GB2604801A - Composite, zone-coated, dual-use ammonia (amox) and nitric oxide oxidation catalyst - Google Patents

Composite, zone-coated, dual-use ammonia (amox) and nitric oxide oxidation catalyst Download PDF

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Publication number
GB2604801A
GB2604801A GB2207144.3A GB202207144A GB2604801A GB 2604801 A GB2604801 A GB 2604801A GB 202207144 A GB202207144 A GB 202207144A GB 2604801 A GB2604801 A GB 2604801A
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United Kingdom
Prior art keywords
catalyst
washcoat
zone
oxidation catalyst
platinum group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
GB2207144.3A
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GB202207144D0 (en
Inventor
Francis Chiffey Andrew
Cole Kieran
Cooper Oliver
Daly Christopher
Edvardsson Jonas
Alexander Gilbert Lee
green Alexander
Greenham Neil
Hanley Robert
Marsh Per
Micallef David
Moreau Francois
Wylie James
Richard Phillips Paul
Platt George
Jenkins Caitlin
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Johnson Matthey PLC
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Johnson Matthey PLC
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Publication date
Priority claimed from GB201914958A external-priority patent/GB201914958D0/en
Priority claimed from GBGB2004769.2A external-priority patent/GB202004769D0/en
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Priority claimed from PCT/GB2020/052625 external-priority patent/WO2021074652A1/en
Publication of GB202207144D0 publication Critical patent/GB202207144D0/en
Publication of GB2604801A publication Critical patent/GB2604801A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9436—Ammonia
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
    • F01N3/106—Auxiliary oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/783—CHA-type, e.g. Chabazite, LZ-218
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
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    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N13/16—Selection of particular materials
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
    • B01D2251/00—Reactants
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2258/012—Diesel engines and lean burn gasoline engines
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    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
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    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
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    • F01N2510/0682—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
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    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
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    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1453—Sprayers or atomisers; Arrangement thereof in the exhaust apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Combustion & Propulsion (AREA)
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  • Health & Medical Sciences (AREA)
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  • Catalysts (AREA)

Abstract

A composite, zone-coated, ammonia and nitric oxide oxidation catalyst (12) comprising a substrate (5) having a total length L and two or more zones (1; 2) comprised of a first catalyst washcoat layer (9) and a second catalyst washcoat layer (11) different therefrom, which two or more zones (1; 2) being arranged axially in series wherein a first zone (1) having a length L1 < L, is defined by the first substrate end (I) and by a first end (15) of a second zone (2) having a length L2, wherein L2< L, wherein the first zone (1) comprises a first refractory metal oxide support and one or more PGM supported thereon; and the second zone comprises a second refractory metal oxide support and one or more PGM supported thereon; and a washcoat overlayer (G) extending axially from the first substrate end for up to 200% of the axial length of the underlying first catalyst washcoat layer, and comprising an aluminosilicate zeolite including at least one of copper, iron and manganese at a loading of > 48.8 g/1 (> 0.8g/in3), wherein a total PGM loading in the first zone (1) in grams per litre of substrate (g/l) is different from the total PGM loading in the second zone (2).

Claims (17)

CLAIMS:
1. A composite, zone-coated, dual-use ammonia and nitric oxide oxidation catalyst for use in an exhaust system for treating an exhaust gas produced by a vehicular compression ignition internal combustion engine, preferably for a heavy-duty diesel vehicle, which exhaust gas also including ammonia, which composite oxidation catalyst comprising: a substrate, optionally a honeycomb flow-through substrate monolith, having a total length L and a longitudinal axis and having a substrate surface extending axially between a first substrate end and a second substrate end; two or more catalyst washcoat zones comprised of a first catalyst washcoat layer comprising a refractory metal oxide support material and one or more platinum group metal components supported thereon and a second catalyst washcoat layer different from the first catalyst washcoat layer and comprising a refractory metal oxide support material and one or more platinum group metal components supported thereon, which two or more catalyst washcoat zones being arranged axially in series on and along the substrate surface, wherein a first catalyst washcoat zone having a length Li, wherein Li < L, is defined at one end by the first substrate end and at a second end by a first end of a second catalyst washcoat zone having a length L2, wherein L2 < L, wherein the first catalyst washcoat zone comprises a first refractory metal oxide support material and one or more platinum group metal components supported thereon; and the second catalyst washcoat zone comprises a second refractory metal oxide support material and one or more platinum group metal components supported thereon; and a washcoat overlayer extending axially from the first substrate end for up to 200% of the axial length of the underlying first catalyst washcoat layer, which washcoat overlayer comprising a particulate metal oxide loading of > 48.8 g/1 (>0.8g/in3), wherein the particulate metal oxide is an aluminosilicate zeolite including at least one of copper, iron and manganese, wherein a total platinum group metal loading in the first catalyst washcoat zone defined in grams of platinum group metal per litre of substrate volume (g/1) is different from the total platinum group metal loading in the second catalyst washcoat zone.
2. A composite oxidation catalyst according to claim 1, wherein the second catalyst washcoat zone is defined at a second end thereof by the second substrate end and wherein the first catalyst washcoat zone comprises the first catalyst washcoat layer and the second catalyst washcoat zone comprises the second catalyst washcoat layer.
3. A composite oxidation catalyst according to claim 1 or 2, wherein the total platinum group metal loading in the first catalyst washcoat zone is less than the total platinum group metal loading in the second catalyst washcoat zone.
4. A composite oxidation catalyst according to claim 1 or 2, wherein the total platinum group metal loading in the first catalyst washcoat zone is greater than a total platinum group metal loading in the second catalyst washcoat zone.
5. A composite oxidation catalyst according to claim 4 comprising three or more catalyst washcoat zones including one zone formed from a two-layer overlap region of the first catalyst washcoat layer and the second catalyst washcoat layer, wherein a third catalyst washcoat zone comprising a third refractory metal oxide support material and one or more platinum group metal components supported thereon is defined at a second end thereof by the second substrate end and wherein a total platinum group metal loading in the third catalyst washcoat zone defined in grams of platinum group metal per litre of substrate volume (g/1) is less than the total platinum group metal loading in the second catalyst washcoat zone.
6. A composite oxidation catalyst according to any one of the preceding claims, wherein the one or more platinum group metal components in the first catalyst washcoat zone consists of both platinum and palladium.
7. A composite oxidation catalyst according to claim 6, wherein a weight ratio of platinum to palladium is >1.
8. A composite oxidation catalyst according to claim 6, wherein a weight ratio of platinum to palladium is <1.
9. A composite oxidation catalyst according to any one of the preceding claims, wherein the washcoat overlayer extends axially for up to 150%, optionally for up to 120%, of the axial length of the underlying first catalyst washcoat layer from the first substrate end.
10. A composite oxidation catalyst according to any one of the preceding claims, wherein where the aluminosilicate zeolite in the washcoat overlayer includes copper, the aluminosilicate zeolite also includes cerium.
11. A composite oxidation catalyst according to any one of the preceding claims, wherein the washcoat loading of the washcoat overlayer is 0.8 to 3.5 g in 3.
12. A composite oxidation catalyst according to any one of the preceding claims, wherein the washcoat overlayer extends axially for >50% of the axial length of the underlying first catalyst washcoat layer from the first substrate end.
13. A composite oxidation catalyst according to any one of the preceding claims, wherein the aluminosilicate zeolite in the washcoat overlayer is faujasite, clinoptilolite, mordenite, silicalite, ferrierite, zeolite X, zeolite Y, ultrastable zeolite Y, AEI zeolite, ZSM-5 zeolite, ZSM-12 zeolite, ZSM-20 zeolite, ZSM-34 zeolite, CHA zeolite, SSZ-13 zeolite, offretite or a beta zeolite.
14. A composite oxidation catalyst according to any one of the preceding claims, wherein the aluminosilicate zeolite in the washcoat overlayer has a mean pore diameter of > 10 nm and/or the washcoat overlayer has a mean interparticle pore diameter of > 10 nm.
15. A composite oxidation catalyst according to any one of the preceding claims, wherein Li is < 50% L.
16. An exhaust system for a vehicular compression ignition engine for treating an exhaust gas comprising inter alia oxides of nitrogen (NOx), which exhaust system comprising a composite oxidation catalyst according to any one of the preceding claims, a first injector for a nitrogenous reductant or a precursor thereof connected to a source of nitrogenous reductant or nitrogenous reductant precursor, which first injector being arranged to inject the nitrogenous reductant or nitrogenous reductant precursor into a flowing exhaust gas upstream from the composite oxidation catalyst and a first substrate comprising a selective catalytic reduction catalyst disposed between the first injector for a nitrogenous reductant or a precursor thereof and the composite oxidation catalyst, wherein the first substrate end of the composite oxidation catalyst is oriented to an upstream side.
17. An exhaust system according to 16 comprising an engine and nitrogenous reductant or nitrogenous reductant precursor electronic control unit(s) comprising a pre programmed computer processor(s) for controlling delivery of ammonia nitrogenous reductant to the first substrate comprising a selective catalytic reduction catalyst at an ammonia-to-NOx ratio of 0.4 to 0.8, optionally 0.4 to 0.6 or 0.7 to 0.8.
GB2207144.3A 2019-10-16 2020-10-16 Composite, zone-coated, dual-use ammonia (amox) and nitric oxide oxidation catalyst Pending GB2604801A (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
EP19203640 2019-10-16
GB201914958A GB201914958D0 (en) 2019-06-26 2019-10-16 Composite, zoned oxidation catalyst for a compression ignition internal combustion engine
GBGB2004768.4A GB202004768D0 (en) 2019-06-26 2020-03-31 Composite, zoned oxidation catalyst for a compression ignition internal combustion engine
GBGB2004769.2A GB202004769D0 (en) 2019-10-16 2020-03-31 Composite, zoned oxidation catalyst for a compression ignition internal combustion engine
EP20068165 2020-06-26
GBGB2009825.7A GB202009825D0 (en) 2019-10-16 2020-06-26 Composite, zoned oxidation catalyst for a compression ignition internal combustion engine
PCT/GB2020/052547 WO2021074605A1 (en) 2019-10-16 2020-10-13 Composite, zoned oxidation catalyst for a compression ignition internal combustion engine
PCT/GB2020/052625 WO2021074652A1 (en) 2019-10-16 2020-10-16 Composite, zone-coated, dual-use ammonia (amox) and nitric oxide oxidation catalyst

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110286900A1 (en) * 2010-05-21 2011-11-24 Basf Corporation PGM-Zoned Catalyst for Selective Oxidation of Ammonia in Diesel Systems
US20170189854A1 (en) * 2013-07-30 2017-07-06 Johnson Matthey Public Limited Company Ammonia slip catalyst
EP3356659A1 (en) * 2015-09-29 2018-08-08 Johnson Matthey Public Limited Company Zoned ammonia slip catalyst for use in combustion turbines
US20180280877A1 (en) * 2017-03-30 2018-10-04 Johnson Matthey Public Limited Company Scr with turbo and asc/doc close-coupled system

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110286900A1 (en) * 2010-05-21 2011-11-24 Basf Corporation PGM-Zoned Catalyst for Selective Oxidation of Ammonia in Diesel Systems
US20170189854A1 (en) * 2013-07-30 2017-07-06 Johnson Matthey Public Limited Company Ammonia slip catalyst
EP3356659A1 (en) * 2015-09-29 2018-08-08 Johnson Matthey Public Limited Company Zoned ammonia slip catalyst for use in combustion turbines
US20180280877A1 (en) * 2017-03-30 2018-10-04 Johnson Matthey Public Limited Company Scr with turbo and asc/doc close-coupled system

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