CN109184860B - 用于净化来自内燃机的废气的方法和系统 - Google Patents

用于净化来自内燃机的废气的方法和系统 Download PDF

Info

Publication number
CN109184860B
CN109184860B CN201810945803.2A CN201810945803A CN109184860B CN 109184860 B CN109184860 B CN 109184860B CN 201810945803 A CN201810945803 A CN 201810945803A CN 109184860 B CN109184860 B CN 109184860B
Authority
CN
China
Prior art keywords
ssz
maintained
filter
exhaust gas
catalyst
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.)
Active
Application number
CN201810945803.2A
Other languages
English (en)
Other versions
CN109184860A (zh
Inventor
M.M.马林
C.F.马蒂
A.E.P.吉梅诺
A.C.卡诺斯
P.N.R.文内斯特罗姆
玛丽·格里尔
A.库斯托夫
J.R.托格森
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.)
Umicore Co ltd
Original Assignee
Umicore Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=46001293&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN109184860(B) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Umicore Co ltd filed Critical Umicore Co ltd
Priority to CN201810945803.2A priority Critical patent/CN109184860B/zh
Publication of CN109184860A publication Critical patent/CN109184860A/zh
Application granted granted Critical
Publication of CN109184860B publication Critical patent/CN109184860B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • 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
    • B01J29/76—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—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
    • 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
    • B01J37/0246—Coatings comprising a zeolite
    • 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
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/001—Gas flow channels or gas chambers being at least partly formed in the structural parts of the engine or machine
    • 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
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/008—Mounting or arrangement of exhaust sensors in or on exhaust apparatus
    • 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
    • F01N3/10—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
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—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
    • B01D2255/915—Catalyst supported on particulate filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9431—Processes characterised by a specific device
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • F01N2330/06—Ceramic, e.g. monoliths
    • 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
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • 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
    • F01N3/023—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 using means for regenerating the filters, e.g. by burning trapped particles
    • 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
    • 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
    • Y02T10/40—Engine management systems

Landscapes

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

Abstract

本发明涉及用于净化来自内燃机的废气的方法和系统。本发明提供了用于纯化来自内燃机的废气的系统和方法，其包括过滤器和SCR催化剂。过滤器周期性地再生，增加废气的温度至850℃以及水蒸气含量至100％体积。SCR催化剂包括具有AEI类型骨架和由铜助催化的水热微孔稳定的沸石和/或类沸石。

Description

用于净化来自内燃机的废气的方法和系统
本申请是申请日为2012年4月27日，申请号为201280072731.6，发明名称为“用于净化来自内燃机的废气的方法和系统”的发明专利申请的分案申请。
本发明涉及在去除或减少有害的化合物方面对来自内燃机的废气的后处理。更具体是，本发明集中在对来自稀燃烧内燃机(并且尤其是柴油发动机) 的发动机废气中颗粒物质的去除和氮氧化物的还原。
稀燃烧发动机公知是能量有效的，但具有形成颗粒物质和氮氧化物的缺点，这些必须在发动机废气中除去或至少减少。
为了防止环境污染以及满足一些政府需求，现代柴油机设有废气净化系统，其包括串联的用于挥发性有机化合物去除的氧化催化剂，用于颗粒物质的去除的颗粒过滤器以及在氮氧化物(NOx)的选择性还原中有活性的催化剂。
还公知的是将SCR催化剂集成到颗粒过滤器。
废气中的NOx的选择性催化还原通常通过与原样或作为其前体导入的氨起反应而实现，氨喷入SCR催化剂的废气上游，用于将主要为二氧化氮和一氧化二氮的氮氧化物(NOx)选择性还原为氮。
为此，在文献中公开了许多催化剂组合物。
近来，用铜或铁助催化的沸石引起了很大的关注，尤其是在汽车应用中使用。
包含用于NH3-SCR应用的沸石催化剂的铜显示在低温下高的活性。然而，在某些应用中，催化剂可能暴露于废气中很高的温度偏移。此外废气包含来自燃烧发动机的高浓度的水蒸汽，这可以降低沸石催化剂性能。水热稳定性对于铜基沸石催化剂通常是个问题，一种可能的催化剂失活机理为由对于水-热条件的不稳定性造成的沸石骨架降解，其由铜的存在而进一步增强。
在NH3-SCR应用中含铜沸石催化剂的失活典型地由因为对于水-热条件的不稳定性造成的沸石骨架降解所引起，这由铜的存在而进一步增强。然而，稳定性对其中催化剂将经历含水废气流中的高温度偏差的汽车应用尤其重要。
催化剂的失活在配备有颗粒过滤器的废气净化系统中尤其是个问题，为了防止载有烟灰的过滤器上的压力积累，其必须周期性地活性再生。
活性再生通过燃烧捕集的烟灰而执行。再生可以通过将燃料喷射进入氧化催化剂上游的废气或通过颗粒过滤器的电加热而开始。
在活性再生期间，取决于过滤器中捕集的烟灰的量，在10至15分钟的时间期间在过滤器出口的废气温度可以达到850℃以上并且水蒸汽的含量为15％以上，最多100％。
本发明的总体目标是提供一种用于除去稀燃内燃机的有害的化合物，例如通过颗粒过滤器去除颗粒物质以及通过与催化剂接触的氮氧化物选择性催化还原而去除氮氧化物，所述催化剂当在颗粒过滤器的活性再生期间暴露于高温和水蒸气浓度时为水热稳定的。
我们已经发现本发明的目标可以通过使用具有水热稳定的AEI类型骨架的沸石或类沸石实现，其中在水热老化条件下即使当铜在沸石或类沸石中存在时，该结构得以保持。
按照上述发现，本发明提供一种用于净化来自内燃机的废气的方法，其包括
通过使气体经过颗粒过滤器降低废气中烟灰的含量；
随后在氨或其前体存在下通过与在NH3-SCR中有活性的催化剂接触，降低氮氧化物的含量；
通过燃烧过滤器中捕集的烟灰并且由此将废气的温度增加至850℃并且将水蒸气含量增加至100％体积，周期性地再生过滤器；以及
在再生过滤器期间使来自过滤器的废气通过催化剂，其中催化剂包括具有 AEI类型骨架并且骨架中结合了铜的水热稳定的沸石和/或类沸石。
“水热稳定”是指沸石和类沸石催化剂能够在暴露于至少600℃的温度和 100％体积的水蒸气含量经13小时后，保持初始表面积的80至90％以及微孔体积的80至90％，并且在暴露于至少750℃的温度和100％体积的水蒸气含量经 13小时后，保持初始表面积和微孔体积的至少30至40％。
优选地，具有AEI类型骨架的水热稳定沸石或类沸石的硅与铝原子比率对于沸石为5-50，或对于类沸石为0.02-0.5。
本发明中使用的最优选的沸石或类沸石催化剂是沸石SSZ-39和类沸石 SAPO-18，两者都具有“AEI”骨架结构，其中通过浸渍、液体离子交换或固体离子交换而引入铜。
原子铜与铝的比率对于沸石优选为约0.01-约1。对于类沸石，优选的原子铜与硅的比率相应为0.01-约1。
通过本发明中采用的上述催化剂，在750度老化后，与对于Cu-CHA催化剂的20％相比，维持在250℃下初始NOx还原的80％。
因此，在本发明的实施方案中，在催化剂已经暴露在750℃的温度和废气中100％的水蒸气含量经13小时后，维持在250℃下氮氧化物初始还原的80％。
本发明另外提供了一种废气净化系统，其包括活性可再生颗粒过滤器和 SCR催化剂，所述催化剂包括具有AEI类型骨架和用铜助催化的水热多微孔稳定的沸石和/或类沸石。
在根据本发明的废气净化系统的一个实施方案中，SCR催化剂集成到颗粒过滤器中。
在另一实施方案中，对于沸石，原子铜与铝的比率为约0.01-约1，对于类沸石，原子铜与硅的比率为0.01-约1。
在又一实施方案中，沸石SCR催化剂中硅与铝的原子比率对于沸石为 5-50，对于类沸石为0.02-0.5。
在另一实施方案中，在催化剂已经暴露在750℃的温度和废气中100％的水蒸气含量经13小时后，SCR催化剂保持在250℃下氮氧化物初始还原的80％。
在另一实施方案中，SCR催化剂在600℃老化后保持初始微孔率的80％至 90％，以及在750℃老化后保持初始微孔率的30至40％。
在又一实施方案中，SCR催化剂是硅酸铝沸石SSZ-39和/或磷酸硅铝 SAPO-18。
在上述实施方案中，SCR催化剂可以沉积在整体式担载结构上。
当用类似的Si/Al比率比较时，Cu-SSZ-39催化剂系统显示与典型的“技术发展水平”的Cu-SSZ-13相比改进的性能。
实施例1：Cu-SSZ-39催化剂制备
具有骨架类型代码AEI的沸石SSZ-39以与美国专利5.958.370给出的使用 1，1，3，5-四甲基哌啶鎓作为有机模板类似的方式来合成。凝胶具有以下组成：30 Si：1.0 Al：0.51NaOH：5.1 OSDA：600H2O，在135℃压热7天，将产物过滤，用水清洗，在空气中干燥和煅烧。最终的SSZ-39由ICP-AES测量具有Si/Al＝9.1。
为了获得Cu-SSZ-39，煅烧的沸石用Cu(CH3COO)2离子交换，以获得在煅烧后具有Cu/Al＝0.52的最终催化剂。
煅烧后Cu-SSZ-39的粉末X射线衍射(PXRD)图案在图1A中示出。
实施例2：催化剂测试
在固定床反应器中测试用于NOx的选择性催化再生的样品的活性，使用 300mL/min的总流率模拟发动机废气流，其由N2中500ppm NO、533ppm NH3、 7％O2，5％H2O组成，在其中测试40毫克催化剂。
来自反应器的出口气体中存在的NOx被连续分析，并且转化率在图2示出。
实施例3：水热耐久性测试
为了测试沸石的水热稳定性，对样品进行蒸汽处理。它们在常规烤箱中在 13小时期间暴露于600或750℃的水进料(2.2mL/min)，然后类似于实施例2 进行测试。
催化剂结果也可以在图2中看到。取决于在水热处理期间使用的温度，经受水热处理的样品已经用600或700℃标记。
还对全部处理的样品执行另外的表征。水热处理后的PXRD图案如图1A 所示，并且处理的样本的BET表面积，微孔面积和微孔体积在以下表1中进行了总结。
实施例4：利用Cu-CHA(Cu-SSZ-13)的比较实施例
Cu-CHA沸石由具有以下摩尔组成的凝胶制备：SiO2：0.033 Al2O3：0.50 OSDA：0.50HF：3H2O，其中OSDA是N，N，N-三甲基-1-金刚烷氢氧化铵。
凝胶在翻滚状态下在150℃热压3天，在冲洗、干燥和煅烧后给出具有 Si/Al＝12.7的最终沸石产物。
为了获得Cu-CHA，煅烧的沸石与Cu(CH3COO)2离子交换以获得具有 Cu/Al＝0.54的最终催化剂。
煅烧后的Cu-CHA的粉末X射线衍射(PXRD)图案在图1B中示出。
该催化剂还根据实施例2测试，并且类似实施例3进行水热耐久性评估。催化结果在附图的图2中概括。处理的CHA样品的PXRD图案在图1B中示出，并且在表1上总结了构造属性(BET表面积，微孔体积，以及微孔面积)。
表1
Figure BDA0001768923940000051
实施例5：Cu-SAPO-18
具有骨架类型代码AEI的磷酸硅铝SAPO-18根据[J.Chen，J.M.Thomas，P.A.Wright，R.P.Townsend，Catal.Lett.28(1994)[241-248]]合成并且用2重量％的Cu浸渍。最终的Cu-SAPO-18催化剂在750℃下在10％的H2O和10％的O2中水热处理并且在与实施例2给出的相同的条件下测试。结果在附图的图3中示出。

Claims (9)

1.一种用于净化来自内燃机的废气的方法，其包括
通过使所述废气通过过滤器，降低废气中烟灰的含量；
随后在氨或其前驱体存在下与在NH3-SCR中有活性的催化剂接触，降低氮氧化物的含量；
通过燃烧所述过滤器中捕集的烟灰周期性地活性地再生所述过滤器；以及
在再生所述过滤器期间使来自所述过滤器的废气通过所述催化剂，其中所述催化剂包括硅与铝的原子比率在5和50之间的沸石SSZ-39，且其中所述沸石SSZ-39用铜助催化。
2.权利要求1所述的方法，其中沸石SSZ-39中原子铜与铝的比率在0.01和1之间。
3.权利要求1或2所述的方法，其中周期性地活性地再生所述过滤器通过燃烧所述过滤器中捕集的烟灰并且由此将所述废气的温度增加至最高达850℃并且将水蒸气含量增加到最高达100%体积来进行。
4.权利要求1或2所述的方法，其中在所述催化剂已经暴露在750℃的温度和所述废气中100%的水蒸气含量经13小时后，维持在250℃下氮氧化物初始还原的80%。
5.权利要求3所述的方法，其中在所述催化剂已经暴露在750℃的温度和所述废气中100%的水蒸气含量经13小时后，维持在250℃下氮氧化物初始还原的80%。
6.权利要求1或2所述的方法，其中在600℃老化后维持SSZ-39的初始微孔率的80%至90%，并且在750℃老化后维持SSZ-39的初始微孔率的30%至40%。
7.权利要求3所述的方法，其中在600℃老化后维持SSZ-39的初始微孔率的80%至90%，并且在750℃老化后维持SSZ-39的初始微孔率的30%至40%。
8.权利要求4所述的方法，其中在600℃老化后维持SSZ-39的初始微孔率的80%至90%，并且在750℃老化后维持SSZ-39的初始微孔率的30%至40%。
9.权利要求5所述的方法，其中在600℃老化后维持SSZ-39的初始微孔率的80%至90%，并且在750℃老化后维持SSZ-39的初始微孔率的30%至40%。
CN201810945803.2A 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统 Active CN109184860B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810945803.2A CN109184860B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201280072731.6A CN104520548B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统
PCT/EP2012/057795 WO2013159825A1 (en) 2012-04-27 2012-04-27 Method and system for the purification of exhaust gas from an internal combustion engine
CN201810945803.2A CN109184860B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201280072731.6A Division CN104520548B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统

Publications (2)

Publication Number Publication Date
CN109184860A CN109184860A (zh) 2019-01-11
CN109184860B true CN109184860B (zh) 2020-12-22

Family

ID=46001293

Family Applications (5)

Application Number Title Priority Date Filing Date
CN201810946299.8A Active CN109268110B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统
CN201810945803.2A Active CN109184860B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统
CN201810945801.3A Active CN109268109B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统
CN201810945728.XA Pending CN109268108A (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统
CN201280072731.6A Active CN104520548B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201810946299.8A Active CN109268110B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统

Family Applications After (3)

Application Number Title Priority Date Filing Date
CN201810945801.3A Active CN109268109B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统
CN201810945728.XA Pending CN109268108A (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统
CN201280072731.6A Active CN104520548B (zh) 2012-04-27 2012-04-27 用于净化来自内燃机的废气的方法和系统

Country Status (13)

Country Link
US (2) US9561468B2 (zh)
EP (6) EP2995790A1 (zh)
JP (1) JP6290181B2 (zh)
KR (1) KR101915552B1 (zh)
CN (5) CN109268110B (zh)
BR (1) BR112014026909B1 (zh)
CA (1) CA2870745C (zh)
DK (1) DK2850294T4 (zh)
ES (3) ES2744546T3 (zh)
PL (2) PL3425182T3 (zh)
RU (1) RU2623356C2 (zh)
WO (1) WO2013159825A1 (zh)
ZA (1) ZA201406863B (zh)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109268110B (zh) * 2012-04-27 2021-05-07 优美科两合公司 用于净化来自内燃机的废气的方法和系统
RU2675821C2 (ru) * 2013-03-15 2018-12-25 Джонсон Мэтти Паблик Лимитед Компани Катализатор для обработки выхлопных газов
JP6513652B2 (ja) * 2013-10-31 2019-05-15 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Ａｅｉゼオライトの合成
WO2015084834A1 (en) * 2013-12-02 2015-06-11 Johnson Matthey Public Limited Company Synthesis of aei zeolite
CN110540215B (zh) * 2014-11-21 2024-02-06 三菱化学株式会社 Aei型铝硅酸盐沸石、催化剂和废气处理方法
ES2586770B1 (es) 2015-04-16 2017-08-14 Consejo Superior De Investigaciones Científicas (Csic) Método de síntesis directa del material cu-silicoaluminato con la estructura zeolítica aei, y sus aplicaciones catalíticas
ES2586775B1 (es) 2015-04-16 2017-08-14 Consejo Superior De Investigaciones Científicas (Csic) Método de preparación de la estructura zeolítica aei en su forma silicoaluminato con grandes rendimientos, y su aplicación en catálisis
ES2589059B1 (es) 2015-05-05 2017-08-17 Consejo Superior De Investigaciones Cientificas SÍNTESIS DIRECTA DE Cu-CHA MEDIANTE LA COMBINACIÓN DE UN COMPLEJO DE Cu Y TETRAETILAMONIO, Y APLICACIONES EN CATÁLISIS
CN108349742A (zh) 2015-11-27 2018-07-31 三菱化学株式会社 八元氧环沸石和aei型沸石的制造方法
KR20180111907A (ko) * 2016-02-01 2018-10-11 우미코레 아게 운트 코 카게 알칼리 금속을 본질적으로 함유하지 않는 Fe-AEI 제올라이트 재료를 포함하는 SCR 촉매의 존재하에 선택적 촉매 환원에 의해 배기 가스로부터 질소 산화물을 제거하는 방법
KR101846918B1 (ko) 2016-11-16 2018-04-09 현대자동차 주식회사 Cu/LTA 촉매 및 이를 포함하는 배기 시스템, 그리고 Cu/LTA 촉매 제조 방법
CN106925341A (zh) * 2017-02-23 2017-07-07 华中科技大学 一种助剂掺杂的Cu‑SSZ‑39催化剂的制备方法及其应用
WO2018168787A1 (ja) 2017-03-13 2018-09-20 三菱ケミカル株式会社 遷移金属担持ゼオライト及びその製造方法、並びに窒素酸化物浄化用触媒及びその使用方法
JP2018159334A (ja) * 2017-03-23 2018-10-11 日本碍子株式会社 排ガス浄化装置
CN107376989B (zh) * 2017-07-21 2021-01-05 中触媒新材料股份有限公司 一种Cu-AEI分子筛催化剂合成及应用
CN112955244A (zh) * 2018-11-02 2021-06-11 巴斯夫公司 用于贫燃发动机的排放物处理系统
KR20210087743A (ko) * 2020-01-03 2021-07-13 현대자동차주식회사 촉매 및 촉매의 제조 방법
KR20220060315A (ko) * 2020-11-04 2022-05-11 현대자동차주식회사 Scr 촉매의 제조 방법 및 이에 의하여 제조된 scr 촉매
CN114950576B (zh) * 2022-06-20 2023-08-22 济南大学 一种提高金属基小孔分子筛水热稳定性的方法及所得产品和应用
DE102022130469A1 (de) 2022-11-17 2024-05-23 Umicore Ag & Co. Kg Verfahren und Vorrichtung zum Herstellen eines Substrats für eine Abgasnachbehandlungseinrichtung

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101668589A (zh) * 2007-02-27 2010-03-10 巴斯福催化剂公司 铜cha沸石催化剂
CN101730575A (zh) * 2007-04-26 2010-06-09 约翰逊马西有限公司 过渡金属/沸石scr催化剂
CN102065997A (zh) * 2008-06-19 2011-05-18 尤米科尔股份公司及两合公司 用于具有柴油机的载重车的氧化催化剂
CN102123946A (zh) * 2008-08-19 2011-07-13 东曹株式会社 高耐热性β型沸石和使用其的SCR催化剂
CN102387851A (zh) * 2009-04-03 2012-03-21 巴斯夫公司 具有氨生成和scr催化剂的排气处理系统
CN102380412A (zh) * 2011-09-06 2012-03-21 太原理工大学 负载过渡元素mfi催化剂的制备方法及其mfi催化剂应用

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2075603C1 (ru) * 1994-07-05 1997-03-20 Владимир Алексеевич Васин Регенерируемый сажевый фильтр выхлопных газов
US5958370A (en) 1997-12-11 1999-09-28 Chevron U.S.A. Inc. Zeolite SSZ-39
US6818198B2 (en) 2002-09-23 2004-11-16 Kellogg Brown & Root, Inc. Hydrogen enrichment scheme for autothermal reforming
RU2362613C2 (ru) * 2003-04-17 2009-07-27 Джонсон Мэттей Паблик Лимитед Компани Выхлопная система для двигателей внутреннего сгорания, двигатель внутреннего сгорания и транспортное средство на его основе
US7229597B2 (en) † 2003-08-05 2007-06-12 Basfd Catalysts Llc Catalyzed SCR filter and emission treatment system
RU2008128363A (ru) * 2005-12-14 2010-01-20 Басф Каталистс Ллк (Us) ЦЕОЛИТНЫЙ КАТАЛИЗАТОР С УЛУЧШЕННЫМ ВОССТАНОВЛЕНИЕМ NOх В SCR
MY179762A (en) * 2007-03-26 2020-11-12 Pq Corp Novel microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same
US7966812B2 (en) * 2007-08-29 2011-06-28 Ford Global Technologies, Llc Multi-stage regeneration of particulate filter
US20090196812A1 (en) * 2008-01-31 2009-08-06 Basf Catalysts Llc Catalysts, Systems and Methods Utilizing Non-Zeolitic Metal-Containing Molecular Sieves Having the CHA Crystal Structure
US8080209B2 (en) * 2008-02-25 2011-12-20 Jgc Catalysts And Chemicals Ltd. Exhaust gas treatment apparatus
JP2009255051A (ja) * 2008-03-21 2009-11-05 Panasonic Corp 排ガス浄化装置
EP2112341B1 (en) * 2008-04-22 2018-07-11 Umicore AG & Co. KG Method for purification of an exhaust gas from a diesel engine
CN101678348B (zh) * 2008-05-20 2012-07-18 揖斐电株式会社 蜂窝结构体
JP2010000499A (ja) * 2008-05-20 2010-01-07 Ibiden Co Ltd ハニカム構造体
US8245500B2 (en) * 2008-07-07 2012-08-21 Delphi Technologies, Inc. Dual catalyst NOx reduction system for exhaust from lean burn internal combustion engines
JP4767296B2 (ja) * 2008-07-31 2011-09-07 本田技研工業株式会社 ＮＯｘ浄化触媒
DE102008049098A1 (de) * 2008-09-26 2009-06-25 Daimler Ag Verfahren zum Betreiben einer Abgasreinigungsanlage mit einem SCR-Katalysator und einem vorgeschalteten oxidationskatalytisch wirksamen Abgasreinigungsbauteil
CN102325580B (zh) * 2008-12-24 2016-04-13 巴斯夫公司 具有催化scr过滤器和下游scr催化剂的排气处理系统及方法
JP5730584B2 (ja) * 2009-01-22 2015-06-10 三菱樹脂株式会社 窒素酸化物浄化用触媒及びその製造方法
CN105749747A (zh) * 2009-04-17 2016-07-13 约翰逊马西有限公司 小孔分子筛负载铜催化剂
JP6023395B2 (ja) * 2009-10-06 2016-11-09 日本碍子株式会社 触媒担持フィルタ
JP2011098336A (ja) * 2009-10-09 2011-05-19 Ibiden Co Ltd ハニカムフィルタ
KR101294098B1 (ko) * 2010-03-11 2013-08-08 존슨 맛쎄이 퍼블릭 리미티드 컴파니 ＮＯｘ의 선택적 촉매 환원을 위한 무질서 분자체 지지체
JP5573453B2 (ja) * 2010-07-21 2014-08-20 三菱樹脂株式会社 窒素酸化物浄化用触媒及びその製造方法
US20110165040A1 (en) * 2010-11-03 2011-07-07 Ford Global Technologies, Llc Device for remediating emissions and method of manufacture
RU2597090C2 (ru) * 2011-05-31 2016-09-10 Джонсон Мэтти Паблик Лимитед Компани Каталитический фильтр с двойной функцией
CN109268110B (zh) * 2012-04-27 2021-05-07 优美科两合公司 用于净化来自内燃机的废气的方法和系统
RU2675821C2 (ru) * 2013-03-15 2018-12-25 Джонсон Мэтти Паблик Лимитед Компани Катализатор для обработки выхлопных газов
WO2016073329A1 (en) * 2014-11-03 2016-05-12 California Institute Of Technology Producing zeolite ssz-39 using isomeric mixtures of organic structure directing agents

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101668589A (zh) * 2007-02-27 2010-03-10 巴斯福催化剂公司 铜cha沸石催化剂
CN101730575A (zh) * 2007-04-26 2010-06-09 约翰逊马西有限公司 过渡金属/沸石scr催化剂
CN102065997A (zh) * 2008-06-19 2011-05-18 尤米科尔股份公司及两合公司 用于具有柴油机的载重车的氧化催化剂
CN102123946A (zh) * 2008-08-19 2011-07-13 东曹株式会社 高耐热性β型沸石和使用其的SCR催化剂
CN102387851A (zh) * 2009-04-03 2012-03-21 巴斯夫公司 具有氨生成和scr催化剂的排气处理系统
CN102380412A (zh) * 2011-09-06 2012-03-21 太原理工大学 负载过渡元素mfi催化剂的制备方法及其mfi催化剂应用

Also Published As

Publication number Publication date
ZA201406863B (en) 2018-05-30
CN109268110B (zh) 2021-05-07
EP3165733B1 (en) 2018-09-05
CN104520548A (zh) 2015-04-15
US9561468B2 (en) 2017-02-07
CN109268109A (zh) 2019-01-25
RU2014147605A (ru) 2016-06-20
DK2850294T3 (en) 2017-08-28
CN109184860A (zh) 2019-01-11
PL3369897T3 (pl) 2019-10-31
EP3425181A1 (en) 2019-01-09
ES2730559T3 (es) 2019-11-11
KR20150003746A (ko) 2015-01-09
JP2015516882A (ja) 2015-06-18
EP3369897A1 (en) 2018-09-05
CN109268109B (zh) 2021-10-29
JP6290181B2 (ja) 2018-03-07
CN109268108A (zh) 2019-01-25
EP3425181B1 (en) 2019-10-30
RU2623356C2 (ru) 2017-06-23
EP3369897B1 (en) 2019-04-03
EP3425182B1 (en) 2019-06-19
BR112014026909A2 (pt) 2017-06-27
CN104520548B (zh) 2018-09-07
CA2870745C (en) 2019-07-09
EP2850294B2 (en) 2019-09-11
ES2633320T5 (es) 2020-05-20
EP2995790A1 (en) 2016-03-16
KR101915552B1 (ko) 2018-11-06
ES2633320T3 (es) 2017-09-20
EP3165733A1 (en) 2017-05-10
EP2850294B1 (en) 2017-06-07
PL3425182T3 (pl) 2020-03-31
US20150118134A1 (en) 2015-04-30
US9855528B2 (en) 2018-01-02
EP3425182A1 (en) 2019-01-09
EP2850294A1 (en) 2015-03-25
BR112014026909B1 (pt) 2021-06-29
US20160354724A1 (en) 2016-12-08
ES2744546T3 (es) 2020-02-25
DK2850294T4 (da) 2019-12-16
CA2870745A1 (en) 2013-10-31
WO2013159825A1 (en) 2013-10-31
CN109268110A (zh) 2019-01-25

Similar Documents

Publication Publication Date Title
CN109184860B (zh) 用于净化来自内燃机的废气的方法和系统
EP2308596B1 (en) Cu/zeolite SCR catalyst for NOx reduction in exhaust gases and manufacture method thereof
KR20120006053A (ko) 질소 산화물의 환원에 대한 희박/농후 노화에 대해 내구적인 소기공 분자 체 지지된 구리 촉매
CN109529924B (zh) 一种doc分子筛催化剂及其制备和催化氧化柴油车尾气的用途
JP7322206B2 (ja) Ｓｃｒ活性コーティングを有する触媒

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