CN107206358A - 三效催化剂及其在排气系统中的应用 - Google Patents

三效催化剂及其在排气系统中的应用 Download PDF

Info

Publication number
CN107206358A
CN107206358A CN201680008746.4A CN201680008746A CN107206358A CN 107206358 A CN107206358 A CN 107206358A CN 201680008746 A CN201680008746 A CN 201680008746A CN 107206358 A CN107206358 A CN 107206358A
Authority
CN
China
Prior art keywords
way catalyst
extrusion
catalyst
component
argentiferous
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.)
Granted
Application number
CN201680008746.4A
Other languages
English (en)
Other versions
CN107206358B (zh
Inventor
H-L·常
陈海鹰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
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 Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of CN107206358A publication Critical patent/CN107206358A/zh
Application granted granted Critical
Publication of CN107206358B publication Critical patent/CN107206358B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • 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
    • 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
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • 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
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/068—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • 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
    • B01J37/0244—Coatings comprising several layers
    • 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
    • B01J37/0248—Coatings comprising impregnated particles
    • 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
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • 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
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • 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
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0821—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with particulate filters
    • 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
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
    • F01N3/0842—Nitrogen oxides
    • 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
    • F01N3/101—Three-way catalysts
    • 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
    • F01N3/18—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
    • 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
    • F01N3/18—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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1025—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/104—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/502—Beta zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/504—ZSM 5 zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/912—HC-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/915—Catalyst supported on particulate filters
    • 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
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Processes For Solid Components From Exhaust (AREA)

Abstract

公开了一种三效催化剂。该三效催化剂包含：包含钯和二氧化铈‑氧化锆‑氧化铝混合氧化物或者复合氧化物的钯组分，以及还包含：包含铑和包含氧化锆的材料的铑组分。该钯组分和铑组分涂覆到含银的挤出的分子筛基底。本发明还包括包含该三效催化剂的排气系统。该三效催化剂导致了改进的烃存储和转化，特别是在冷启动周期过程中。

Description

三效催化剂及其在排气系统中的应用
发明领域
本发明涉及一种三效催化剂，它在内燃机排气系统中的用途和处理内燃机废气的方法。
发明背景
内燃机产生了含有多种污染物的废气，包括烃，一氧化碳和氮氧化物(“NOx”)。排放控制系统，包括废气催化剂，广泛用于降低排放到大气中的这些污染物的量。一种用于汽油机应用的常用催化剂是“三效催化剂”(TWC)。TWC发挥了三个主要功能：(1)CO的氧化；(2)未燃烧的烃的氧化；和(3)NOx还原成N2。
TWC如同其他废气催化剂那样，一旦它们达到它们的运行温度(典型地200℃和更高)，典型地实现了非常高的效率。但是，这些系统在低于它们的运行温度(“冷启动”期间)时是相对低效的。由于甚至更严格的国家和地区立法降低了可以从柴油机或汽油机排放的污染物的量，因此降低冷启动期间的排放变成一个主要挑战。因此，要持续开发用于降低冷启动条件期间排放的NOx和烃的水平的方法。
对于冷启动烃控制来说，已经研究了烃(HC)阱，其包括沸石作为烃捕集组分。在这些系统中，沸石组分在启动期过程中吸收和存储烃，并且当废气温度高到足以解吸烃时释放所存储的烃。所解吸的烃随后通过并入HC阱中的TWC组件或者通过位于HC阱下游的分开的TWC来转化。
例如美国专利No.5772972公开了一种烃捕集材料和钯基三效催化剂材料的杂合系统。美国专利No.6617276教导了一种催化剂结构，其包含基本组成为烃吸附性沸石和浸渍到该沸石上的K、Rb或者Cs活性金属的第一层，基本组成为至少一种铂族金属的至少一种另外的层，和该第一层和一种或多种另外的层位于其上的催化剂基底。在EP1129774中，教导了烃吸附性元件，其包含这样的沸石，其SiO2：Al2O3摩尔比是100或者更高和平均初级粒径是1μm或者更低，并且它没有单价金属元素。美国专利No.6074973教导了一种催化的烃阱材料，其包含分散在高表面积金属氧化物载体上的钯和银和沸石材料例如ZSM-5，Beta，Y和其他合适的沸石中的一种或多种。
美国申请公开No.2012/0117953A1教导了一种三效催化剂，其包含挤出的实心体，该实心体包含10-100重量％的至少一种粘合剂/基质组分，5-90重量％的沸石分子筛，非沸石分子筛或者其任意两种或更多种的混合物，和0-80重量％的任选稳定化的二氧化铈。该催化剂包含至少一种贵金属和任选地至少一种非贵金属，其中：(i)该至少一种贵金属负载于挤出的实心体表面上的一个或多个涂层中；(ii)至少一种金属存在于整个挤出的实心体中，和至少一种贵金属也负载于挤出的实心体表面上的一个或多个涂层中；或者(iii)至少一种金属存在于整个挤出的实心体中，其在挤出的实心体的表面处的存在浓度较高，和至少一种贵金属也负载在该挤出的实心体表面上的一个或多个涂层中。共同待决的美国专利申请系列No.14/528139公开了一种三效催化剂，其包含含银的挤出的沸石基底。另外，美国申请公开No.2012/0308439A1教导了一种冷启动催化剂，其包含(1)沸石催化剂，其包含贱金属、贵金属和沸石，和(2)负载型铂族金属催化剂，其包含一种或多种铂族金属和一种或多种无机氧化物载体。
对于任何汽车系统和方法，令人期望的是在废气处理系统中，特别是在冷启动条件下获得仍然进一步的改进。我们已经发现一种新的三效催化剂，其提供了对于内燃机废气增强的清洁性。
发明内容
本发明是一种用于排气系统的三效催化剂。该三效催化剂包含：包含钯和二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物的钯组分；和包含铑和包含氧化锆的材料的铑组分。该钯组分和铑组分涂覆于含银的挤出的分子筛基底上。本发明还包括包含该三效催化剂的排气系统，和用该三效催化剂处理废气的方法。
具体实施方式
本发明的三效催化剂包含钯组分，其包含钯和二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物。该二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物可以通过任何已知的方法来生产。例如该二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物可以如下来生产：将铈和锆盐前体浸渍到氧化铝氧化物上(参见例如日本未审专利No.7-300315)，沉淀铈-锆氢氧化物，然后与氧化铝混合(参见例如美国专利No.5883037)，通过铈/锆/铝盐前体共沉淀(参见例如美国专利No.6306794和6150288和PCT国际申请WO2006/070201)，通过将氧化铝表面涂覆到铈-锆氧化物上(参见例如美国申请公开No.2007/0191220A1)，通过将铈-锆复合氧化物与γ-氧化铝粉末一起球磨(参见例如美国申请公开No.2011/0171092A1)，或者通过铈/锆/铝前体的火焰喷射热解。
优选，该二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物是如下来生产的：首先将铈(IV)化合物和锆(IV)化合物与氧化铝浆料在大于40℃的温度合并来生产反应浆料；将该反应浆体与沉淀剂接触来将不溶性铈和锆化合物沉淀到氧化铝上和形成铈-锆-铝氧化物粒子；和煅烧该铈-锆-铝氧化物粒子来生产二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物，如美国申请公开No.2013/0108530所述，其教导在此引入作为参考。
任选地，该二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物可以包含稀土，碱土金属化合物或者过渡金属化合物。例如，用于二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物的氧化铝前体可以是稀土金属或者碱土金属稳定化的氧化铝，例如含有选自下面的稀土金属或者碱土金属：镧，钕，镨，钇，钡和锶。优选，该稀土金属或者碱土金属稳定化的氧化铝包含0.1-20重量％的稀土金属或者碱土金属。也可以添加稀土金属、碱土金属或者过渡金属化合物来制备该二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物，例如添加的稀土金属优选选自镧、钕、镨和钇化合物或者过渡金属优选选自铁、锰、钴和铜化合物。
优选该二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物包含重量比是0.1-70：0.1-70：95-10，更优选5-60：5-60：90-20的CeO2：ZrO2：Al2O3。Ce：Zr摩尔比优选是0.05-19和更优选是0.25-1.5。
将钯组分中的钯优选引入二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物中，并且可以通过任何已知的手段负载到二氧化铈-氧化锆-氧化铝氧化物上，添加方式不被认为是特别关键的。例如，可以通过浸渍、吸附、初湿含浸法、沉淀、喷雾干燥等将钯化合物(例如硝酸钯)添加到二氧化铈-氧化锆-氧化铝氧化物中，来生产该钯组分。合适的钯负载量是0.04-7.1g/L(1-200g/ft3)催化剂体积。
本发明的三效催化剂还包含铑组分，其包含铑和含氧化锆的材料。该含氧化锆的材料可以是任何已知的含氧化锆的材料，例如氧化锆或者任何含氧化锆的混合氧化物或者复合氧化物。该含氧化锆的材料可以是稀土金属或者碱土金属稳定化的氧化锆，例如含有选自下面的稀土金属或者碱土金属：铈、镧、钕、镨、钇、钡和锶。二氧化铈-氧化锆混合氧化物或者复合氧化物是特别优选的含氧化锆的材料。该二氧化铈-氧化锆混合氧化物或者复合氧化物可以是任何已知的二氧化铈-氧化锆氧化物。对于该二氧化铈-氧化锆混合氧化物或者复合氧化物，Ce：Zr摩尔比范围优选是0.01-19和更优选是0.25-1.5。
优选将该铑组分中的铑引入含氧化锆的材料中，并且可以通过任何已知的手段负载到该含氧化锆的材料上，添加方式不被认为是特别关键的。可以通过浸渍、吸附、初湿含浸法、沉淀、喷雾干燥等将例如铑化合物(例如硝酸铑)添加到该含氧化锆的材料(例如二氧化铈-氧化锆氧化物)中，来生产该铑组分。合适的铑负载量是0.04-7.1g/L(1-200g/ft3)催化剂体积。
将该钯组分和铑组分涂覆到含银的挤出的分子筛基底上。
该含银的挤出的分子筛基底的分子筛可以是任何天然或者合成分子筛，包括沸石，优选由铝，硅和/或磷组成。分子筛典型地具有通过共用氧原子连接的SiO4、AlO4和/或PO4的三维排列。该分子筛骨架典型地是通过电荷补偿性阳离子来抗衡的阴离子型，所述阳离子典型的是碱金属和碱土金属元素(例如Na、K、Mg、Ca、Sr和Ba)以及质子。可以将其他金属(例如Fe、Ti和Ga)引入该分子筛骨架中来生产引入了金属的分子筛(例如钛硅酸盐)。
优选该分子筛选自铝硅酸盐沸石、金属取代的铝硅酸盐沸石、铝磷酸盐沸石、金属取代的铝磷酸盐沸石、硅铝磷酸盐沸石或者金属取代的硅铝磷酸盐沸石。特别优选的分子筛具有骨架类型：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、ZON、MFI、FER、MWW、EUO、CON、BEA、FAU、MOR、和EMT以及任意两种或更多种的混合物或者共生物。最优选该分子筛的骨架类型是AEI(例如SAPO-18，SSZ-39)、CHA(例如SAPO-34、SSZ-13)、CON(例如SSZ-33)、LEV(例如SAPO-35)、BEA(例如β沸石)、FAU(例如沸石Y)或者MFI(例如ZSM-5)。
优选的分子筛包括SAPO-34，SSZ-33，SSZ-13，SSZ-39，β沸石，ZSM-5沸石或者Y-沸石。该分子筛最优选是β沸石、ZSM-5沸石或者SSZ-39。
可以通过任何已知的手段形成该含银的挤出的分子筛基底。典型地，将该含银的分子筛挤出来形成流通式或者滤过式基底，并且优选挤出来形成蜂窝流通式整料。挤出的分子筛基底和蜂窝体及其制造方法是本领域已知的。参见例如美国专利No.5492883，5565394，和5633217和美国专利No.Re.34804。典型地，将该分子筛材料与耐久性粘合剂例如硅酮树脂和临时粘合剂例如甲基纤维素混合，并且将该混合物挤出来形成生坯蜂窝体，然后煅烧和烧结来形成最终的挤出的分子筛基底。
该含银的挤出的分子筛基底可以作为流通式或者滤过式基底来形成。优选该含银的挤出的分子筛基底是流通式基底。
如果形成为流通式基底，那么优选是具有蜂窝结构的流通式整料，其中有许多小的平行的薄壁通道轴向穿过该基底，并且从基底的入口或出口贯穿延伸。基底的通道横截面可以是任何形状，但是优选是正方形、正弦形、三角形、矩形、六边形、梯形、圆形或者椭圆形。
如果形成为滤过式基底，那么该含银的挤出的分子筛基底优选是壁流式整料过滤器。壁流式过滤器的通道是交替封闭的，其允许废气流从入口进入通道，然后流过通道壁，并且从导向出口的不同通道离开过滤器。废气流中的颗粒因此捕集在过滤器中。
在挤出前，该分子筛可以包含银，以使得含银的挤出的分子筛基底是通过挤出程序来生产的。如果该分子筛在挤出前包含银，那么银可以通过任何已知的手段添加到该分子筛中来形成含银的分子筛，添加方式不认为是特别关键的。例如可以通过浸渍、吸附、离子交换、初湿含浸法，沉淀，喷雾干燥等将银化合物(例如硝酸银)添加到该分子筛中。
如果首先形成无银的挤出的分子筛基底，那么将该挤出的分子筛整料然后负载银来生产含银的挤出的分子筛基底。优选将该挤出的分子筛整料进行浸渍程序来将银负载于分子筛整料上。
优选该含银的挤出的分子筛基底包含1-700g/ft3银，更优选10-200g/ft3银。
优选通过使用活性涂覆(washcoat)程序将三效催化剂组合物沉积在含银的挤出的分子筛基底上来制备三效催化剂。活性涂覆是本领域公知的。使用活性涂覆程序来制备该三效催化剂的一种代表性方法如下所述。将理解下面的方法可以根据本发明不同的实施方案而变化。
该活性涂覆优选如下来进行：首先将细微分散的三效催化剂粒子在适当的溶剂，优选水中制浆，来形成浆料。该浆料优选包含5-70重量％的固体，更优选10-50重量％的固体。优选将该粒子研磨或者进行另一粉碎方法，来确保在形成浆料之前，基本上全部的固体粒子的粒度都具有小于20微米的平均粒径。另外的组分例如稳定剂或者促进剂也可以作为水溶性或者水分散性化合物或者络合物的混合物引入该浆料中。
然后可以用浆料将该含银的挤出的分子筛基底涂覆一次或多次，以使得在该含银的挤出的分子筛基底上将沉积期望负载量的三效催化剂。
在该含银的挤出的分子筛基底已经用该三效催化剂组合物浆料涂覆之后，优选将该涂覆的基底干燥，然后通过在提高的温度下加热来煅烧以形成三效催化剂。优选该煅烧在400-600℃进行大约1-8小时。
该三效催化剂涂层可以覆盖含银的挤出的分子筛基底的总长度，或者可替代地可以仅仅覆盖该基底总长度的一部分，以使得仅仅形成催化剂涂层的入口区或者出口区。优选该含银的挤出的分子筛基底的整个长度涂覆有该三效催化剂浆料，以使得该三效催化剂的活性涂层覆盖了基底的整个表面。
在一种实施方案中，该钯组分和铑组分位于该三效催化剂的同一层中，以使得它们一起活性涂覆在该含银的挤出的分子筛基底上。在一种分开的实施方案中，该钯组分和铑组分位于不同的层中。优选该第一层包含该钯组分，和该第二层包含铑组分。该第一层优选位于基底上，和该第二层优选沉积在该第一层上。这两层优选使用上述活性涂覆程序来沉积。可替代地，可以作为单个层内的入口区和出口区来将该钯组分和铑组分分区。
本发明还包括内燃机排气系统，其包含该三效催化剂。该排气系统优选包含一种或多种另外的后处理装置，其能够从内燃机废气中除去污染物。
优选该排气系统包含紧耦合催化剂和本发明的三效催化剂。该紧耦合催化剂位于该三效催化剂上游。优选也可以向该系统中添加颗粒过滤器。该颗粒过滤器可以位于紧耦合催化剂下游和三效催化剂上游，或者具体的过滤器可以位于该三效催化剂下游。
紧耦合催化剂是本领域公知的。紧耦合催化剂典型的用于降低发动机启动后，当在三效催化剂处所测量的温度低于大约150-220℃的温度范围时，冷启动过程中的烃排放。紧耦合催化剂位于发动机隔室中，典型地与排气集管相邻和处于引擎罩下面；因此在发动机升温后，它们曝露于刚刚离开发动机的高温废气。
该紧耦合催化剂优选包含基底结构，其涂覆有含有选自Pt、Pd和Rh的至少一种贵金属的耐热无机氧化物的催化剂层。该耐热基底典型的是整料基底，并优选是陶瓷基底或者金属基底。该陶瓷基底可以由任何合适的耐热难熔材料制成，例如氧化铝、二氧化硅、二氧化钛、二氧化铈、氧化锆、氧化镁、沸石、氮化硅、碳化硅、硅酸锆、硅酸镁、铝硅酸盐和金属铝硅酸盐(例如堇青石和锂辉石)，或者其任意两种或更多种的混合物或者混合氧化物。该金属基底可以由任何合适的金属制成，并且特别是耐热金属和金属合金例如钛和不锈钢以及含有铁、镍、铬和/或铝以及其他痕量金属(典型地，稀土金属)的铁酸盐合金。
该基底优选是流通式基底，但是也可以是滤过式基底。该流通式基底优选具有蜂窝结构，其中带有许多小的平行的薄壁通道轴向穿过该基底，并且贯穿基底延伸。如果该基底是滤过式基底，那么优选是壁流式整料过滤器。壁流式过滤器的通道是交替封闭的，其允许废气流从入口进入通道，然后流过通道壁，并且从导向出口的不同通道离开过滤器。废气流中的颗粒因此捕集在过滤器中。
将该紧耦合催化剂的催化剂层典型地作为活性涂层添加到基底，其优选包含一种或多种无机氧化物和一种或多种铂族金属。该无机氧化物最通常包括第2、3、4、5、13和14族元素的氧化物。有用的无机氧化物优选的表面积是10-700m2/g，孔体积是0.1-4mL/g和孔径是大约10-1000埃。该无机氧化物优选是氧化铝、二氧化硅、二氧化钛、氧化锆、氧化铌、氧化钼、稀土氧化物(特别是二氧化铈、氧化镧或者氧化钕)，或者其任意两种或更多种的混合氧化物或者复合氧化物，例如二氧化硅-氧化铝、二氧化铈-氧化锆或者氧化铝-二氧化铈-氧化锆，并且也可以是沸石。PGM包含铂、钯和铑中的一种或多种。该紧耦合催化剂也可以包含其他金属或者金属氧化物。
在另一有用的实施方案中，该排气系统也可以优选包含常规氧化催化剂组分和本发明的三效催化剂。在这种构造中，该排气系统将优选包含阀或者其他导气机构，以使得冷启动期期间(低于大约150-220℃范围的温度，在该三效催化剂处测量)，废气在流到该常规氧化催化剂组分之前，被引导来与该三效催化剂接触。一旦后处理装置达到了运行温度(大约150-220℃，在该三效催化剂处测量)，再引导该废气流与该常规氧化催化剂组分接触，然后与该三效催化剂接触。也可以向旁路系统添加颗粒过滤器。美国专利No.5656244，其教导在此引入作为参考，例如教导了在冷启动和正常运行条件过程中用于控制废气流动的机构。
下面的实施例仅仅说明本发明。本领域技术人员将认可许多变化处于本发明的主旨和权利要求的范围内。
实施例1：制备本发明的催化剂
催化剂1A：在挤出的β沸石+Pd-Rh层上的Ag
将β沸石整料(300cpsi，10.5密耳厚度，通过将β沸石挤出成蜂窝整料来形成，并且含有55％β沸石；参见例如美国专利No.5492883，5565394和5633217)用硝酸银水溶液浸渍，随后干燥，并通过在500℃加热4小时煅烧来实现Ag负载量是140g/ft3。
然后将该Ag/β沸石整料用Pd-Rh TWC层涂覆，其组成为作为用于Pd的载体的二氧化铈-氧化锆-氧化铝混合氧化物和作为用于Rh载体的二氧化铈-氧化锆混合氧化物。Pd负载量是68g/ft3和Rh负载量是2g/ft3。将该涂覆的基底干燥，然后通过在500℃加热4小时来煅烧。
实施例2：对比催化剂制备
对比催化剂2A：陶瓷基底+Pd-Rh层
根据与催化剂1A相同的程序来制备对比催化剂2A，不同在于使用堇青石基底整料(400cpsi，6.5密耳厚度)代替Ag/β沸石整料。Pd负载量是68g/ft3和Rh负载量是2g/ft3。
对比催化剂2B：陶瓷基底+Pd层和Rh层
将陶瓷整料(900cpsi，2.5密耳厚度)用组成为Pd、二氧化铈-氧化锆-氧化铝混合氧化物和氢氧化钡的第一层进行涂覆。将该涂覆的基底干燥，并且在500℃加热4小时来煅烧。然后将组成为Rh、二氧化铈-氧化锆混合氧化物和氧化铝的第二层涂覆到该第一层上，随后干燥并在500℃煅烧4小时。Pd负载量是78g/ft3和Rh负载量是2g/ft3。
对比催化剂2C：陶瓷基底+Pd层和Rh层
将陶瓷整料(900cpsi，2.5密耳厚度)用组成为Pd、二氧化铈-氧化锆混合氧化物、氧化铝和氢氧化钡的第一层进行涂覆。将该涂覆的基底干燥，并且在500℃加热4小时来煅烧。然后将组成为Rh、二氧化铈-氧化锆混合氧化物和氧化铝的第二层涂覆到该第一层上，随后干燥和在500℃煅烧4小时。Pd负载量是78g/ft3和Rh负载量是2g/ft3。
实施例3：实验室测试程序及结果
将催化剂1A和对比催化剂2A的芯样品(2.54cmx8.4cm)在流通式条件下在炉子中在水热条件(5％H2O，余量空气)在800℃老化80小时。该芯然后在实验室反应器中，使用供料气流(通过调节单个废气组分的质量流量来制备)测试烃吸附。气体流速保持在21.2Lmin-1，产生30000h-1的气时空速(GHSV＝30000h-1)。
该催化剂在650℃在2250ppm O2、10％CO2、10％H2O和余量氮气的气流中预热，然后冷却到室温。在预处理之后，将该催化剂进行烃(HC)吸附步骤，在其中该催化剂与含HC的气体接触30秒，该气体组成为1500ppm(C1基)烃(17vol％甲苯、24vol％异戊烷和59vol％丙烯)、1000ppm NO、1000ppm CO、2250ppm O2、10％H2O、10％CO2和余量氮气。该HC吸附步骤之后是HC解吸期，在其中该催化剂经历了组成为200ppm(C1基)烃，300ppm O2，10％H2O，10％CO2和余量氮气的解吸气体。
表1显示了在吸附期和氧化期过程中的HC排放结果，以及所除去的总HC。
实施例4：发动机测试程序
系统4A包含处于紧耦合位置的对比催化剂2B和处于地板下位置的下游催化剂1A。对比系统4B包含处于紧耦合位置的对比催化剂2C和处于地板下位置的下游对比催化剂2A。每个系统在3.5L汽油机中在4-模式条件下老化100小时，并且紧耦合催化剂床峰值温度处于1610°F。将该老化的系统然后在3.5L汽油机上评价。表2比较了基于联邦测试程序(FTP)循环，来自于尾气管的NMHC(非甲烷烃)和NOx排放。系统4A显示了降低的NMHC排放和相当的NOx排放。
表1：HC存储能力和氧化结果
*对比例
表2：NMHC和NOx排放结果
系统 NMHC排放(g/英里) NOx排放(g/英里)
4A 0.015±0.001 0.034±0.004
4B* 0.022±0.002 0.028±0.006
*对比例。

Claims (12)

1.一种三效催化剂，其包含：(1)包含钯和二氧化铈-氧化锆-氧化铝混合氧化物或者复合氧化物的钯组分；和(2)包含铑和包含氧化锆的材料的铑组分，其中该钯组分和铑组分涂覆到含银的挤出的分子筛基底上。
2.权利要求1的三效催化剂，其中该钯组分和铑组分位于同一层中。
3.权利要求1的三效催化剂，其中该钯组分和铑组分位于不同的层中。
4.权利要求1的三效催化剂，其中该含氧化锆的材料是二氧化铈-氧化锆混合氧化物或者复合氧化物。
5.权利要求1的三效催化剂，其中该含银的挤出的分子筛基底是流通式基底。
6.权利要求1的三效催化剂，该含银的挤出的分子筛基底是滤过式基底。
7.权利要求1的三效催化剂，其中该含银的挤出的分子筛基底包含具有选自下面的骨架类型的分子筛：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、ZON、MFI、FER、MWW、EUO、CON、BEA、FAU、MOR和EMT。
8.权利要求7的三效催化剂，其中该分子筛选自SAPO-34、SSZ-33、SSZ-13、SSZ-39、β沸石、ZSM-5沸石和Y-沸石。
9.权利要求1的三效催化剂，其中该含银的挤出的分子筛基底包含1-700g/ft3的银。
10.一种内燃机排气系统，其包含权利要求1的三效催化剂。
11.权利要求10的排气系统，其进一步包含：选择性催化还原催化剂系统；颗粒过滤器；选择性催化剂还原过滤器系统；NOx吸附剂催化剂；或者其组合。
12.一种处理内燃机废气的方法，其包括将该废气与权利要求1的三效催化剂接触。
CN201680008746.4A 2015-02-06 2016-02-05 三效催化剂及其在排气系统中的应用 Expired - Fee Related CN107206358B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201562113016P 2015-02-06 2015-02-06
US62/113,016 2015-02-06
PCT/US2016/016679 WO2016127012A1 (en) 2015-02-06 2016-02-05 Three-way catalyst and its use in exhaust systems

Publications (2)

Publication Number Publication Date
CN107206358A true CN107206358A (zh) 2017-09-26
CN107206358B CN107206358B (zh) 2021-03-16

Family

ID=55641851

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201680008746.4A Expired - Fee Related CN107206358B (zh) 2015-02-06 2016-02-05 三效催化剂及其在排气系统中的应用

Country Status (10)

Country Link
US (1) US9656209B2 (zh)
EP (1) EP3253488A1 (zh)
JP (1) JP6700290B2 (zh)
KR (1) KR20170116074A (zh)
CN (1) CN107206358B (zh)
BR (1) BR112017016475B1 (zh)
DE (1) DE102016102028A1 (zh)
GB (2) GB2538130B (zh)
RU (1) RU2693482C2 (zh)
WO (1) WO2016127012A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019109999A1 (zh) * 2017-12-08 2019-06-13 庄信万丰(上海)化工有限公司 用于汽油机废气处理的新型多区twc催化剂

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3045226A1 (de) * 2015-01-19 2016-07-20 Umicore AG & Co. KG Doppelschichtiger Dreiweg-Katalysator mit verbesserter Alterungsstabilität
EP3466535A4 (en) * 2016-05-25 2020-01-22 N.E. Chemcat Corporation THREE-WAY CATALYST FOR GASOLINE ENGINE EXHAUST GAS CLEANING
RU2741425C2 (ru) * 2016-07-13 2021-01-26 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Каталитическая композиция, содержащая цеолит типа con и цеолит типа zsm-5, получение и способ применения указанной композиции
GB2553339A (en) 2016-09-02 2018-03-07 Johnson Matthey Plc Improved NOx trap
CN107824185B (zh) * 2016-09-15 2021-03-26 丰田自动车株式会社 排气净化催化剂及其制造方法
EP3579970B1 (en) * 2017-02-08 2022-04-06 BASF Corporation Catalytic article
CN110785232B (zh) * 2017-04-28 2022-09-23 优美科触媒日本有限公司 废气净化用催化剂及使用其的废气净化方法
WO2019055040A1 (en) * 2017-09-18 2019-03-21 Ford Global Technologies, Llc CATALYST FOR CONTROLLING THE EMISSIONS OF MOTOR VEHICLES
JP7177143B2 (ja) 2017-09-27 2022-11-22 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 排気ガス浄化用途のための低ウォッシュコート充填量単層触媒
CN109701619B (zh) * 2017-10-26 2021-10-01 中国石油化工股份有限公司 Ssz-13/ssz-39复合结构分子筛及其合成方法
JP2021505367A (ja) 2017-12-08 2021-02-18 ジョンソン マッセイ （シャンハイ） ケミカルズ リミテッド ガソリン排ガス用途における新規３ゾーン２層ｔｗｃ触媒
US20190353067A1 (en) 2018-05-18 2019-11-21 Umicore Ag & Co. Kg Exhaust treatment systems and methods involving oxygen supplementation and hydrocarbon trapping
US10781735B2 (en) 2018-05-18 2020-09-22 Umicore Ag & Co Kg Exhaust emission reduction system having an HC-trap and NOx-trap combination designed for operating under strategic lean conditions
GB2577372B (en) * 2018-07-27 2023-03-29 Johnson Matthey Plc Improved TWC catalsts containing high dopant support
US20200102868A1 (en) 2018-09-28 2020-04-02 Johnson Matthey Public Limited Company Novel twc catalysts for gasoline exhaust gas applications
CN111001434B (zh) * 2018-10-08 2021-03-16 中自环保科技股份有限公司 一种当量燃烧天然气车集成催化剂体系及其制备方法
CN110052150A (zh) * 2019-05-20 2019-07-26 宁夏英力特化工股份有限公司 单塔双循环烟气脱硫aft塔浆液密度或ph值测定排浆收集方法及装置
US11788450B2 (en) * 2020-10-30 2023-10-17 Johnson Matthey Public Limited Company TWC catalysts for gasoline engine exhaust gas treatments

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1803263A (zh) * 2005-12-17 2006-07-19 王六杞 净化汽车尾气三效催化剂及制备方法
CN1919457A (zh) * 2006-09-13 2007-02-28 胡琳 一种以天然沸石为主要原料的蜂窝状催化剂载体的制作工艺
CN101370566A (zh) * 2005-12-01 2009-02-18 Basf催化剂有限责任公司 用于小烯烃分子的水热稳定的银-沸石阱
CN101479023A (zh) * 2006-06-29 2009-07-08 乌米科雷股份两合公司 三元催化剂
CN101585004A (zh) * 2008-05-20 2009-11-25 揖斐电株式会社 蜂窝结构体
JP2011116627A (ja) * 2009-11-05 2011-06-16 Ngk Insulators Ltd ゼオライト構造体及びその製造方法
CN102811797A (zh) * 2010-02-01 2012-12-05 约翰逊马西有限公司 挤出的scr过滤器

Family Cites Families (62)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US34804A (en) 1862-03-25 Improvement in harvesters
US4631267A (en) 1985-03-18 1986-12-23 Corning Glass Works Method of producing high-strength high surface area catalyst supports
ATE78717T1 (de) * 1987-10-30 1992-08-15 Degussa Platin-freier dreiweg-katalysator.
US5116800A (en) * 1990-12-11 1992-05-26 Allied-Signal Inc. High durability and exhuast catalyst with low hydrogen sulfide emissions
US5407880A (en) * 1992-11-09 1995-04-18 Nissan Motor Co., Ltd. Catalysts for adsorption of hydrocarbons
US5894068A (en) * 1992-12-14 1999-04-13 Kharas; Karl C. C. Reduction of NOx in the exhaust gases from internal combustion engines containing excess oxygen
JPH07300315A (ja) 1994-04-28 1995-11-14 Nissan Motor Co Ltd 複合体、その複合体を用いた触媒体及びそれらの製造方法
FR2720296B1 (fr) 1994-05-27 1996-07-12 Rhone Poulenc Chimie Composés à base d'alumine, d'oxyde de cérium et d'oxyde de zirconium à réductibilité élevée, leur procédé de préparation et leur utilisation dans la préparation de catalyseurs.
US5633217A (en) 1994-09-12 1997-05-27 Corning Incorporated Method of making a high strength catalyst, catalyst support or adsorber
US5565394A (en) 1994-10-11 1996-10-15 Corning Incorporated Low expansion molecular sieves and method of making same
US5492883A (en) 1994-11-21 1996-02-20 Corning Incorporated Molecular sieve structures using aqueous emulsions
US5772972A (en) 1995-01-09 1998-06-30 Ford Global Technologies, Inc. Catalyst/hydrocarbon trap hybrid system
US5656244A (en) 1995-11-02 1997-08-12 Energy And Environmental Research Corporation System for reducing NOx from mobile source engine exhaust
DE69728341T2 (de) 1996-10-07 2004-12-30 Kabushiki Kaisha Toyota Chuo Kenkyusho Verbundoxid, Verbundoxidträger und Katalysator
JPH10180099A (ja) * 1996-12-20 1998-07-07 Ngk Insulators Ltd 排ガス浄化用触媒及び排ガス浄化システム
US6348430B1 (en) * 1997-06-20 2002-02-19 Degussa Ag Exhaust gas treatment catalyst for internal combustion engines with two catalytically active layers on a carrier structure
GB9713428D0 (en) * 1997-06-26 1997-08-27 Johnson Matthey Plc Improvements in emissions control
US6074973A (en) * 1998-03-20 2000-06-13 Engelhard Corporation Catalyzed hydrocarbon trap material and method of making the same
WO2000024507A1 (fr) 1998-10-28 2000-05-04 Toyota Jidosha Kabushiki Kaisha Agent adsorbant pour hydrocarbure et catalyseur pour la purification de gaz d'echappement
US6294140B1 (en) * 1999-04-23 2001-09-25 Degussa Ag Layered noble metal-containing exhaust gas catalyst and its preparation
US6261989B1 (en) * 1999-05-19 2001-07-17 Daihatsu Motor Co., Ltd. Catalytic converter for cleaning exhaust gas
DK1129764T3 (da) * 2000-03-01 2006-01-23 Umicore Ag & Co Kg Katalysator til rensning af udstödningsgas fra dieselmotorer og fremgangsmåde til dens fremstilling
US6617276B1 (en) 2000-07-21 2003-09-09 Johnson Matthey Public Limited Company Hydrocarbon trap/catalyst for reducing cold-start emissions from internal combustion engines
GB0028240D0 (en) * 2000-11-20 2001-01-03 Johnson Matthey Plc Three-way catalyst composition
US7276212B2 (en) * 2001-10-01 2007-10-02 Engelhard Corporation Exhaust articles for internal combustion engines
US7022646B2 (en) * 2003-01-31 2006-04-04 Engelhard Corporation Layered catalyst composite
US7202194B2 (en) 2003-03-17 2007-04-10 Umicore Ag & Co. Kg Oxygen storage material, process for its preparation and its application in a catalyst
JP4460844B2 (ja) * 2003-04-17 2010-05-12 株式会社アイシーティー 排ガス浄化用触媒および排気ガスの浄化方法
US7875250B2 (en) * 2003-12-11 2011-01-25 Umicore Ag & Co. Kg Exhaust treatment device, and methods of making the same
US7795172B2 (en) * 2004-06-22 2010-09-14 Basf Corporation Layered exhaust treatment catalyst
WO2006030763A1 (ja) 2004-09-16 2006-03-23 Daiichi Kigenso Kagaku Kogyo Co., Ltd. セリウム－ジルコニウム系複合酸化物、その製造方法、それを用いた酸素吸蔵放出材料、排気ガス浄化触媒、及び排気ガス浄化方法
JP5200315B2 (ja) * 2004-12-22 2013-06-05 日産自動車株式会社 排気ガス浄化触媒、及び排気ガス浄化触媒の製造方法
GB0428555D0 (en) 2004-12-30 2005-02-09 Magnesium Elektron Ltd Composite material for automotive catalyst applications and method of manufacturing
WO2007007889A1 (en) * 2005-07-12 2007-01-18 Toyota Jidosha Kabushiki Kaisha Exhaust gas purifying catalyst and process for producing it
JP2007296514A (ja) * 2006-04-07 2007-11-15 Ngk Insulators Ltd 触媒体とその製造方法
US7550124B2 (en) * 2006-08-21 2009-06-23 Basf Catalysts Llc Layered catalyst composite
US7758834B2 (en) * 2006-08-21 2010-07-20 Basf Corporation Layered catalyst composite
US7517510B2 (en) * 2006-08-21 2009-04-14 Basf Catalysts Llc Layered catalyst composite
US20080072578A1 (en) * 2006-09-21 2008-03-27 Kumar Sanath V Treatment Systems and Methods for Internal Combustion Engine Exhaust Streams
JP5100085B2 (ja) * 2006-10-31 2012-12-19 株式会社キャタラー 排ガス浄化用触媒
CN100998941B (zh) * 2007-01-04 2012-09-05 华东理工大学 一种前置催化剂及其制备方法
US8007750B2 (en) * 2007-07-19 2011-08-30 Basf Corporation Multilayered catalyst compositions
US8038951B2 (en) * 2007-08-09 2011-10-18 Basf Corporation Catalyst compositions
DE102007046158B4 (de) * 2007-09-27 2014-02-13 Umicore Ag & Co. Kg Verwendung eines katalytisch aktiven Partikelfilters zur Entfernung von Partikeln aus dem Abgas von mit überwiegend stöchiometrischem Luft/Kraftstoff-Gemisch betriebenen Verbrennungsmotoren
DE502007002874D1 (de) * 2007-09-28 2010-04-01 Umicore Ag & Co Kg Entfernung von Partikeln aus dem Abgas von mit überwiegend stöchiometrischem Luft/Kraftstoff-Gemisch betriebenen Verbrennungsmotoren
BRPI0916334B1 (pt) * 2008-07-31 2019-10-15 Basf Se Catalisador para armazenamento de óxido de nitrogênio, sistema e método de tratamento para uma corrente de gás de escapamento de automóvel, e, método para produzir um catalisador de armazenamento de óxido de nitrogênio
JP5651685B2 (ja) * 2009-05-04 2015-01-14 ビーエーエスエフ コーポレーション 希薄燃焼ガソリンエンジンのためのｔｗｃの改善された希薄ｈｃ変換
WO2010147163A1 (ja) * 2009-06-16 2010-12-23 株式会社 キャタラー 排ガス浄化用触媒、粉末材料、及び排ガス浄化用触媒の製造方法
US8833064B2 (en) * 2009-11-06 2014-09-16 Basf Corporation Small engine layered catalyst article and method of making
US8828343B2 (en) * 2010-03-05 2014-09-09 Basf Corporation Carbon monoxide conversion catalyst
US8950174B2 (en) * 2010-09-02 2015-02-10 Basf Se Catalysts for gasoline lean burn engines with improved NH3-formation activity
US9242242B2 (en) * 2010-09-02 2016-01-26 Basf Se Catalyst for gasoline lean burn engines with improved NO oxidation activity
US8323599B2 (en) * 2010-11-22 2012-12-04 Umicore Ag & Co. Kg Three-way catalyst having an upstream multi-layer catalyst
US8617496B2 (en) * 2011-01-19 2013-12-31 Basf Corporation Three way conversion catalyst with alumina-free rhodium layer
US20120308439A1 (en) 2011-06-01 2012-12-06 Johnson Matthey Public Limited Company Cold start catalyst and its use in exhaust systems
CA2844732A1 (en) * 2011-08-10 2013-02-14 Clean Diesel Technologies, Inc. Palladium solid solution catalyst and methods of making
JP5709005B2 (ja) * 2011-10-26 2015-04-30 トヨタ自動車株式会社 排ガス浄化用触媒及びその製造方法
US20130108530A1 (en) 2011-10-27 2013-05-02 Johnson Matthey Public Limited Company Process for producing ceria-zirconia-alumina composite oxides and applications thereof
GB2503243A (en) * 2012-06-18 2013-12-25 Johnson Matthey Plc Combined particulate filter and hydrocarbon trap
WO2015066312A1 (en) * 2013-10-30 2015-05-07 Johnson Mathew Public Limited Comapny Three-way catalyst comprising a silver-containing extruded zeolite substrate and its use in exhaust systems
JP6662778B2 (ja) * 2013-12-06 2020-03-11 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 コールドスタート触媒、及び排気システム中でのそれの使用
US9579604B2 (en) * 2014-06-06 2017-02-28 Clean Diesel Technologies, Inc. Base metal activated rhodium coatings for catalysts in three-way catalyst (TWC) applications

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101370566A (zh) * 2005-12-01 2009-02-18 Basf催化剂有限责任公司 用于小烯烃分子的水热稳定的银-沸石阱
CN1803263A (zh) * 2005-12-17 2006-07-19 王六杞 净化汽车尾气三效催化剂及制备方法
CN101479023A (zh) * 2006-06-29 2009-07-08 乌米科雷股份两合公司 三元催化剂
CN1919457A (zh) * 2006-09-13 2007-02-28 胡琳 一种以天然沸石为主要原料的蜂窝状催化剂载体的制作工艺
CN101585004A (zh) * 2008-05-20 2009-11-25 揖斐电株式会社 蜂窝结构体
JP2011116627A (ja) * 2009-11-05 2011-06-16 Ngk Insulators Ltd ゼオライト構造体及びその製造方法
CN102811797A (zh) * 2010-02-01 2012-12-05 约翰逊马西有限公司 挤出的scr过滤器

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019109999A1 (zh) * 2017-12-08 2019-06-13 庄信万丰(上海)化工有限公司 用于汽油机废气处理的新型多区twc催化剂
US11439987B2 (en) 2017-12-08 2022-09-13 Johonson Matthey (Shanghai) Chemicals Co., Ltd Multi-region TWC for treatment of exhaust gas from gasoline engine

Also Published As

Publication number Publication date
US20160228818A1 (en) 2016-08-11
WO2016127012A1 (en) 2016-08-11
BR112017016475B1 (pt) 2022-04-12
RU2017131232A (ru) 2019-03-06
GB2538130A (en) 2016-11-09
EP3253488A1 (en) 2017-12-13
JP2018505778A (ja) 2018-03-01
GB2549039A (en) 2017-10-04
JP6700290B2 (ja) 2020-05-27
US9656209B2 (en) 2017-05-23
GB201602073D0 (en) 2016-03-23
DE102016102028A1 (de) 2016-08-11
KR20170116074A (ko) 2017-10-18
GB2549039B (en) 2018-09-05
RU2017131232A3 (zh) 2019-03-20
GB201711197D0 (en) 2017-08-23
CN107206358B (zh) 2021-03-16
GB2538130B (en) 2017-08-23
BR112017016475A2 (pt) 2018-04-10
RU2693482C2 (ru) 2019-07-03

Similar Documents

Publication Publication Date Title
CN107206358A (zh) 三效催化剂及其在排气系统中的应用
JP7179697B2 (ja) 貴金属及び小細孔モレキュラーシーブを含む受動的ＮＯｘアドソーバ
CN105813745B (zh) 包含两种不同贵金属-分子筛催化剂的废气催化剂
EP3485964B1 (en) Cold start catalyst and its use in exhaust systems
CN107250497B (zh) 被动NOx吸附剂
US20170001169A1 (en) PASSIVE NOx ADSORBER
CN107427777A (zh) 包含贵金属和具有OFF骨架类型的分子筛的被动NOx吸附剂
CN105682792B (zh) 包含含银挤出沸石基材的三元催化剂及其在排气系统中的用途

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210316