WO2004067171A1 - Catalyseur d'echappement pour moteurs a essence - Google Patents

Catalyseur d'echappement pour moteurs a essence Download PDF

Info

Publication number
WO2004067171A1
WO2004067171A1 PCT/IB2004/000289 IB2004000289W WO2004067171A1 WO 2004067171 A1 WO2004067171 A1 WO 2004067171A1 IB 2004000289 W IB2004000289 W IB 2004000289W WO 2004067171 A1 WO2004067171 A1 WO 2004067171A1
Authority
WO
WIPO (PCT)
Prior art keywords
ceramic
solution
substrate
ceramic powder
engine exhaust
Prior art date
Application number
PCT/IB2004/000289
Other languages
English (en)
Inventor
James Anthony Cairns
Graham James Berry
Gary John Callon
Robert Dermot Smith
Original Assignee
Aktina Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aktina Limited filed Critical Aktina Limited
Publication of WO2004067171A1 publication Critical patent/WO2004067171A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • 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
    • F01N3/24—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 constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • 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 the manufacture of an exhaust catalyst comprising a support substrate coated with a ceramic layer having metals or metal oxides dispersed therein. More particularly, the invention relates to a petrol engine exhaust catalyst comprising a zirconia layer incorporating catalytic metal(s), such as palladium or platinum, in highly dispersed form.
  • catalytic material is applied to substrates by immersing the substrate in a washcoat slurry, which may also contain the catalytic material. Lately, organic solutions of metal organic precursors of catalytic material have become widely used instead of slurries.
  • a catalyst is prepared by pre-oxidising a substrate, preparing a solution comprising a ceramic oxide precursor, such as alumina or silica, and a solution containing a catalyst precursor, depositing precursors onto the substrate, such as a fiber board, and thermally treating the board to decompose the precursor into the catalyst.
  • the precursors are deposited by immersing, spraying or the like methods.
  • the metallic fiber board obtained thereby comprises a plurality of metallic fibers, preferably produced from a Fe-Cr-AI alloy, wherein the fibers are coated with a dense oxide covering the surfaces of the fibers, onto which a porous oxide layer is deposited covering the exterior surface of the dense layer, and the catalyst is a noble metal distributed across the exterior surface of the porous oxide layer or incorporated within it.
  • US 5,980,843 discloses another catalytic system obtained from a perforated foil or a metallic grid on which a porous ceramic layer, preferably of alumina or zirconia, is deposited by means of techniques including plasma spraying, flame spraying, and detonation spraying. The ceramic layer is then impregnated with a catalyst precursor solution or suspension. After suitable thermal treatments the final catalytic system is obtained.
  • the production processes described above are disadvantageous in that, predominantly, the ceramic oxide layer formed from precursor solutions has an amorphous structure, and hence, low structural strength, insufficient thermal stability and low adhesion to the substrate.
  • An effective approach has been developed recently by the inventors of the present invention as described in PCT/GB02/04086 filed 30.08.02, the entire disclosure of which application is incorporated herein by reference.
  • a thin film stabilised porous ceramic such as zirconia, can be effectively used in making catalysts and gas sensors.
  • This process includes introducing the stabilising moiety into the precursor solution, so that the transformation of the amorphous porous ceramic layer into a crystalline structure occurs at lower temperatures and relatively milder conditions than usually employed to effect such a transformation. The result is that the porous oxide layer is bonded strongly to the substrate and has a high structural strength that avoids the necessity of providing additional treatment of the composite material.
  • Still one more objective is to provide a catalytic member for combustion of gases, having a high thermal conductivity and low flow resistivity but at the same time improved mass transfer characteristics and high catalytic activity.
  • a method for making a petrol engine exhaust catalyst comprising the steps of: - preparing a solution by admixing to a ceramic precursor solution a nanoscale ceramic powder as the major constituent to the ceramic precursor solution; - contacting a substrate with a solution so as to form a coating directly on the substrate,
  • a petrol engine exhaust catalyst comprising - a substrate supported layer of porous ceramic incorporating nanoscale ceramic particles and one or more catalytic metals, the ceramic layer being strongly adhered directly to the substrate.
  • the nanoscale ceramic powder is composed primarily of ceria and zirconia, with the addition of a small percentage of the oxides of lanthanum and neodymium.
  • the surface area of the coating is increased and thereby the efficiency of interaction between the coating and the exhaust gas is improved.
  • Thermal stability of an engine exhaust catalyst is an important consideration, as the device can be exposed to temperatures of up to 1000°C under certain operating conditions and to even higher temperatures if an engine fault should develop.
  • a catalyst must be able to withstand such conditions for an operational lifetime of at least 100000 miles (160000km).
  • Washcoat A solution is made up of zirconium propionate dissolved in tetrahydrofuran at a concentration of between 20g and 200g of zirconium propionate per litre of solution, preferably between 50 and 100g per litre. To this is added a quantity of the ceria/zirconia/lanthana/neodymia powder mentioned above, of between 100 and 300g per litre of solution, and preferably between 120 and 180g per litre.
  • the mixture thus created is deposited onto a suitable substrate, such as a Fecralloy steel monolith, which is then dried to remove the solvent and heated to a temperature of at least 300°C to decompose the zirconium propionate and achieve good adhesion of the washcoat layer to the substrate.
  • a suitable substrate such as a Fecralloy steel monolith
  • a solution of palladium acetate and rhodium acetate in tetrahydrofuran is made up, comprising between 2 and 5g of rhodium acetate per litre of solution, preferably between 2.4 and 3g per litre, and between 0.5 and 5g of palladium acetate per litre of solution, preferably between 0.7 and 2.5g per litre.
  • This is applied to the monolith coated with washcoat and then dried to remove the solvent and heated to a temperature of at least 300°C to decompose the precursors and form metallic rhodium and palladium.
  • a solution was prepared consisting of 25g zirconium propionate per litre of tetrahydrofuran. To this was added 150g of nanoscale powder per litre.
  • the nanoscale powder was composed of zirconium oxide (47.10%), cerium oxide (45.95%), lanthanum oxide (1.87%) and neodymium oxide (5.08%).
  • the catalyst prepared as above was tested in the exhaust system of a stationary 1.81 4-cylinder 8-valve Volkswagen petrol engine connected to a dynamometer. Two load conditions were employed. The first was a standard load condition using an engine speed of 2500rpm and a torque of 100Nm. The second was a full-throttle high load condition using an engine speed of 3300rpm and 130Nm of torque. The results are shown below in table 1 :
  • the catalyst was then subjected to accelerated ageing by heating it in air at 900°C for four hours. After cooling it was tested again, and showed only a small degradation, as can be seen from table 2:

Landscapes

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

Abstract

La présente invention concerne la fabrication d'un catalyseur d'échappement présentant un substrat support enduit d'une couche céramique pourvue de métaux ou d'oxydes métalliques dispersés. Ladite invention concerne également un procédé de production d'un catalyseur métal-céramique consistant à enduire le substrat d'une solution contenant des précurseurs céramiques puis à soumettre le substrat enduit à un traitement thermique ultérieur, une poudre céramique à l'échelle nanométrique étant ajoutée, en tant que constituant majeur, à la solution de précurseurs céramiques avant le traitement thermique dudit substrat de façon à permettre la décomposition des composés précurseurs. La couche céramique poreuse ainsi obtenue est ensuite imprégnée d'un ou de plusieurs métaux catalytiques ou oxydes métalliques.
PCT/IB2004/000289 2003-01-31 2004-01-29 Catalyseur d'echappement pour moteurs a essence WO2004067171A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44385103P 2003-01-31 2003-01-31
US60/443,851 2003-01-31

Publications (1)

Publication Number Publication Date
WO2004067171A1 true WO2004067171A1 (fr) 2004-08-12

Family

ID=32825383

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2004/000289 WO2004067171A1 (fr) 2003-01-31 2004-01-29 Catalyseur d'echappement pour moteurs a essence

Country Status (1)

Country Link
WO (1) WO2004067171A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8034738B2 (en) * 2007-03-14 2011-10-11 Taiyo Nippon Sanso Corporation Process for producing catalyst body for production of brush-shaped carbon nanostructure
CN107849962A (zh) * 2015-05-19 2018-03-27 巴斯夫公司 用于钝化选择性催化还原的催化烟灰过滤器

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5888464A (en) * 1997-04-08 1999-03-30 Engelhard Corporation Catalyst composition containing an intimately combined cerium-zirconium oxide
EP0955267A1 (fr) * 1996-12-27 1999-11-10 Anan Kasei Co., Ltd Oxyde de compose zirconium et cerium, procede d'elaboration correspondant et co-catalyseur d'epuration des gaz
US6040265A (en) * 1996-02-21 2000-03-21 Asec Manufacturing General Partnership Methods of making highly dispersed substantially uniform cerium and zirconium mixed-metal-oxide composite supports for exhaust conversion catalysts
WO2003082740A1 (fr) * 2002-03-28 2003-10-09 Utc Fuel Cells, Llc Structure d'oxyde metallique mixte a base d'oxyde de cerium, procede de realisation et utilisation associes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6040265A (en) * 1996-02-21 2000-03-21 Asec Manufacturing General Partnership Methods of making highly dispersed substantially uniform cerium and zirconium mixed-metal-oxide composite supports for exhaust conversion catalysts
EP0955267A1 (fr) * 1996-12-27 1999-11-10 Anan Kasei Co., Ltd Oxyde de compose zirconium et cerium, procede d'elaboration correspondant et co-catalyseur d'epuration des gaz
US5888464A (en) * 1997-04-08 1999-03-30 Engelhard Corporation Catalyst composition containing an intimately combined cerium-zirconium oxide
WO2003082740A1 (fr) * 2002-03-28 2003-10-09 Utc Fuel Cells, Llc Structure d'oxyde metallique mixte a base d'oxyde de cerium, procede de realisation et utilisation associes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8034738B2 (en) * 2007-03-14 2011-10-11 Taiyo Nippon Sanso Corporation Process for producing catalyst body for production of brush-shaped carbon nanostructure
US8530374B2 (en) 2007-03-14 2013-09-10 Taiyo Nippon Sanso Corporation Catalyst body for production of brush-shaped carbon nanostructure
CN107849962A (zh) * 2015-05-19 2018-03-27 巴斯夫公司 用于钝化选择性催化还原的催化烟灰过滤器

Similar Documents

Publication Publication Date Title
US10413880B2 (en) Compositions for passive NOx adsorption (PNA) systems and methods of making and using same
EP1436445B1 (fr) Procede pour produire des composites en ceramique-metal en films minces poreux et composites obtenus par ce procede
KR101797252B1 (ko) 소형 엔진 층상 촉매 물품 및 제조 방법
US8518857B2 (en) Ceramic structures having hydrophobic coatings
US20170151552A1 (en) Compositions of lean nox trap (lnt) systems and methods of making and using same
WO2017029971A1 (fr) Catalyseur de purification de gaz d'échappement
US20130213018A1 (en) Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions
US7605110B2 (en) Ceramic body, ceramic catalyst body and related manufacturing methods
US5202299A (en) Catalytic washcoat for treatment of diesel exhaust
US20170189892A1 (en) Layered catalysts for gasoline engine exhaust
WO2006057067A1 (fr) Catalyseur pour la purification de gaz d’echappement
EP2512664A1 (fr) Catalyseurs perfectionnés pour applications automobiles
US7399728B2 (en) Catalyst formulation, exhaust system, and gas treatment device
CN106999849A (zh) 使用混合催化颗粒的三效催化转化器
JP2006281155A (ja) 触媒体
JP2015199066A (ja) 内燃機関の排ガス浄化装置及びその製造方法、並びに排ガス浄化装置作製用塗料
US7067454B2 (en) Low cost quick response catalyst system
US9029288B2 (en) Catalyst and a manufacturing method thereof
JP2013063421A (ja) 排気浄化触媒及び内燃機関の排気浄化装置
WO2004067171A1 (fr) Catalyseur d'echappement pour moteurs a essence
EP2659968B1 (fr) Utilisation d'un catalyseur de combustion particulaire et d'un filtre particulaire, les procédés de production de ceux-ci
JP5014086B2 (ja) 排ガス浄化用触媒
JP2008155198A (ja) 繊維状触媒
KR101351469B1 (ko) 디젤산화촉매와 탈질소산화물촉매가 코팅된 디젤입자필터의 제조방법
JP5412104B2 (ja) 排ガス浄化用触媒

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase