WO1995003877A1 - Catalyseur en un metal commun, support pour ce catalyseur et procede de purification en deux etapes des gaz d'echappement de vehicules - Google Patents

Catalyseur en un metal commun, support pour ce catalyseur et procede de purification en deux etapes des gaz d'echappement de vehicules Download PDF

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Publication number
WO1995003877A1
WO1995003877A1 PCT/GB1994/001635 GB9401635W WO9503877A1 WO 1995003877 A1 WO1995003877 A1 WO 1995003877A1 GB 9401635 W GB9401635 W GB 9401635W WO 9503877 A1 WO9503877 A1 WO 9503877A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
support
oxides
oxide
mixed
Prior art date
Application number
PCT/GB1994/001635
Other languages
English (en)
Inventor
Ashok Kumar Bhattacharya
Original Assignee
Rover Group 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 Rover Group Limited filed Critical Rover Group Limited
Priority to EP94921750A priority Critical patent/EP0711198A1/fr
Priority to JP7505661A priority patent/JPH09501348A/ja
Priority to GB9600502A priority patent/GB2295780A/en
Publication of WO1995003877A1 publication Critical patent/WO1995003877A1/fr

Links

Classifications

    • 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
    • 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
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • 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

  • This invention relates to a catalyst for
  • combustion such as motor vehicle exhaust gases.
  • the catalytic component of such exhaust gas catalysts that are used at present consists of
  • Platinum group metals are in short supply
  • One objective of this invention is therefore to provide an effective exhaust gas catalyst that does not rely on a scarce and expensive material such as platinum or other platinum-group metal.
  • base metal catalytic systems have been found to exhibit varied resistance to sulphur poisoning and have specific activities lower than those of platinum-group metal systems.
  • the present invention overcomes the above problems.
  • a catalyst comprising:
  • copper component we mean a mixture containing A(i) cuprous oxide and cupric oxide either on their own or mixed with metallic copper or A(i) and A(ii) one or more oxides of transition metals,
  • the lanthanide oxide component B(i) is selected from oxides of cerium, lanthanum and yttrium.
  • component B(i) is cerium dioxide either on its own or mixed with one or more other lanthanide oxides.
  • Group II component B(ii) is selected from one or more oxides of magnesium, calcium, strontium and barium.
  • Group IV component B(iv) is selected from oxides of one or more of zirconium, titanium and Hafnium.
  • the Group IIIb component B(iii) is preferably alumina (Al 2 O 3 ).
  • the components of the mixed support B may each be present in an amount of from 0.005 to 99.0 per cent by weight based on the total weight (W) of the support, with the total amount of components B(i) to B(iv) always adding up to 100 wt %.
  • the constituents of the copper component to be disposed or loaded on the support may each be present in an amount of from 0.005 to 25 wt % based on the total weight (W) of the support.
  • the catalysts of the invention exhibited good stability and a catalytic activity comparable to or better than a commercial platinum group metal catalyst.
  • Catalysts of the invention can be prepared by a variety of different methods which are within the knowledge of a worker well versed in the art.
  • urea Suitable, but by no means the only methods for preparation of the support include: urea
  • Suitable, but not the only methods for dispersion of the copper component on the support include deposition by copper acetate, copper formate, copper ammine complex, copper carbonate and copper nitrate.
  • the catalyst In order to promote efficient NOx removal at high space velocities the catalyst should be prepared so that the following NOx removal reaction:-
  • the invention provides a two-stage process for the purification of exhaust gases comprising:
  • the highly acidic support may comprise:-
  • a solid solution comprising two or more of zirconium oxide (ZrO 2 ) preferably present in an amount of from 3 to 15% and more preferably 7%, tungsten oxide (WO 3 ) molybdenum oxide (MoO 3 ), alumina (Al 2 O 3 ); optionally carried on a high surface area support such as alumina (Al 2 O 3 ) , preferably stabilized with magnesium oxide; or
  • the first catalyst may comprise (ii) cuprous oxide and cupric oxide and optionally metallic copper on the mixed support B in combination with a second catalyst comprising a platinum group metal dispersed on the mixed support B.
  • the platinum group metal comprises palladium and a mixture of metallic palladium and palladium oxide is particularly preferred.
  • the invention provides the mixed oxide support B for a base metal or platinum-group metal catalyst used in the purification of exhaust gases.
  • a catalyst embodying the invention will now be described, by way of
  • Figs. 1a and 1b show results obtained with a base metal catalyst outside the scope of the
  • invention comprising copper oxide supported on ⁇ - Al 2 O 3 .
  • Requisite quantities of nitrate were added to 400 ml of distilled water and heated to 60°C. To this solution, about 35 ml of (1:1) NH 4 OH was added quickly with stirring. Final pH was 9. The slurry was digested at 70°-80°C for 4 hours, filtered, washed 4 times, each with 200 ml of cold water, dried overnight at 110°C and powdered.
  • composition Mg 0.935 Ce 0.03 Zr 0.03 La 0.005 Al 2 O 4 with a surface area of 137 m 2 /g.
  • the catalyst of the invention is able to achieve over 90% conversion of NO at 525°C.
  • Fig. 3 shows the catalytic conversion of a synthetic exhaust gas composition at a space velocity of 15000 hr GHSV in a two-stage process of the invention in which the catalyst in the first stage comprises the catalyst of Fig. 2 and the catalyst in the second stage comprises the copper component of the catalyst of Fig. 2 dispersed on a zeolite support.
  • the two-stage process of the invention it is possible to obtain 100% NO conversion at a temperature of 225°C.
  • Fig. 4 shows the catalytic conversion of a synthetic exhaust gas composition at a space velocity of 5000 hr -1 GHSV of a synthetic exhaust gas
  • composition in a two-stage process of the invention in which the catalyst in the first stage comprises the catalyst of Fig. 2 and the catalyst in the second stage comprises the mixed oxide support B of the catalyst of Fig. 2 having palladium dispersed thereon and an amount of 1% weight based on the total weight of the support.
  • the catalyst in the first stage comprises the catalyst of Fig. 2
  • the catalyst in the second stage comprises the mixed oxide support B of the catalyst of Fig. 2 having palladium dispersed thereon and an amount of 1% weight based on the total weight of the support.

Landscapes

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

Abstract

L'invention concerne un catalyseur pour traiter les gaz d'échappement de véhicules comprenant: (A) un composant à base de cuivre, contenant de l'oxyde cuivreux et de l'oxyde cuivrique dispersés sur, (B) un support mixte contenant (i) un ou plusieurs oxydes de lanthanides; (ii) un ou plusieurs oxydes d'éléments du groupe II; (iii) un ou plusieurs oxydes d'éléments du groupe IIIb; et (iv) un ou plusieurs oxydes d'éléments du groupe IV du système de Mendeléeff.
PCT/GB1994/001635 1993-07-29 1994-07-28 Catalyseur en un metal commun, support pour ce catalyseur et procede de purification en deux etapes des gaz d'echappement de vehicules WO1995003877A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94921750A EP0711198A1 (fr) 1993-07-29 1994-07-28 Catalyseur en un metal commun et procede de purification en deux etapes des gaz d'echappement de vehicules
JP7505661A JPH09501348A (ja) 1993-07-29 1994-07-28 自動車排ガス浄化のための卑金属触媒と触媒担体さらに二段階プロセス
GB9600502A GB2295780A (en) 1993-07-29 1994-07-28 Base metal catalyst, catalytic support and two-stage process for the purification of vehicle exhaust gases

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB939315679A GB9315679D0 (en) 1993-07-29 1993-07-29 Base metal catalyst,catalytic support and two-stage process for the purification of vehicle exhaust gases
GB9315679.2 1993-07-29

Publications (1)

Publication Number Publication Date
WO1995003877A1 true WO1995003877A1 (fr) 1995-02-09

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1994/001635 WO1995003877A1 (fr) 1993-07-29 1994-07-28 Catalyseur en un metal commun, support pour ce catalyseur et procede de purification en deux etapes des gaz d'echappement de vehicules

Country Status (4)

Country Link
EP (1) EP0711198A1 (fr)
JP (1) JPH09501348A (fr)
GB (2) GB9315679D0 (fr)
WO (1) WO1995003877A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10252103A1 (de) * 2002-11-08 2004-05-27 Süd-Chemie AG Ce/Cu/Mn-Katalysatoren
DE102007037796A1 (de) * 2007-08-10 2009-02-12 Süd-Chemie AG Verfahren zur Entfernung von CO, H2 und/oder CH4 aus dem Anodenabgas einer Brennstoffzelle mit Mischoxidkatalysatoren umfassend Cu, Mn und gegebenenfalls mindestens ein Seltenerdmetall
WO2013163523A1 (fr) * 2012-04-26 2013-10-31 Basf Corporation Catalyseur de métal de base et procédé pour l'utiliser
US8668890B2 (en) 2012-04-26 2014-03-11 Basf Corporation Base metal catalyst composition and methods of treating exhaust from a motorcycle
CN111151262A (zh) * 2020-01-14 2020-05-15 西安理工大学 一种Mn-Cu2O改性光催化剂及其制备方法
CN111565838A (zh) * 2018-02-23 2020-08-21 株式会社Lg化学 用于烃的氧氯化工艺的催化剂、其制备方法和使用该催化剂制备烃的氧氯化化合物的方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4045002B2 (ja) * 1998-02-02 2008-02-13 三井金属鉱業株式会社 複合酸化物及びそれを用いた排ガス浄化用触媒
JP2012066166A (ja) * 2010-09-21 2012-04-05 Denso Corp 排気浄化用触媒
JP5567999B2 (ja) * 2010-12-10 2014-08-06 トヨタ自動車株式会社 ベースメタル系排ガス浄化触媒
JP5715518B2 (ja) * 2011-07-25 2015-05-07 ダイハツ工業株式会社 排ガス浄化用触媒

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2342909A1 (de) * 1972-08-25 1974-04-04 Hitachi Ltd Katalysator
EP0370617A1 (fr) * 1988-10-20 1990-05-30 ROVER GROUP LIMITED (Registered Number 1595268) Catalyseur
EP0415410A1 (fr) * 1989-08-31 1991-03-06 Tosoh Corporation Procédé de réduction catalytique des oxydes d'azote de gaz d'échappement
WO1992004965A1 (fr) * 1990-09-20 1992-04-02 Rover Group Limited Catalyseurs en metal du groupe de platine supporte
EP0513469A1 (fr) * 1991-05-13 1992-11-19 Imcs Ab Catalyseur contenant des terres rares et support
US5182249A (en) * 1990-10-22 1993-01-26 East China University Of Chemical Technology Non-precious metal three way catalyst
EP0526896A1 (fr) * 1991-08-07 1993-02-10 Toyota Jidosha Kabushiki Kaisha Catalyseur pour la purification des effluents gazeux
EP0541271A1 (fr) * 1991-11-08 1993-05-12 Ford Motor Company Limited Système catalytique pour le traitement des gaz d'échappement d'un moteur à essence à combustion pauvre

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2342909A1 (de) * 1972-08-25 1974-04-04 Hitachi Ltd Katalysator
EP0370617A1 (fr) * 1988-10-20 1990-05-30 ROVER GROUP LIMITED (Registered Number 1595268) Catalyseur
EP0415410A1 (fr) * 1989-08-31 1991-03-06 Tosoh Corporation Procédé de réduction catalytique des oxydes d'azote de gaz d'échappement
WO1992004965A1 (fr) * 1990-09-20 1992-04-02 Rover Group Limited Catalyseurs en metal du groupe de platine supporte
US5182249A (en) * 1990-10-22 1993-01-26 East China University Of Chemical Technology Non-precious metal three way catalyst
EP0513469A1 (fr) * 1991-05-13 1992-11-19 Imcs Ab Catalyseur contenant des terres rares et support
EP0526896A1 (fr) * 1991-08-07 1993-02-10 Toyota Jidosha Kabushiki Kaisha Catalyseur pour la purification des effluents gazeux
EP0541271A1 (fr) * 1991-11-08 1993-05-12 Ford Motor Company Limited Système catalytique pour le traitement des gaz d'échappement d'un moteur à essence à combustion pauvre

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10252103A1 (de) * 2002-11-08 2004-05-27 Süd-Chemie AG Ce/Cu/Mn-Katalysatoren
US7329627B2 (en) 2002-11-08 2008-02-12 Sud-Chemie Ag Ce/Cu/Mn-catalysts
DE102007037796A1 (de) * 2007-08-10 2009-02-12 Süd-Chemie AG Verfahren zur Entfernung von CO, H2 und/oder CH4 aus dem Anodenabgas einer Brennstoffzelle mit Mischoxidkatalysatoren umfassend Cu, Mn und gegebenenfalls mindestens ein Seltenerdmetall
CN104364003A (zh) * 2012-04-26 2015-02-18 巴斯夫公司 基本金属催化剂及其使用方法
US8668890B2 (en) 2012-04-26 2014-03-11 Basf Corporation Base metal catalyst composition and methods of treating exhaust from a motorcycle
US8765085B2 (en) 2012-04-26 2014-07-01 Basf Corporation Base metal catalyst and method of using same
WO2013163523A1 (fr) * 2012-04-26 2013-10-31 Basf Corporation Catalyseur de métal de base et procédé pour l'utiliser
CN109550504A (zh) * 2012-04-26 2019-04-02 巴斯夫公司 基本金属催化剂及其使用方法
CN111565838A (zh) * 2018-02-23 2020-08-21 株式会社Lg化学 用于烃的氧氯化工艺的催化剂、其制备方法和使用该催化剂制备烃的氧氯化化合物的方法
EP3721993A4 (fr) * 2018-02-23 2021-01-20 Lg Chem, Ltd. Catalyseur pour le traitement d'oxychloration d'hydrocarbure, son procédé de préparation et procédé de préparation d'un composé oxychloré d'hydrocarbure l'utilisant
US11179703B2 (en) 2018-02-23 2021-11-23 Lg Chem. Ltd. Catalyst for processing oxychlorination of hydrocarbon, preparation method therefor, and preparation method of oxychlorinated compound of hydrocarbon using same
CN111565838B (zh) * 2018-02-23 2023-09-26 株式会社Lg化学 用于烃的氧氯化工艺的催化剂、其制备方法和使用该催化剂制备烃的氧氯化化合物的方法
CN111151262A (zh) * 2020-01-14 2020-05-15 西安理工大学 一种Mn-Cu2O改性光催化剂及其制备方法

Also Published As

Publication number Publication date
JPH09501348A (ja) 1997-02-10
GB2295780A (en) 1996-06-12
EP0711198A1 (fr) 1996-05-15
GB9315679D0 (en) 1993-09-15
GB9600502D0 (en) 1996-03-27

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