WO2020256326A1 - Nox-adsorbing ruthenium-containing silicoaluminate - Google Patents

Nox-adsorbing ruthenium-containing silicoaluminate Download PDF

Info

Publication number
WO2020256326A1
WO2020256326A1 PCT/KR2020/007430 KR2020007430W WO2020256326A1 WO 2020256326 A1 WO2020256326 A1 WO 2020256326A1 KR 2020007430 W KR2020007430 W KR 2020007430W WO 2020256326 A1 WO2020256326 A1 WO 2020256326A1
Authority
WO
WIPO (PCT)
Prior art keywords
nox
catalyst
molecular sieve
cha
cold start
Prior art date
Application number
PCT/KR2020/007430
Other languages
French (fr)
Korean (ko)
Inventor
라오 코마테디나라야나
전준홍
김은석
Original Assignee
희성촉매 주식회사
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 희성촉매 주식회사 filed Critical 희성촉매 주식회사
Publication of WO2020256326A1 publication Critical patent/WO2020256326A1/en

Links

Images

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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/9404—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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • 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
    • F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction 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
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—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
    • B01D2255/91—NOx-storage component incorporated in the catalyst
    • 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
    • B01D2257/402—Dinitrogen oxide
    • 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
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to an internal combustion engine exhaust system comprising a NOx adsorptive ruthenium-containing silicoaluminate, more specifically a ruthenium-containing CHA and/or FER NOx adsorption material, a cold start catalyst comprising such a NOx adsorption material, and a cold start catalyst. It is about.
  • NOx storage and release catalysts for cold start control under lean burn conditions are intensively studied and known. These catalysts adsorb NOx in the cold start section and thermally desorb NOx at higher exhaust temperatures (abbreviated as NSC or NAC). The desorbed NOx is reduced to nitrogen by selective catalytic reduction (SCR) or NOx adsorbent (NSR) disposed downstream.
  • SCR selective catalytic reduction
  • NSR NOx adsorbent
  • Representative low temperature NOx adsorbing materials consist of inorganic oxides such as alumina, silica, ceria, zirconia, titania or mixed oxides coated with at least one platinum group metal.
  • NOx trapping materials of Pd-Fe/Zeolite are known.
  • a passive NOx adsorption catalyst comprising a first noble metal and a molecular sieve having an LTL framework type
  • the first noble metal is palladium, platinum, rhodium, gold, silver, iridium, ruthenium, osmium, or a mixture thereof
  • It further comprises a second molecular sieve catalyst, wherein the second molecular sieve catalyst comprises a second noble metal and a second molecular sieve, wherein the second molecular sieve does not have an LTL framework type, in particular CHA (Carbazai The catalyst for passive NOx adsorption is known.
  • CHA Carbazai
  • the known system does not have sufficient NOx adsorption capacity in the cold start section, and a palladium component is essential as an expensive platinum group component.
  • the present invention discloses a NOx adsorption material effective in adsorbing NOx in a cold start section and releasing the adsorbed NOx at a temperature higher than the cold start section.
  • the NOx adsorption materials of the present invention include Ru and CHA or FER molecular sieves.
  • the invention also includes an exhaust system comprising a NOx adsorbing material, and a method of using the same to treat exhaust gas of an internal combustion engine.
  • the cold start catalyst material according to the present invention is effective in adsorbing NOx in the cold start section and converting and discharging the adsorbed NOx at a higher temperature than the cold start section.
  • DRIFTS pretreatment conditions RT to 400C in Air+N2, 5min @ 400C in H2/N2, ramp-down to 200C in N2+Air, Adsorption @ 100C for 20min (NOx and Air), Ramp-up to 450C in Air+N2 .
  • the molecular sieve is preferably a small pore molecular sieve having a maximum ring size of 8 tetrahedral atoms, a mesoporous molecular sieve having a maximum ring size of 10 tetrahedral atoms or a large pore having a maximum ring size of 12 tetrahedral atoms It is a molecular sieve. More preferably, the molecular sieve has a framework structure of SSZ-13, LTA, AEI, SAPO-34, FU-9, ZSM, FER, BEA, CHA, or a mixture thereof, more preferably FER or CHA structure Have.
  • the NOx adsorption material can be prepared by any known means.
  • ruthenium can be added to the molecular sieve by any known means to form the NOx adsorbing material, and the mode of addition is not considered particularly important.
  • ruthenium compounds eg ruthenium chloride, ruthenium nitrate
  • ruthenium compounds can be supported on molecular sieves by impregnation, adsorption, ion-exchange, initial infiltration, precipitation, spray drying, and the like.
  • ruthenium can be added during the synthesis of the molecular sieve.
  • Other metals may additionally be added to the NOx adsorbent.
  • the NOx adsorbent is coated on the flow-through substrate or filter substrate.
  • the pierceable or filter substrate is a substrate that may contain a catalytic material and may be applied to the pierceable or filter substrate by any known means. Using the washcoat procedure, for example
  • a comparative material was prepared by adding palladium to the CHA type zeolite according to the following procedure:
  • a powder catalyst material was prepared by wet impregnation of the zeolite using a soluble palladium compound as a precursor. After drying at 105° C., the sample was fired at 500° C. and then subjected to hydrothermal aging at 750° C. in an air atmosphere containing 10% H 2 O. The Pd loading of the comparative material was 1% by weight.

Abstract

The present invention relates to: a NOx-adsorbing ruthenium-containing silicoaluminate, and more specifically, to: a NOx adsorption material of CHA and/or FER containing ruthenium; a cold start catalyst including such a NOx adsorption material; and an internal combustion engine exhaust system including the cold start catalyst.

Description

NOX 흡착성 루테늄-함유 실리코알루미네이트NOX Adsorbable Ruthenium-Containing Silicoaluminate
본 발명은 NOx 흡착성 루테늄-함유 실리코알루미네이트, 더욱 상세하게는 루테늄 함유 CHA 및/또는 FER의 NOx 흡착물질, 이러한 NOx 흡착물질을 포함하는 냉간 시동 촉매, 및 냉간 시동 촉매를 포함하는 내연 기관 배기 시스템에 관한 것이다.The present invention relates to an internal combustion engine exhaust system comprising a NOx adsorptive ruthenium-containing silicoaluminate, more specifically a ruthenium-containing CHA and/or FER NOx adsorption material, a cold start catalyst comprising such a NOx adsorption material, and a cold start catalyst. It is about.
내연기관에서 배출될 수 있는 오염 물질을 낮추는 문제에 있어서, 냉간 시동 구간에서 배출을 줄이는 것은 중대한 도전이 되고 있다. 특히 린번 조건하에서 냉간 시동 제어를 위한 NOx 저장 및 방출 촉매들이 집중적으로 연구되고, 공지된다. 이러한 촉매는 냉 시동 구간에서 NOx를 흡착하고 더 높은 배기 온도에서 열적으로 NOx를 탈착한다 (NSC 또는 NAC로 약칭). 탈착된 NOx는 하류에 배치되는 선택적 촉매 환원(SCR) 또는 NOx 흡착제 (NSR)에 의해 질소로 환원된다. 이러한 목적으로 저온 또는 냉간 시동 구간에서 NOx 저장능력이 우수한 NOx 트랩 또는 저장 물질이 지속적으로 요구된다.In the problem of lowering the pollutants that can be emitted from internal combustion engines, reducing emissions in the cold start section is a significant challenge. In particular, NOx storage and release catalysts for cold start control under lean burn conditions are intensively studied and known. These catalysts adsorb NOx in the cold start section and thermally desorb NOx at higher exhaust temperatures (abbreviated as NSC or NAC). The desorbed NOx is reduced to nitrogen by selective catalytic reduction (SCR) or NOx adsorbent (NSR) disposed downstream. For this purpose, a NOx trap or storage material having excellent NOx storage capacity is continuously required in a low temperature or cold start section.
대표적인 저온 NOx 흡착 물질은 적어도 하나의 백금족 금속으로 코팅된 알루미나, 실리카, 세리아, 지르코니아, 티타니아 또는 혼합 산화물과 같은 무기 산화물로 구성된다. 또한, Pd-Fe/Zeolite의 NOx 트랩 물질이 공지되어 있다. Representative low temperature NOx adsorbing materials consist of inorganic oxides such as alumina, silica, ceria, zirconia, titania or mixed oxides coated with at least one platinum group metal. In addition, NOx trapping materials of Pd-Fe/Zeolite are known.
한편, 제1 귀금속 및 LTL 프레임워크 유형을 갖는 분자체를 포함하는 passive NOx 흡착 촉매가 공지되고, 제1 귀금속은 팔라듐, 백금, 로듐, 금, 은, 이리듐, 루테늄, 오스뮴, 또는 그의 혼합물이고; 제2 분자체 촉매를 추가로 포함하며, 여기서 제2 분자체 촉매는 제2 귀금속 및 제2 분자체를 포함하고, 여기서 제2 분자체는 LTL 프레임워크 유형을 갖지 않는 것이고, 특히 CHA (카바자이트)인 passive NOx 흡착 촉매가 공지된다. 마지막으로, 분자체 촉매 (Pd/CHA) + 백금족/무기산화물을 포함한 냉간 시동 (200도 이하) 촉매가 알려져 있다.On the other hand, a passive NOx adsorption catalyst comprising a first noble metal and a molecular sieve having an LTL framework type is known, and the first noble metal is palladium, platinum, rhodium, gold, silver, iridium, ruthenium, osmium, or a mixture thereof; It further comprises a second molecular sieve catalyst, wherein the second molecular sieve catalyst comprises a second noble metal and a second molecular sieve, wherein the second molecular sieve does not have an LTL framework type, in particular CHA (Carbazai The catalyst for passive NOx adsorption is known. Finally, a molecular sieve catalyst (Pd/CHA) + a cold start (200°C or less) catalyst including platinum group/inorganic oxide is known.
그러나 공지된 시스템은 냉 시동 구간에서 NOx 흡착 용량이 충분하지 않을 뿐 아니라 고가의 백금족 성분으로 팔라듐 성분이 필수적이다.However, the known system does not have sufficient NOx adsorption capacity in the cold start section, and a palladium component is essential as an expensive platinum group component.
본 발명은 NOx를 냉 시동 구간에서 흡착시키고, 흡착된 NOx를 상기 냉 시동 구간보다 높은 온도에서 방출하는데 효과적인 NOx 흡착 물질을 개시하는 것이다. 본 발명의 NOx 흡착 물질은 Ru 및 CHA 또는 FER 분자체를 포함한다. 본 발명은 또한 NOx 흡착 물질을 포함하는 배기 시스템, 및 이를 이용하여 내연 기관의 배기 가스를 처리하는 방법을 포함한다.The present invention discloses a NOx adsorption material effective in adsorbing NOx in a cold start section and releasing the adsorbed NOx at a temperature higher than the cold start section. The NOx adsorption materials of the present invention include Ru and CHA or FER molecular sieves. The invention also includes an exhaust system comprising a NOx adsorbing material, and a method of using the same to treat exhaust gas of an internal combustion engine.
본 발명에 의한 냉간 시동 촉매물질은 냉 시동 구간에서 NOx를 흡착하고 그 흡착된 NOx를 냉 시동 구간 이상의 고온에서 변환하고 방출하기에 효과적이다. 특히 종래 고가의 Pd 대신 Ru을 사용하면서도 NOx 저장 성능을 크게 향상시킬 수 있다.The cold start catalyst material according to the present invention is effective in adsorbing NOx in the cold start section and converting and discharging the adsorbed NOx at a higher temperature than the cold start section. In particular, it is possible to significantly improve the NOx storage performance while using Ru instead of the conventional expensive Pd.
도 1은 실시예 및 비교예에서 생성된 파우더에 대한 DRIFT 측정 결과를 도시한 것이다. DRIFTS 전처리 조건: RT to 400C in Air+N2, 5min @ 400C in H2/N2, ramp-down to 200C in N2+Air, Adsorption @ 100C for 20min (NOx and Air), Ramp-up to 450C in Air+N2.1 shows DRIFT measurement results for powders produced in Examples and Comparative Examples. DRIFTS pretreatment conditions: RT to 400C in Air+N2, 5min @ 400C in H2/N2, ramp-down to 200C in N2+Air, Adsorption @ 100C for 20min (NOx and Air), Ramp-up to 450C in Air+N2 .
도 2는 실시예 및 비교예에서 생성된 파우더에 대한 TPD 측정 결과를 도시한 것이다. NOx TPD 전처리 조건: RT to 400C in O2/N2, 5min @ 400Cin H2/N2, ramp-down to 100˚C in N2, NOx Adsorption: 50mg sample, NOx+O2 adsorption 50 or 100C for 10min, NOx TPD: 50 or 100C to 600C Ramp-up @ 10˚C/min.2 shows TPD measurement results for powders produced in Examples and Comparative Examples. NOx TPD pretreatment conditions: RT to 400C in O2/N2, 5min @ 400Cin H2/N2, ramp-down to 100˚C in N2, NOx Adsorption: 50mg sample, NOx+ O2 adsorption 50 or 100C for 10min, NOx TPD: 50 or 100C to 600C Ramp-up @ 10˚C/min.
도 3은 Ru 함량 증가에 따른 NOx 성능 평가 결과이다.3 is an evaluation result of NOx performance according to an increase in Ru content.
도 4는 실시예에서 제조된 촉매에 대한 파일럿 테스트 결과이다. 파일럿 테스트 조건: Adsorption temp ~100C for 10min (NOx = 400 ppm) with other gas composition (HC, CO2, CO, O2, H2O), 5min N2 purge, Desorption: 100 to 700C desorption.4 is a result of a pilot test for the catalyst prepared in Example. Pilot test conditions: Adsorption temp ~100C for 10min (NOx = 400 ppm) with other gas composition (HC, CO2, CO, O2, H2O), 5min N2 purge, Desorption: 100 to 700C desorption.
본 발명의 NOx 흡착 물질은 분자체에 루테늄 구조를 포함한다. 본 발명에서 NOx 흡착 물질은 촉매 물질로도 칭하고, 이는 촉매 물질이 기재 (substrate)에 코팅되어 사용되는 촉매 물품 또는 간단히 촉매와는 개념상 구분된다. 본 발명에서 냉 또는 냉간 시동 구간이라 함은, 약 200℃ 이하의 구간으로 정의된다.The NOx adsorption material of the present invention contains a ruthenium structure in a molecular sieve. In the present invention, the NOx adsorbing material is also referred to as a catalyst material, which is conceptually distinguished from a catalyst article or simply a catalyst in which the catalyst material is coated on a substrate and used. In the present invention, the cold or cold start section is defined as a section of about 200°C or less.
본 발명에서 분자체는 제올라이트를 포함하여, 어떠한 천연 또는 합성 분자체일 수 있고, 바람직하게 알루미늄, 규소 및/또는 인으로 구성된다. 분자체는 전형적으로 산소 원자를 공유함으로써 결합된 SiO 4, AlO 4 및/또는 PO 4의 3-차원배열을 갖지만, 또한 2-차원 구조일 수도 있다. 분자체 프레임워크는 전형적으로 음이온성으로, 전하 보상 양이온, 전형적으로 알칼리 및 알칼리토 원소들 (예컨대 Na, K, Mg, Ca, Sr 및 Ba), 암모늄 이온 및 또한 양성자에 의해 균형이 이루어진다. 분자체는 바람직하게 8개의 4면체 원자의 최대 고리 크기를 가지는 작은 기공 분자체, 10개의 4면체 원자의 최대 고리 크기를 가지는 중간 기공 분자체 또는 12개의 4면체 원자의 최대 고리 크기를 가지는 큰 기공 분자체이다. 보다 바람직하게, 분자체는 SSZ-13, LTA, AEI, SAPO-34, FU-9, ZSM, FER, BEA, CHA, 또는 그것들의 혼합물의 프레임워크 구조를 가지고, 더욱 바람직하게는 FER 또는 CHA 구조를 가진다. In the present invention, the molecular sieve may be any natural or synthetic molecular sieve, including zeolite, and is preferably composed of aluminum, silicon and/or phosphorus. Molecular sieves typically have a three-dimensional arrangement of SiO 4 , AlO 4 and/or PO 4 bonded by sharing oxygen atoms, but may also have a two-dimensional structure. The molecular sieve framework is typically anionic, balanced by charge compensating cations, typically alkaline and alkaline earth elements (such as Na, K, Mg, Ca, Sr and Ba), ammonium ions and also protons. The molecular sieve is preferably a small pore molecular sieve having a maximum ring size of 8 tetrahedral atoms, a mesoporous molecular sieve having a maximum ring size of 10 tetrahedral atoms or a large pore having a maximum ring size of 12 tetrahedral atoms It is a molecular sieve. More preferably, the molecular sieve has a framework structure of SSZ-13, LTA, AEI, SAPO-34, FU-9, ZSM, FER, BEA, CHA, or a mixture thereof, more preferably FER or CHA structure Have.
NOx 흡착 물질은 임의의 공지된 수단에 의해 제조될 수 있다. 예를들면, 루테늄이 임의의 공지된 수단에 의해 분자체에 첨가되어 NOx 흡착 물질을 형성할 수 있으며, 첨가 방식은 특히 중요한 것으로 고려되지 않는다. 예를들면, 루테늄 화합물 (예컨대 염화루테늄, 질산루테늄)은 함침, 흡착, 이온-교환, 초기 침윤, 침전, 분무 건조 등에 의해 분자체 상에 지지될 수 있다. 대안적으로, 루테늄은 분자체의 합성 동안에 첨가될 수 있다. 다른 금속이 추가로 NOx 흡착물질에 첨가될 수 있다.The NOx adsorption material can be prepared by any known means. For example, ruthenium can be added to the molecular sieve by any known means to form the NOx adsorbing material, and the mode of addition is not considered particularly important. For example, ruthenium compounds (eg ruthenium chloride, ruthenium nitrate) can be supported on molecular sieves by impregnation, adsorption, ion-exchange, initial infiltration, precipitation, spray drying, and the like. Alternatively, ruthenium can be added during the synthesis of the molecular sieve. Other metals may additionally be added to the NOx adsorbent.
바람직하게는, NOx 흡착물질은 관통형 기재 또는 필터 기재에 코팅된다. 관통형 또는 필터 기재는 촉매 물질을 함유할 수 있는 기재이며, 임의의 공지된 수단에 의해 관통형 또는 필터 기재에 도포될 수 있다. 예컨대 워시코트 절차를 사용Preferably, the NOx adsorbent is coated on the flow-through substrate or filter substrate. The pierceable or filter substrate is a substrate that may contain a catalytic material and may be applied to the pierceable or filter substrate by any known means. Using the washcoat procedure, for example
하여 NOx 흡착물질을 기재에 코팅한다. 간단하게, 미분의 NOx 흡착물질을 적절한 용매, 바람직하게는 물에 슬러리화하여 슬러리를 형성하고 추가의 성분, 예컨대 전이 금속 산화물, 결합제, 안정화제, 점도조절제 또는 촉진제를 슬러리에 혼합하여 워시코트를 형성할 수 있다.The NOx adsorption material is coated on the substrate. Briefly, the finely divided NOx adsorbent is slurried in a suitable solvent, preferably water, to form a slurry, and additional components such as transition metal oxides, binders, stabilizers, viscosity modifiers or accelerators are mixed into the slurry to form a washcoat. Can be formed.
본 발명은 또한 NOx 흡착물질을 포함하는, 내연 기관을 위한 배기 시스템을 포함한다. 배기 시스템은 바람직하게는 정상 작동 온도에서 내연 기관 배기가스로부터의 오염물을 제거할 수 있는 1개 이상의 추가의 후처리 장치를 포함한다. 바람직하게는, 배기 시스템은 NOx 흡착 촉매 및 (1) 선택적 촉매 환원 (SCR) 촉매, (2) 미립자 필터, (3) SCR 필터, (4) NOx 흡착제 (NSR, NOx Storage Reduction), (5) 3원 촉매, (6) 산화 촉매, 또는 그의 임의의 조합으로부터 선택된 1종 이상의 다른 촉매를 포함한다.The invention also includes an exhaust system for an internal combustion engine, comprising a NOx adsorbent. The exhaust system preferably comprises at least one additional aftertreatment device capable of removing contaminants from internal combustion engine exhaust gases at normal operating temperatures. Preferably, the exhaust system comprises a NOx adsorption catalyst and (1) selective catalytic reduction (SCR) catalyst, (2) particulate filter, (3) SCR filter, (4) NOx adsorbent (NSR, NOx Storage Reduction), (5) And one or more other catalysts selected from three-way catalysts, (6) oxidation catalysts, or any combination thereof.
본 발명에 의한 NOx 흡착 물질 또는 NOx 촉매 물질 (NSC)은 바람직하게는 임의의 상기 후처리 장치와 별개의 성분이다. 대안적으로, NOx 흡착물질은 임의의 상기 후처리 장치 내로 성분으로서 혼입될 수 있다. 즉, NOx 흡착물질은 다른 촉매 성분을 함유하는 기재상의 구역으로서 혼입되거나 또는 다른 촉매 성분을 함유하는 기재상의 층으로서 혼입될 수 있다. 예시적인 예로서, NOx 흡착물질은 디젤 산화 촉매 (DOC)를 후방 구역으로서 함유하는 기재상의 전방 구역일 수 있거나; 또는 NOx 흡착물질은 기재상의 하층이고 디젤 산화 촉매는 상층을 형성할 수 있다.The NOx adsorption material or NOx catalyst material (NSC) according to the invention is preferably a separate component from any of the above post-treatment devices. Alternatively, the NOx adsorption material can be incorporated as a component into any of the above post-treatment devices. That is, the NOx adsorbent may be incorporated as a zone on the substrate containing other catalyst components or as a layer on the substrate containing other catalyst components. As an illustrative example, the NOx adsorbent may be a front zone on a substrate containing a diesel oxidation catalyst (DOC) as a back zone; Alternatively, the NOx adsorption material may form the lower layer on the substrate and the diesel oxidation catalyst may form the upper layer.
실시예 1: NOx 흡착물질 (Ru/CHA) 제조Example 1: Preparation of NOx adsorption material (Ru/CHA)
전구체로서 가용성 루테늄 화합물 RuCl 3의 수용액에 CHA (카바자이트) 제올라이트를 첨가하고 격렬하게 교반하였다. 혼합물을 60℃ 내지 80℃로 가열하고 이온-교환을 위하여 수시간 유지하였다. 150℃에서 건조시킨 후에, 샘플을 550℃에서 5시간 소성시키고 (신규 물질이라 칭함), 이어서 수열 분위기 (750℃/25h)에서 열수 노화시켰다. 비교물질의 Ru 로딩량은 1 중량%였다.CHA (carbazite) zeolite was added to an aqueous solution of a soluble ruthenium compound RuCl 3 as a precursor, followed by vigorous stirring. The mixture was heated to 60° C. to 80° C. and held for several hours for ion-exchange. After drying at 150° C., the sample was calcined at 550° C. for 5 hours (referred to as a new material), followed by hot water aging in a hydrothermal atmosphere (750° C./25 h). The Ru loading of the comparative material was 1% by weight.
실시예 2: NOx 흡착물질 (Ru/FER) 제조Example 2: Preparation of NOx adsorption material (Ru/FER)
실시예 1과 동일하게 제조하되, CHA (카바자이트) 제올라이트 대신 FER (ferrierite, 페리어라이트) 유형의 제올라이트를 첨가하여 Ru/FER를 제조하였다.In the same manner as in Example 1, but instead of CHA (carbazite) zeolite, FER (ferrierite) type zeolite was added to prepare Ru/FER.
실시예 1 및 2외에도 적용 가능한 제올라이트로서 SSZ-13, LTA, AEI, SAPO-34, FU-9 및 ZSM 등을 적용할 수 있으며, Ru 로딩량은 바람직하게는 분말 형태의 흡착 물질 총중량 기준으로 1 내지 2중량%로 함침될 수 있다.As zeolites applicable in addition to Examples 1 and 2, SSZ-13, LTA, AEI, SAPO-34, FU-9, and ZSM may be applied, and the Ru loading is preferably 1 based on the total weight of the adsorbed material in powder form. It may be impregnated with to 2% by weight.
실시예 1 및 2는 분말 형태로서 흡착 물질을 제조하는 방식을 기술한 것이나, 당업자 수준에서 이해되는 바와 같이, 기재에 직접 도포 가능한 슬러리 형태로 흡착 물질을 제조하는 것도 가능하다. 간략하게는, Ru 전구체를 증류수에 분산시킨 후 해당 제올라이트 예컨대 CHA 또는 FER을 첨가하여 혼합물을 형성한 후, 이에 결합제 및 점도 조절제 예컨대 유기 고분자를 부가한다. pH를 조정한 후 기재에 도포하고, 도포된 기재를 건조하고 550℃로 소성하여 촉매 물품을 완성한다. 이어서 수열 분위기 (800℃/25h)에서 열수 노화시킨다.Examples 1 and 2 describe a method of preparing the adsorbent material in the form of a powder, but, as understood by those skilled in the art, it is also possible to prepare the adsorbent material in the form of a slurry that can be applied directly to a substrate. Briefly, after the Ru precursor is dispersed in distilled water, a zeolite such as CHA or FER is added to form a mixture, and a binder and a viscosity modifier such as an organic polymer are added thereto. After adjusting the pH, it is applied to a substrate, and the applied substrate is dried and fired at 550°C to complete a catalyst article. Then, it is subjected to hydrothermal aging in a hydrothermal atmosphere (800°C/25h).
비교예: 종래 NOx 흡착물질 (1% Pd/CHA) 제조Comparative Example: Preparation of conventional NOx adsorption material (1% Pd/CHA)
팔라듐을 다음 절차에 따라 CHA 유형의 제올라이트에 첨가하여 비교 물질을 제조하였다: 전구체로서 가용성 팔라듐 화합물을 사용하여 제올라이트의 습식 함침에 의해 분말 촉매물질을 제조하였다. 105℃에서 건조시킨 후에, 샘플을 500℃에서 소성시키고 이어서 10% H 2O를 함유하는 공기 분위기에서 750℃에서 열수 노화시켰다. 비교물질의 Pd 로딩량은 1 중량%였다.A comparative material was prepared by adding palladium to the CHA type zeolite according to the following procedure: A powder catalyst material was prepared by wet impregnation of the zeolite using a soluble palladium compound as a precursor. After drying at 105° C., the sample was fired at 500° C. and then subjected to hydrothermal aging at 750° C. in an air atmosphere containing 10% H 2 O. The Pd loading of the comparative material was 1% by weight.
실시예 3: (NA-DOC/NSC) 이중층 촉매 제조Example 3: (NA-DOC/NSC) bilayer catalyst preparation
실시예 1-2 및 비교예에서 제조된 흡착물질을 하층으로, NA-DOC 물질을 상층으로 구성한 촉매 물품을 제작하였다. NA-DOC 물질은 Pt/Pd/Al 2O 3+SOC로 구성된다. A catalyst article comprising the adsorbent material prepared in Example 1-2 and Comparative Example as a lower layer and an NA-DOC material as an upper layer was prepared. The NA-DOC material is composed of Pt/Pd/Al 2 O 3 +SOC.
실험예 1:Experimental Example 1:
실시예 1, 2 및 비교예의 생성 파우더에 대한 DRIFTS (100℃에서 NOx 흡착 능력)를 측정한 결과 노화 (aging) 전후 모두 Ru/CHA 물질이 Pd/CHA 물질보다 100℃에서의 NOx 흡착능력이 우수하다. Ru/FER 물질은 CHA의 경우와 매우 유사한 개선 경향을 보이므로, 이하 실험 결과는 CHA 경우만을 제시한다.As a result of measuring the DRIFTS (NOx adsorption capacity at 100°C) for the powders produced in Examples 1 and 2 and Comparative Examples, the Ru/CHA material has better NOx adsorption capacity at 100°C than the Pd/CHA material both before and after aging. Do. Since the Ru/FER material shows a very similar improvement trend to that of CHA, the following experimental results are presented only in the case of CHA.
실험예 2:Experimental Example 2:
실시예 1, 2 및 비교예의 생성 파우더에 대한 TPD (온도 증가에 따른 NOx 흡착 능력)를 측정한 결과, Ru의 NOx 흡착 능력이 50℃ 및 100℃ 모두에서 우수하다.As a result of measuring TPD (NOx adsorption ability according to temperature increase) for the powders produced in Examples 1 and 2 and Comparative Examples, the NOx adsorption ability of Ru is excellent at both 50°C and 100°C.
실험예 3: Ru 함량 증가에 따른 NOx 성능을 평가한 결과에 의하면, Ru 로딩 함량이 증가할수록 NOx 전환율은 개선되며, 바람직하게는 흡착물질 총 중량 기준으로 1 내지 2 중량%가 적합하다.Experimental Example 3: According to the results of evaluating the NOx performance according to the increase of the Ru content, the NOx conversion rate is improved as the Ru loading content increases, and preferably 1 to 2% by weight based on the total weight of the adsorbed material is suitable.
실험예 4:Experimental Example 4:
실시예 3에서 제작된 촉매를 대상으로 NOx 흡착 성능에 대한 pilot 테스트 결과 Ru/CHA의 경우가 약 17% 이상의 저장 능력이 우수하다.As a result of a pilot test on the NOx adsorption performance for the catalyst prepared in Example 3, the case of Ru/CHA has excellent storage capacity of about 17% or more.

Claims (7)

  1. Ru 및 실리코알루미네이트 분자체를 포함하는 NOx 흡착물질.NOx adsorption material comprising Ru and silicoaluminate molecular sieve.
  2. 제1항에 있어서, 상기 실리코알루미네이트 분자체는 8, 10 및 12 원 고리 구조체를 가지는, NOx 흡착물질.The NOx adsorption material according to claim 1, wherein the silicoaluminate molecular sieve has 8, 10 and 12 membered ring structures.
  3. 제1항 또는 제2항에 있어서, 상기 실리코알루미네이트 분자체는 CHA, FER, SSZ-13, LTA, AEI, SAPO-34, FU-9 및 ZSM로 이루어 군에서 선택되는, NOx 흡착물질.The NOx adsorption material according to claim 1 or 2, wherein the silicoaluminate molecular sieve is selected from the group consisting of CHA, FER, SSZ-13, LTA, AEI, SAPO-34, FU-9 and ZSM.
  4. 제3항에 있어서, 상기 실리코알루미네이트 분자체는 CHA 또는 FER인, NOx 흡착물질.The NOx adsorbent according to claim 3, wherein the silicoaluminate molecular sieve is CHA or FER.
  5. 제1항, 제2항, 제3항 또는 제4항의 NOx 흡착물질을 포함하는, 냉간 시동 촉매.A cold starting catalyst comprising the NOx adsorbent of claim 1, 2, 3 or 4.
  6. 제5항의 냉간 시동 촉매를 포함하는 내연 기관 배기 시스템. An internal combustion engine exhaust system comprising the cold start catalyst of claim 5.
  7. 제6항에 있어서, 선택적 촉매 환원 (SCR) 촉매, 미립자 필터, SCR 필터, NOx 흡착제, 삼원 촉매, 산화 촉매 및 그것들의 조합으로 구성되는 군으로부터 선택된 촉매 성분을 더 포함하는 것을 특징으로 하는 배기 시스템.The exhaust system of claim 6, further comprising a catalyst component selected from the group consisting of a selective catalytic reduction (SCR) catalyst, a particulate filter, an SCR filter, an NOx adsorbent, a three-way catalyst, an oxidation catalyst, and combinations thereof. .
PCT/KR2020/007430 2019-06-17 2020-06-09 Nox-adsorbing ruthenium-containing silicoaluminate WO2020256326A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020190071640A KR20200143938A (en) 2019-06-17 2019-06-17 Ru containing Silico-Aluminate materials for NOx adsorption
KR10-2019-0071640 2019-06-17

Publications (1)

Publication Number Publication Date
WO2020256326A1 true WO2020256326A1 (en) 2020-12-24

Family

ID=74037477

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2020/007430 WO2020256326A1 (en) 2019-06-17 2020-06-09 Nox-adsorbing ruthenium-containing silicoaluminate

Country Status (2)

Country Link
KR (1) KR20200143938A (en)
WO (1) WO2020256326A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160094997A (en) * 2013-12-06 2016-08-10 존슨 맛쎄이 퍼블릭 리미티드 컴파니 An exhaust gas catalyst containing two different noble metal-molecular sieve catalysts
KR20160094996A (en) * 2013-12-06 2016-08-10 존슨 맛쎄이 퍼블릭 리미티드 컴파니 PASSIVE NOx ADSORBER COMPRISING NOBLE METAL AND SMALL PORE MOLECULAR SIEVE
KR20160096108A (en) * 2013-12-06 2016-08-12 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Cold start catalyst and its use in exhaust systems
KR20160140878A (en) * 2014-04-01 2016-12-07 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Diesel oxidation catalyst with nox adsorber activity
KR20170132158A (en) * 2015-03-25 2017-12-01 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Passive NOx adsorbent including precious metal and molecular sieve with OFF framework type

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160094997A (en) * 2013-12-06 2016-08-10 존슨 맛쎄이 퍼블릭 리미티드 컴파니 An exhaust gas catalyst containing two different noble metal-molecular sieve catalysts
KR20160094996A (en) * 2013-12-06 2016-08-10 존슨 맛쎄이 퍼블릭 리미티드 컴파니 PASSIVE NOx ADSORBER COMPRISING NOBLE METAL AND SMALL PORE MOLECULAR SIEVE
KR20160096108A (en) * 2013-12-06 2016-08-12 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Cold start catalyst and its use in exhaust systems
KR20160140878A (en) * 2014-04-01 2016-12-07 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Diesel oxidation catalyst with nox adsorber activity
KR20170132158A (en) * 2015-03-25 2017-12-01 존슨 맛쎄이 퍼블릭 리미티드 컴파니 Passive NOx adsorbent including precious metal and molecular sieve with OFF framework type

Also Published As

Publication number Publication date
KR20200143938A (en) 2020-12-28

Similar Documents

Publication Publication Date Title
RU2675905C1 (en) Passive nox adsorber comprising noble metal and small pore molecular sieve
US11185854B2 (en) Cold start catalyst and its use in exhaust systems
EP3077112B1 (en) Exhaust gas catalyst containing two different palladium-molecular sieve catalysts
US6432859B1 (en) Method of producing exhaust gas purifying catalyst and catalyst produced thereby
JP6236389B2 (en) High HC gas conversion rate and high CO gas conversion rate diesel oxidation catalyst with layered structure containing ceria composition as palladium support material
US20190217269A1 (en) Passive nox adsorber
EP0845289B1 (en) Nitrogen oxide trap for an internal combustion engine
KR20170116074A (en) Three-way catalyst and its use in exhaust systems
BR112017002568B1 (en) EXHAUST SYSTEM AND METHOD FOR TREATMENT AN EXHAUST GAS
US10850264B2 (en) Hydrocarbon trap catalyst
KR20160048134A (en) Co slip catalyst and method of using
US20190351398A1 (en) Hydrocarbon trap catalyst
US5950421A (en) Tungsten-modified platinum NOx traps for automotive emission reduction
EP4237128A1 (en) Nox adsorber (na) catalyst with tunable nox adsorption and desorption properties
WO2020256326A1 (en) Nox-adsorbing ruthenium-containing silicoaluminate
KR101716174B1 (en) A catalyst composition for preventing white smoke output from diesel engine
US6537511B1 (en) Modified platinum NOx trap for automotive emission reduction
WO2021060740A1 (en) Low temperature nox absorption composition and diesel oxidation catalyst containing same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20827501

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20827501

Country of ref document: EP

Kind code of ref document: A1