Limited Company Exhaust system and use of a washcoat
US8986635B2 (en) 2011-12-12 2015-03-24 Johnson Matthey Public Limited Company Exhaust system for a lean-burn IC engine comprising a PGM component and a SCR catalyst
DE102012222804A1 (en) 2011-12-12 2013-06-27 Johnson Matthey Public Limited Company Substrate monolith comprising an SCR catalyst
US9597661B2 (en) 2011-12-12 2017-03-21 Johnson Matthey Public Limited Company Catalysed substrate monolith
EP3636336A1 (en) 2011-12-12 2020-04-15 Johnson Matthey Public Limited Company Exhaust system comprising catalysed substrate monolith including washcoat for trapping volatilised pt upstream from scr catalyst
US9259684B2 (en) 2011-12-12 2016-02-16 Johnson Matthey Public Limited Company Exhaust system for a lean-burn internal combustion engine including SCR catalyst
US8667785B2 (en) 2011-12-12 2014-03-11 Johnson Matthey Public Limited Company Catalysed substrate monolith
US9333461B2 (en) 2011-12-12 2016-05-10 Johnson Matthey Public Limited Company Substrate monolith comprising SCR catalyst
JP2018140387A (en) * 2012-01-31 2018-09-13 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Catalyst blends
GB2514945A (en) * 2012-01-31 2014-12-10 Johnson Matthey Plc Catalyst blends
US9126180B2 (en) 2012-01-31 2015-09-08 Johnson Matthey Public Limited Company Catalyst blends
US9999876B2 (en) * 2012-01-31 2018-06-19 Johnson Matthey Public Limited Company Catalyst blends
WO2013114172A1 (en) * 2012-01-31 2013-08-08 Johnson Matthey Public Limited Company Catalyst blends
GB2514945B (en) * 2012-01-31 2018-01-31 Johnson Matthey Plc Catalyst blends
RU2642443C2 (en) * 2012-01-31 2018-01-25 Джонсон Мэтти Паблик Лимитед Компани Catalytic mixtures
EP3326714A1 (en) * 2012-01-31 2018-05-30 Johnson Matthey Public Limited Company Catalyst blends
US20150238946A1 (en) * 2012-02-24 2015-08-27 Ut-Battelle, Llc Hydrothermally stable, low-temperature nox reduction nh3-scr catalyst
US9475039B2 (en) * 2012-02-24 2016-10-25 Ut-Battelle, Llc Hydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst
WO2013126619A1 (en) * 2012-02-24 2013-08-29 Ut-Battelle, Llc Hydrothermally stable, low-temperature nox reduction nh3-scr catalyst
US9352279B2 (en) 2012-04-24 2016-05-31 Johnson Matthey Public Limited Company Filter substrate comprising three-way catalyst
US9561468B2 (en) 2012-04-27 2017-02-07 Haldor Topsoe A/S Method and system for the purification of exhaust gas from an internal combustion engine
EP3425181A1 (en) * 2012-04-27 2019-01-09 Umicore Ag & Co. Kg Method and system for the purification of exhaust gas from an internal combustion engine
EP2995790A1 (en) * 2012-04-27 2016-03-16 Haldor Topsøe A/S System for the purification of exhaust gas from an internal combustion engine
EP2850294B1 (en) * 2012-04-27 2017-06-07 Haldor Topsøe A/S Method and system for the purification of exhaust gas from an internal combustion engine
EP3425182A1 (en) * 2012-04-27 2019-01-09 Umicore Ag & Co. Kg Method and system for the purification of exhaust gas from an internal combustion engine
CN104520548A (en) * 2012-04-27 2015-04-15 赫多特普索化工设备公司 Method and system for the purification of exhaust gas from an internal combustion engine
EP3165733A1 (en) * 2012-04-27 2017-05-10 Haldor Topsøe A/S Method for the purification of exhaust gas from an internal combustion engine
US9855528B2 (en) 2012-04-27 2018-01-02 Haldor Topsoe A/S System for the purification of exhaust gas from an internal combustion engine
CN109268108A (en) * 2012-04-27 2019-01-25 优美科两合公司 For purifying the method and system of the exhaust gas from internal combustion engine
EP3369897A1 (en) * 2012-04-27 2018-09-05 Umicore Ag & Co. Kg Method and system for the purification of exhaust gas from an internal combustion engine
WO2013159828A1 (en) 2012-04-27 2013-10-31 Haldor Topsøe A/S Process for the direct synthesis of cu-sapo-34
CN102671691A (en) * 2012-05-28 2012-09-19 四川君和环保工程有限公司 Low-temperature SCR (Selective Catalytic Reduction) denitrification catalyst, as well as preparation method and application thereof
RU2767067C1 (en) * 2012-10-19 2022-03-16 Басф Корпорейшн 8-ring molecular sieve with small pores as high-temperature scr catalyst
RU2704617C2 (en) * 2012-10-19 2019-10-30 Басф Корпорейшн 8-ring molecular sieve with small pores as high-temperature scr catalyst
EP4070884A1 (en) 2012-11-21 2022-10-12 Johnson Matthey Public Limited Company Exhaust system for a compression ignition engine comprising oxidation catalyst
DE102013223845A1 (en) 2012-11-21 2014-05-22 Johnson Matthey Public Limited Company Oxidation catalyst for the treatment of exhaust gas of an internal combustion engine
US9034286B2 (en) 2012-11-21 2015-05-19 Johnson Matthey Public Limited Company Oxidation catalyst for treating the exhaust gas of a compression ignition engine
US9527035B2 (en) 2012-11-21 2016-12-27 Johnson Matthey Public Limited Company Catalysed soot filter for treating the exhaust gas of a compression ignition engine
US9057310B2 (en) 2012-11-21 2015-06-16 Johnson Matthey Public Limited Company Catalysed soot filter for treating the exhaust gas of a compression ignition engine
US9527034B2 (en) 2012-11-21 2016-12-27 Johnson Matthey Public Limited Company Oxidation catalyst for treating the exhaust gas of a compression ignition engine
DE102013223839A1 (en) 2012-11-21 2014-05-22 Johnson Matthey Public Limited Company Catalyzed soot filter for treating the exhaust gas of a compression ignition engine
WO2014080200A1 (en) 2012-11-21 2014-05-30 Johnson Matthey Public Limited Company Oxidation catalyst for treating the exhaust gas of a compression ignition engine
WO2014080202A1 (en) 2012-11-21 2014-05-30 Johnson Matthey Public Limited Company Catalysed soot filter for treating the exhaust gas of a compression ignition engine
US8992869B2 (en) 2012-12-20 2015-03-31 Caterpillar Inc. Ammonia oxidation catalyst system
US9802182B2 (en) 2013-03-13 2017-10-31 Basf Corporation Stabilized metal-exchanged SAPO material
US9931620B2 (en) 2013-03-13 2018-04-03 Basf Corporation Stabilized metal-exchanged SAPO material
GB2532342A (en) * 2013-03-15 2016-05-18 Johnson Matthey Plc Catalyst for treating exhaust gas
WO2014141200A1 (en) * 2013-03-15 2014-09-18 Johnson Matthey Public Limited Company Catalyst for treating exhaust gas
GB2532342B (en) * 2013-03-15 2018-07-18 Johnson Matthey Plc Catalyst for treating exhaust gas
GB2558467B (en) * 2013-03-15 2019-01-30 Johnson Matthey Plc Catalyst for treating exhaust gas
US9044744B2 (en) 2013-03-15 2015-06-02 Johnson Matthey Public Limited Company Catalyst for treating exhaust gas
RU2675821C2 (en) * 2013-03-15 2018-12-25 Джонсон Мэтти Паблик Лимитед Компани Catalyst for treating exhaust gases
RU2771714C2 (en) * 2013-03-15 2022-05-11 Джонсон Мэтти Паблик Лимитед Компани Catalyst for exhaust gas processing
GB2558467A (en) * 2013-03-15 2018-07-11 Johnson Matthey Plc Catalyst for treating exhaust gas
DE202013012229U1 (en) 2013-04-05 2015-10-08 Umicore Ag & Co. Kg CuCHA material for SCR catalysis
US9327239B2 (en) 2013-04-05 2016-05-03 Johnson Matthey Public Limited Company Filter substrate comprising three-way catalyst
DE102013005749A1 (en) 2013-04-05 2014-10-09 Umicore Ag & Co. Kg CuCHA material for SCR catalysis
US9347349B2 (en) 2013-04-24 2016-05-24 Johnson Matthey Public Limited Company Positive ignition engine and exhaust system comprising catalysed zone-coated filter substrate
EP3753626A1 (en) 2013-04-24 2020-12-23 Johnson Matthey Public Limited Company Filter substrate comprising zone-coated catalyst washcoat
EP3753625A1 (en) 2013-04-24 2020-12-23 Johnson Matthey Public Limited Company Filter substrate comprising zone-coated catalyst washcoat
DE102014105739A1 (en) 2013-04-24 2014-10-30 Johnson Matthey Public Limited Company Filter substrate comprising a zoned catalyst washcoat
US9366166B2 (en) 2013-04-24 2016-06-14 Johnson Matthey Public Limited Company Filter substrate comprising zone-coated catalyst washcoat
DE102014105736A1 (en) 2013-04-24 2014-10-30 Johnson Matthey Public Limited Company A spark-ignition engine and exhaust system comprising a catalyzed zoned filter substrate
US9403157B2 (en) 2013-04-29 2016-08-02 Ford Global Technologies, Llc Three-way catalyst comprising mixture of nickel and copper
DE102014106944A1 (en) 2013-05-17 2014-11-20 Johnson Matthey Public Limited Company Oxidation catalyst for a compression ignition engine
US11794169B2 (en) 2013-05-17 2023-10-24 Johnson Matthey Public Limited Company Oxidation catalyst for a compression ignition engine
DE102014106943A1 (en) 2013-05-17 2014-11-20 Johnson Matthey Public Limited Company OXIDATION CATALYST FOR A COMPRESSION IGNITION ENGINE
US9707542B2 (en) 2013-05-17 2017-07-18 Johnson Matthey Public Limited Company Oxidation catalyst for a compression ignition engine
US9643161B2 (en) 2013-05-17 2017-05-09 Johnson Matthey Public Limited Company Oxidation catalyst for a compression ignition engine
US9630146B2 (en) 2013-06-03 2017-04-25 Ford Global Technologies, Llc Particulate filter containing a nickel-copper catalyst
KR20160020422A (en) 2013-06-14 2016-02-23 도소 가부시키가이샤 Lev-type zeolite and production method therefor
US9968917B2 (en) 2013-06-14 2018-05-15 Tosoh Corporation LEV-type zeolite and production method therefor
WO2014199945A1 (en) 2013-06-14 2014-12-18 東ソー株式会社 Lev-type zeolite and production method therefor
WO2015018815A1 (en) * 2013-08-09 2015-02-12 Basf Se Process for the oxygen free conversion of methane to ethylene on zeolite catalysts
DE102014117672A1 (en) 2013-12-02 2015-06-03 Johnson Matthey Public Limited Company WALL CURRENT FILTER CONTAINING A CATALYTIC WASHCOAT
WO2015084834A1 (en) * 2013-12-02 2015-06-11 Johnson Matthey Public Limited Company Synthesis of aei zeolite
US9480976B2 (en) 2013-12-02 2016-11-01 Johnson Matthey Public Limited Company Synthesis of AEI zeolite
GB2522977B (en) * 2013-12-06 2017-02-08 Johnson Matthey Plc Passive NOx adsorber
GB2522977A (en) * 2013-12-06 2015-08-12 Johnson Matthey Plc Passive NOx adsorber
US20150231620A1 (en) * 2014-02-19 2015-08-20 Ford Global Technologies, Llc IRON-ZEOLITE CHABAZITE CATALYST FOR USE IN NOx REDUCTION AND METHOD OF MAKING
US20150231617A1 (en) * 2014-02-19 2015-08-20 Ford Global Technologies, Llc Fe-SAPO-34 CATALYST FOR USE IN NOX REDUCTION AND METHOD OF MAKING
GB2527398A (en) * 2014-03-27 2015-12-23 Johnson Matthey Plc SCR method for reducing oxides of nitrogen and method for producing a catalyst for such method
GB2527398B (en) * 2014-03-27 2019-05-08 Johnson Matthey Plc SCR method for reducing oxides of nitrogen and method for producing a catalyst for such method
US20150290632A1 (en) * 2014-04-09 2015-10-15 Ford Global Technologies, Llc IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION
US10443463B2 (en) 2014-08-13 2019-10-15 Umicore Ag & Co. Kg Catalyst system for reducing nitrogen oxides
EP2985068A1 (en) 2014-08-13 2016-02-17 Umicore AG & Co. KG Catalyst system for the reduction of nitrogen oxides
US10792648B2 (en) * 2014-10-30 2020-10-06 Basf Corporation Mixed metal large crystal molecular sieve catalyst compositions, catalytic articles, systems and methods
US20170333883A1 (en) * 2014-10-30 2017-11-23 Basf Corporation Mixed metal large crystal molecular sieve catalyst compositions, catalytic articles, systems and methods
GB2538877B (en) * 2014-12-08 2017-04-26 Johnson Matthey Plc Passive NOx adsorber
GB2538877A (en) * 2014-12-08 2016-11-30 Johnson Matthey Plc Passive NOx adsorber
US11103855B2 (en) 2015-02-16 2021-08-31 Johnson Matthey Public Limited Company Catalyst with stable nitric oxide (NO) oxidation performance
DE102016102527A1 (en) 2015-02-16 2016-08-18 Johnson Matthey Public Limited Company Catalyst with stable nitrogen monoxide (NO) oxidation performance
EP3307434B1 (en) 2015-04-09 2021-06-09 PQ Corporation Stabilized microporous crystalline material, the method of making the same, and the use for selective catalytic reduction of nox
EP3574983A2 (en) 2015-06-28 2019-12-04 Johnson Matthey Public Limited Company Catalytic wall-flow filter having a membrane
WO2017001829A1 (en) 2015-06-28 2017-01-05 Johnson Matthey Public Limited Company Catalytic wall-flow filter having a membrane
DE102016111766A1 (en) 2015-06-28 2016-12-29 Johnson Matthey Public Limited Company CATALYTIC WALL CURRENT FILTER WITH A MEMBRANE
EP3411145A4 (en) * 2016-02-03 2019-10-02 BASF Corporation Copper and iron co-exchanged chabazite catalyst
US11311867B2 (en) 2016-02-03 2022-04-26 Basf Corporation Copper and iron co-exchanged chabazite catalyst
US10105691B2 (en) 2016-03-31 2018-10-23 Ford Global Technologies, Llc Multiple zeolite hydrocarbon traps
US10092897B2 (en) * 2016-04-20 2018-10-09 Ford Global Technologies, Llc Catalyst trap
US11014077B2 (en) 2016-05-03 2021-05-25 Umicore Ag & Co. Kg Active SCR catalyst
WO2017207969A1 (en) * 2016-05-31 2017-12-07 Johnson Matthey Public Limited Company Method and exhaust system for treating nox in exhaust gas from stationary emission sources
WO2018029328A1 (en) 2016-08-11 2018-02-15 Umicore Ag & Co. Kg Scr-active material
US10799831B2 (en) 2016-08-11 2020-10-13 Umicore Ag & Co. Kg SCR-active material
EP3281698A1 (en) 2016-08-11 2018-02-14 Umicore AG & Co. KG Scr active material
WO2018029329A1 (en) 2016-08-11 2018-02-15 Umicore Ag & Co. Kg Scr-active material having enhanced thermal stability
US10914214B2 (en) 2016-09-20 2021-02-09 Umicore Ag & Co. Kg SCR diesel particle filter with oxidation catalyst and oxygen storage catalyst loadings, and exhaust system including the same
WO2018054929A1 (en) 2016-09-20 2018-03-29 Umicore Ag & Co. Kg Diesel particle filter
WO2018069199A1 (en) 2016-10-10 2018-04-19 Umicore Ag & Co. Kg Catalytic converter arrangement
DE102017125192A1 (en) 2016-10-28 2018-05-03 Johnson Matthey Public Limited Company Catalytic wall-flow filter with partial surface coating
WO2018078559A1 (en) 2016-10-28 2018-05-03 Johnson Matthey Public Limited Company Catalytic wall-flow filter with partial surface coating
US10500574B2 (en) 2016-10-31 2019-12-10 Johnson Matthey Public Limited Company LTA catalysts having extra-framework iron and/or manganese for treating exhaust gas
WO2018081682A1 (en) * 2016-10-31 2018-05-03 Johnson Matthey Public Limited Company Lta catalysts having extra-framework iron and/or manganese for treating exhaust gas
WO2018100368A1 (en) * 2016-12-01 2018-06-07 Johnson Matthey Public Limited Company METHOD OF EXTENDING THE USEFUL LIFE OF AN AGED SCR CATALYST BED IN AN EXHAUST SYSTEM OF A STATIONARY SOURCE OF NOx
US10961871B2 (en) 2016-12-01 2021-03-30 Johnson Matthey Public Limited Company Method of extending the useful life of an aged SCR catalyst bed in an exhaust system of a stationary source of NOX
CN110050110A (en) * 2016-12-01 2019-07-23 庄信万丰股份有限公司 Extend the method for the SCR catalyst bed service life of aging in the exhaust system in the fixed source NOx
GB2570831A (en) * 2016-12-01 2019-08-07 Johnson Matthey Plc Method of extending the useful life of an aged SCR catalyst bed in an exhaust system of a stationary source of NOx
EP3357558A1 (en) 2017-02-03 2018-08-08 Umicore Ag & Co. Kg Catalyst for cleaning diesel engine exhaust gases
US10213767B2 (en) 2017-02-03 2019-02-26 Umicore Ag & Co. Kg Catalyst for purifying the exhaust gases of diesel engines
WO2018141887A1 (en) 2017-02-03 2018-08-09 Umicore Ag & Co. Kg Catalytic converter for cleaning the exhaust gases of diesel engines
US10926251B2 (en) 2017-03-31 2021-02-23 Johnson Matthey Catalysts (Germany) Gmbh Selective catalytic reduction catalyst
DE102018204802A1 (en) 2017-03-31 2018-10-04 Friedrich-Alexander-Universität Erlangen-Nürnberg Catalyst composition for selective catalytic reduction
DE102018204690A1 (en) 2017-03-31 2018-10-04 Johnson Matthey Catalysts (Germany) Gmbh Selective catalytic reduction catalyst
CN109250729B (en) * 2017-07-12 2022-02-25 中国科学院大连化学物理研究所 Cu-SAPO-34 molecular sieve synthesis method, synthesized molecular sieve and application
CN109250729A (en) * 2017-07-12 2019-01-22 中国科学院大连化学物理研究所 The molecular sieve and application of Cu-SAPO-34 Zeolite synthesis method and synthesis
WO2019042883A1 (en) 2017-08-31 2019-03-07 Umicore Ag & Co. Kg Palladium/zeolite-based passive nitrogen oxide adsorber catalyst for purifying exhaust gas
EP3450015A1 (en) 2017-08-31 2019-03-06 Umicore Ag & Co. Kg Palladium-zeolite-based passive nitrogen oxide adsorber catalyst for exhaust gas treatment
US11161100B2 (en) 2017-08-31 2021-11-02 Umicore Ag & Co. Kg Use of a palladium/platinum/zeolite-based catalyst as passive nitrogen oxide adsorber for purifying exhaust gas
EP3450016A1 (en) 2017-08-31 2019-03-06 Umicore Ag & Co. Kg Palladium-zeolite-based passive nitrogen oxide adsorber catalyst for exhaust gas treatment
WO2019042884A1 (en) 2017-08-31 2019-03-07 Umicore Ag & Co. Kg Use of a palladium/platinum/zeolite-based catalyst as passive nitrogen oxide adsorber for purifying exhaust gas
US11141717B2 (en) 2017-08-31 2021-10-12 Umicore Ag & Co. Kg Palladium/zeolite-based passive nitrogen oxide adsorber catalyst for purifying exhaust gas
EP3449999A1 (en) 2017-08-31 2019-03-06 Umicore Ag & Co. Kg Passive nitric oxide adsorber
DE102018121503A1 (en) 2017-09-05 2019-03-07 Umicore Ag & Co. Kg Exhaust gas purification with NO oxidation catalyst and SCR-active particle filter
WO2019077111A1 (en) 2017-10-20 2019-04-25 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber catalyst
US10711674B2 (en) 2017-10-20 2020-07-14 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber catalyst
WO2019134958A1 (en) 2018-01-05 2019-07-11 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber
WO2019141718A1 (en) 2018-01-16 2019-07-25 Umicore Ag & Co. Kg Method for producing an scr catalytic converter by way of pre-drying
DE102018100833A1 (en) 2018-01-16 2019-07-18 Umicore Ag & Co. Kg Process for producing an SCR catalyst
DE102018100834A1 (en) 2018-01-16 2019-07-18 Umicore Ag & Co. Kg Process for producing an SCR catalyst
US11400443B2 (en) 2018-01-16 2022-08-02 Umicore Ag & Co. Kg Ultrasound-assisted method for producing an SCR catalytic converter
WO2019141719A1 (en) 2018-01-16 2019-07-25 Umicore Ag & Co. Kg Ultrasound-assisted method for producing an scr catalytic converter
US11230955B2 (en) 2018-01-16 2022-01-25 Umicore Ag & Co. Kg Method for producing an SCR catalytic converter by way of pre-drying
WO2019145198A1 (en) 2018-01-23 2019-08-01 Umicore Ag & Co. Kg Scr catalyst and exhaust gas cleaning system
US10898889B2 (en) 2018-01-23 2021-01-26 Umicore Ag & Co. Kg SCR catalyst and exhaust gas cleaning system
US10456746B2 (en) 2018-02-12 2019-10-29 GM Global Technology Operations LLC Selective catalytic reduction filter for reducing nitrous oxide formation and methods of using the same
EP3613503A1 (en) 2018-08-22 2020-02-26 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber
WO2020039015A1 (en) 2018-08-22 2020-02-27 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber
EP3616792A1 (en) 2018-08-28 2020-03-04 Umicore Ag & Co. Kg Nitrogen oxide storage catalyst
US11376550B2 (en) 2018-08-28 2022-07-05 Umicore Ag & Co. Kg Nitrogen oxide storage catalyst
WO2020043578A1 (en) 2018-08-28 2020-03-05 Umicore Ag & Co. Kg Nitrogen oxide storage catalyst
WO2020089043A1 (en) 2018-11-02 2020-05-07 Basf Corporation Exhaust treatment system for a lean burn engine
US11511228B2 (en) 2018-11-02 2022-11-29 Basf Corporation Exhaust treatment system for a lean burn engine
US11439952B2 (en) 2018-11-16 2022-09-13 Umicore Ag & Co. Kg Low temperature nitrogen oxide adsorber
WO2020099253A1 (en) 2018-11-16 2020-05-22 Umicore Ag & Co. Kg Low temperature nitrogen oxide adsorber
US11278874B2 (en) 2018-11-30 2022-03-22 Johnson Matthey Public Limited Company Enhanced introduction of extra-framework metal into aluminosilicate zeolites
WO2020109810A1 (en) 2018-11-30 2020-06-04 Johnson Matthey Public Limited Company Enhanced introduction of extra-frame work metal into aluminosilicate zeolites
WO2020144195A1 (en) 2019-01-08 2020-07-16 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber having oxidation-catalytically active function
US11772077B2 (en) 2019-01-08 2023-10-03 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber having oxidation-catalytically active function
WO2020148186A1 (en) 2019-01-14 2020-07-23 Friedrich-Alexander-Universität Erlangen-Nürnberg Iron-loaded small pore aluminosilicate cha zeolites and method of making metal loaded small pore aluminosilicate cha zeolites
EP3695902A1 (en) 2019-02-18 2020-08-19 Umicore Ag & Co. Kg Catalyst for reducing nitrogen oxides
WO2020169600A1 (en) 2019-02-18 2020-08-27 Umicore Ag & Co. Kg Catalyst for reduction of nitrogen oxides
EP3791955A1 (en) 2019-09-10 2021-03-17 Umicore Ag & Co. Kg Scr-catalytic material containing copper-zeolite and copper/alumina, exhaust gas treatment process with said material and method for producing said material
EP3812034A1 (en) 2019-10-24 2021-04-28 Dinex A/S Durable copper-scr catalyst
WO2021078977A1 (en) 2019-10-24 2021-04-29 Dinex A/S Durable copper-scr catalyst
EP3824988A1 (en) 2019-11-20 2021-05-26 UMICORE AG & Co. KG Catalyst for reducing nitrogen oxides
WO2021099361A1 (en) 2019-11-20 2021-05-27 Umicore Ag & Co. Kg Catalyst for reducing nitrogen oxides
EP3885040A1 (en) 2020-03-24 2021-09-29 UMICORE AG & Co. KG Ammonia oxidation catalyst
WO2022069465A1 (en) 2020-09-30 2022-04-07 Umicore Ag & Co. Kg Bismut containing dieseloxidation catalyst
EP3978100A1 (en) 2020-09-30 2022-04-06 UMICORE AG & Co. KG Bismuth-containing zoned diesel oxidation catalyst
WO2022079141A1 (en) 2020-10-14 2022-04-21 Umicore Ag & Co. Kg Passive nitrogen oxide adsorber
WO2022200310A1 (en) 2021-03-23 2022-09-29 Umicore Ag & Co. Kg Filter for the aftertreatment of exhaust gases of internal combustion engines
EP4063003A1 (en) 2021-03-23 2022-09-28 UMICORE AG & Co. KG Filter for the aftertreatment of exhaust gases of internal combustion engines
WO2023067134A1 (en) 2021-10-22 2023-04-27 Johnson Matthey Catalysts (Germany) Gmbh Method and catalyst article

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