KR102476636B1 - SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas - Google Patents

SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas Download PDF

Info

Publication number
KR102476636B1
KR102476636B1 KR1020200181354A KR20200181354A KR102476636B1 KR 102476636 B1 KR102476636 B1 KR 102476636B1 KR 1020200181354 A KR1020200181354 A KR 1020200181354A KR 20200181354 A KR20200181354 A KR 20200181354A KR 102476636 B1 KR102476636 B1 KR 102476636B1
Authority
KR
South Korea
Prior art keywords
catalyst
tio
cocatalyst
extruding
exhaust gas
Prior art date
Application number
KR1020200181354A
Other languages
Korean (ko)
Other versions
KR20220090300A (en
Inventor
김수현
유지호
프라짓노 헤르마완
정순관
황선미
김상도
이시훈
최호경
전동혁
임정환
임혁
Original Assignee
한국에너지기술연구원
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 한국에너지기술연구원 filed Critical 한국에너지기술연구원
Priority to KR1020200181354A priority Critical patent/KR102476636B1/en
Publication of KR20220090300A publication Critical patent/KR20220090300A/en
Application granted granted Critical
Publication of KR102476636B1 publication Critical patent/KR102476636B1/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
    • 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
    • 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
    • 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
    • B01J21/063—Titanium; 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J37/0027—Powdering
    • 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
    • B01J37/0201—Impregnation
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment
    • 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]
    • 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

Abstract

본 발명은 SCR 촉매, 이의 제조 방법, 및 배가스 정화용 촉매에 관한 것이다. 구체적으로, 본 발명에 따르면 V2O5/TiO2 촉매 분말을 조촉매 전구체 분말과 물리적으로 혼합하는 단계를 포함하는, 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매의 제조 방법이 제공된다. 또한, 본 발명에 따르면 상기 제조 방법에 의해 제조된 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매 및 이를 포함하는 배가스 정화용 촉매가 제공된다. 상기 SCR 촉매는 저온에서도 높은 질소산화물(NOx) 전환율을 나타내어 저온 활성이 우수하고, 장기간 사용하여도 우수한 촉매 활성이 유지될 수 있고 H2O 또는 SO2에도 저항성이 우수하였다.The present invention relates to an SCR catalyst, a method for preparing the same, and a catalyst for purifying exhaust gas. Specifically, according to the present invention, a method for preparing a V 2 O 5 /TiO 2 -based SCR catalyst externally doped with a cocatalyst, comprising physically mixing V 2 O 5 /TiO 2 catalyst powder with a cocatalyst precursor powder. is provided. In addition, according to the present invention, a V 2 O 5 /TiO 2 based SCR catalyst externally doped with the cocatalyst prepared by the above manufacturing method and a catalyst for purifying exhaust gas including the same are provided. The SCR catalyst exhibits high nitrogen oxide (NOx) conversion even at low temperatures, so it has excellent low-temperature activity, can maintain excellent catalytic activity even after long-term use, and has excellent resistance to H 2 O or SO 2 .

Description

저온 활성이 개선된 SCR 촉매, 이의 제조 방법, 및 배가스 정화용 촉매 {SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas}SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas}

본 발명은 저온 활성이 개선된 SCR 촉매, 이의 제조 방법, 및 상기 SCR 촉매를 포함하는 배가스 정화용 촉매에 관한 것이다.The present invention relates to an SCR catalyst with improved low-temperature activity, a method for preparing the same, and a catalyst for purifying exhaust gas including the SCR catalyst.

선택적 촉매 환원(Selective Catalytic Reduction, SCR) 기술은 질소산화물(NOx)을 SCR 촉매에 접촉시켜서 인체에 무해한 질소와 물로 전환한 후 배출시킨다. 이 때 암모니아(NH3)나 요소수가 환원제로 사용되며 고온 가열된 촉매에 환원제가 분사되어 질소산화물만 선택적으로 환원시킨다. 이러한 SCR 기술은 주로 엔진으로부터 배출되는 배기가스 중의 질소산화물을 정화하려는 목적으로 이용되고 있다.Selective Catalytic Reduction (SCR) technology contacts nitrogen oxides (NOx) with an SCR catalyst to convert them into harmless nitrogen and water, and then discharge them. At this time, ammonia (NH 3 ) or urea water is used as a reducing agent, and the reducing agent is sprayed on the heated catalyst to selectively reduce only nitrogen oxides. Such SCR technology is mainly used for the purpose of purifying nitrogen oxides in exhaust gas discharged from an engine.

최근에는 산업체에서도 배가스 중의 질소산화물을 제거하려는 목적으로 SCR 촉매를 이용하는 방안이 연구되고 있다. 그러나, 현재 상용화되어 있는 SCR 기술의 최적 온도는 300 내지 350℃ 전후 영역인데 반해, 산업체에서의 배가스는 온도가 그보다 낮기 때문에 SCR 기술을 적용하기 위해서는 배가스 온도를 높여야 한다. 그러나, 이러한 온도 상승을 위해서는 막대한 에너지가 필요로 하게 된다. 따라서, 이러한 에너지 비용을 절감하고, 이와 동시에 미세먼지 전구체인 질소산화물을 효과적으로 제거하기 위해서는 저온에서도 우수한 활성을 보이는 SCR 촉매를 개발할 필요성이 있다.Recently, a method of using an SCR catalyst for the purpose of removing nitrogen oxides in exhaust gas has been studied in industries. However, the optimum temperature of the currently commercialized SCR technology is around 300 to 350 ° C., whereas the exhaust gas temperature in the industry is lower than that, so the exhaust gas temperature must be increased to apply the SCR technology. However, an enormous amount of energy is required for such a temperature rise. Therefore, there is a need to develop an SCR catalyst showing excellent activity even at low temperatures in order to reduce such energy costs and at the same time effectively remove nitrogen oxides, which are fine dust precursors.

본 발명의 일 목적은 저온에서도 우수한 활성을 보이는 SCR 촉매의 제조 방법을 제공하는 것이다.One object of the present invention is to provide a method for preparing an SCR catalyst exhibiting excellent activity even at low temperatures.

본 발명의 다른 일 목적은 저온에서도 우수한 활성을 보이는 SCR 촉매를 제공하는 것이다.Another object of the present invention is to provide an SCR catalyst exhibiting excellent activity even at low temperatures.

본 발명의 또다른 일 목적은 상기 SCR 촉매를 포함하는 배가스 정화용 촉매를 제공하는 것이다.Another object of the present invention is to provide a catalyst for purifying exhaust gas comprising the SCR catalyst.

본 발명의 일 양태에 따르면, V2O5/TiO2 촉매 분말을 조촉매 전구체 분말과 물리적으로 혼합하는 단계를 포함하는 조촉매가 외부 도핑 (external doping)된 V2O5/TiO2계 SCR 촉매의 제조 방법이 제공된다.According to one aspect of the present invention, a V 2 O 5 /TiO 2 based SCR externally doped with a cocatalyst comprising physically mixing a V 2 O 5 /TiO 2 catalyst powder with a cocatalyst precursor powder A method for preparing the catalyst is provided.

본 발명의 일 구현예에 따르면, 상기 물리적 혼합은 가압 하의 혼합 또는 밀링(milling)에 의해 수행될 수 있다. According to one embodiment of the present invention, the physical mixing may be performed by mixing or milling under pressure.

본 발명의 다른 일 구현예에 따르면, 상기 제조 방법은 TiO2 지지체를 V2O5 용액으로 함침 처리후 건조시켜 V2O5/TiO2 촉매 분말을 얻는 단계를 추가로 포함할 수 있다.According to another embodiment of the present invention, the preparation method may further include obtaining a V 2 O 5 /TiO 2 catalyst powder by impregnating the TiO 2 support with a V 2 O 5 solution and drying it.

본 발명의 또다른 일 구현예에 따르면, 상기 조촉매는 알칼리 토금속, 전이금속, 및 희토류 금속으로 이루어진 군에서 선택되는 1종 이상의 금속을 포함하는 것일 수 있다. According to another embodiment of the present invention, the cocatalyst may include one or more metals selected from the group consisting of alkaline earth metals, transition metals, and rare earth metals.

본 발명의 또다른 일 구현예에 따르면, 상기 조촉매는 MoO3, SiO2, CeO2, Sb2O3, WO3, GeO2, Nb2O3, Bi2O3, TiO2, MnO2, CuO, Ga2O3, La2O3, SmO2, Nd2O3, Gd2O3, GdxCe1-xO2-x, SmxCe1-xO2-x, La2-xSrxGa3Ox, 및 (ErO1.5)x(BiO1.5)1-x로 이루어진 군에서 선택되는 적어도 1종일 수 있다.According to another embodiment of the present invention, the cocatalyst is MoO 3 , SiO 2 , CeO 2 , Sb 2 O 3 , WO 3 , GeO 2 , Nb 2 O 3 , Bi 2 O 3 , TiO 2 , MnO 2 , CuO, Ga 2 O 3 , La 2 O 3 , SmO 2 , Nd 2 O 3 , Gd 2 O 3 , Gd x Ce 1-x O 2-x , Sm x Ce 1-x O 2-x , La 2 It may be at least one selected from the group consisting of -x Sr x Ga 3 O x , and (ErO 1.5 ) x (BiO 1.5 ) 1-x .

본 발명의 다른 일 양태에 따르면, 전술한 제조 방법에 의해 제조된 것을 특징으로 하는, 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매가 제공된다.According to another aspect of the present invention, a V 2 O 5 /TiO 2 based SCR catalyst externally doped with a cocatalyst, characterized in that manufactured by the above-described manufacturing method, is provided.

본 발명의 또다른 일 양태에 따르면, SOx의 선택적 흡착용 촉매, ABS(Ammonium Bisulfate) 분해용 촉매, 및 SO3로의 SO2 산화용 촉매로 이루어진 군에서 선택되는 적어도 1종의 촉매를, 전술한 제조 방법에 의해 제조된, 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매와 함께 포함하는 배가스 정화용 촉매가 제공된다.According to another aspect of the present invention, at least one catalyst selected from the group consisting of a catalyst for selective adsorption of SOx, a catalyst for decomposition of ABS (Ammonium Bisulfate), and a catalyst for oxidation of SO 2 to SO 3 is used as described above. Provided is a catalyst for purifying flue gas including a cocatalyst externally doped with a V 2 O 5 /TiO 2 -based SCR catalyst prepared by a manufacturing method.

본 발명의 일 구현예에 따르면, 상기 배가스 정화용 촉매는 본 발명의 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매와 SOx의 선택적 흡착용 촉매를 함께 혼합하고 압출하여 형성된 촉매층을 포함할 수 있다.According to one embodiment of the present invention, the exhaust gas purification catalyst includes a catalyst layer formed by mixing and extruding a V 2 O 5 /TiO 2 based SCR catalyst externally doped with the cocatalyst of the present invention and a catalyst for selective adsorption of SOx. can do.

본 발명의 다른 일 구현예에 따르면, 상기 배가스 정화용 촉매는 본 발명의 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매를 압출하여 형성된 제1 촉매층, 및 상기 제1 촉매층 상에 SOx의 선택적 흡착용 촉매를 압출하여 형성된 제2 촉매층을 포함할 수 있다.According to another embodiment of the present invention, the exhaust gas purification catalyst includes a first catalyst layer formed by extruding a V 2 O 5 /TiO 2 based SCR catalyst externally doped with the cocatalyst of the present invention, and SOx on the first catalyst layer. It may include a second catalyst layer formed by extruding a catalyst for selective adsorption of.

본 발명의 또다른 일 구현예에 따르면, 상기 배가스 정화용 촉매는 본 발명의 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매와 SOx의 선택적 흡착용 촉매를 함께 혼합하고 압출하여 형성된 제1 촉매층를 포함하고, 상기 제1 촉매층 상에 ABS(Ammonium Bisulfate) 분해용 촉매를 압출하여 형성된 제2 촉매층 또는 상기 제1 촉매층 상에 ABS(Ammonium Bisulfate) 분해용 촉매를 압출하여 형성된 제2 촉매층 및 SO3로의 SO2 산화용 촉매를 압출하여 형성된 제3 촉매층이 병렬로 형성된 것일 수 있다.According to another embodiment of the present invention, the exhaust gas purification catalyst is formed by mixing and extruding a V 2 O 5 /TiO 2 based SCR catalyst externally doped with the cocatalyst of the present invention and a catalyst for selective adsorption of SOx. It includes a first catalyst layer, and a second catalyst layer formed by extruding a catalyst for decomposing ABS (Ammonium Bisulfate) on the first catalyst layer or a second catalyst layer formed by extruding a catalyst for decomposing ABS (Ammonium Bisulfate) on the first catalyst layer, and SO A third catalyst layer formed by extruding a catalyst for SO 2 oxidation into 3 may be formed in parallel.

본 발명의 제조 방법에 따르면, 저온에서도 높은 질소산화물(NOx) 전환율을 나타내어 저온 활성이 우수하고, 장기간 사용하거나 H2O 또는 SO2의 영향에도 우수한 촉매 활성을 유지하는 SCR 촉매가 제공될 수 있다.According to the manufacturing method of the present invention, an SCR catalyst exhibiting a high nitrogen oxide (NOx) conversion rate even at low temperatures, having excellent low-temperature activity, and maintaining excellent catalytic activity even when used for a long time or under the influence of H 2 O or SO 2 can be provided. .

도 1은 본 발명에 따른 배가스 정화용 촉매의 구성을 개략적으로 도시하는 개략도이다.
도 2은 실험예 1에서 실시한, 180oC에서 H2O 또는 SO2의 영향에 따른 SCR 촉매의 NOx 전환율 변화를 나타내는 그래프이다.
도 3는 온도에 따른 SCR 촉매의 NOx 전환율을 나타내는 그래프이다.1 is a schematic diagram schematically showing the configuration of a catalyst for purification of exhaust gas according to the present invention.
FIG. 2 is a graph showing the change in NOx conversion rate of the SCR catalyst according to the influence of H 2 O or SO 2 at 180 ° C, as in Experimental Example 1. FIG.
3 is a graph showing the NOx conversion rate of the SCR catalyst according to temperature.

이하, 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 출원에서 사용한 용어는 단지 특정한 구현예를 설명하기 위해 사용된 것으로서 본 발명을 한정하려는 의도가 아니다. 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. The terms used in this application are only used to describe specific embodiments and are not intended to limit the present invention. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다, "함유”한다, "가지다"라고 할 때, 이는 특별히 달리 정의되지 않는 한, 다른 구성 요소를 더 포함할 수 있다는 것을 의미한다.Throughout the specification, when a part "includes", "includes", or "has" a certain component, it means that it may further include other components unless otherwise specifically defined.

통상 SCR 촉매는 촉매 활성을 나타내는 활성 물질과, 촉매 활성을 높이거나 촉매 수명을 연장시키는 등의 효과를 위한 조촉매, 이러한 활성 물질과 조촉매를 지지해 주고 높은 표면적을 제공해 반응 면적을 높이는 역할을 하는 분말 형태의 지지체(Support)를 포함하여 구성된다. In general, an SCR catalyst has an active material that exhibits catalytic activity, a cocatalyst for effects such as increasing catalytic activity or extending catalyst life, supporting these active materials and cocatalyst and providing a high surface area to increase the reaction area. It is configured to include a support (Support) in the form of a powder to do.

지지체는 비표면적, 기공 부피가 크고, 활성 금속을 담지시킬 경우 담지 분산도가 높은 것을 사용하는 것이 바람직하며, 본 발명에서는 티타니아(TiO2) 지지체를 사용한다. 상기 티타니아 지지체는 전자 이동이 Al2O3 또는 제올라이트에 비해 우수하다는 특징이 있다.As the support, it is preferable to use a support having a large specific surface area and a large pore volume, and having a high dispersion degree when supporting an active metal. In the present invention, a titania (TiO 2 ) support is used. The titania support is characterized by excellent electron transfer compared to Al 2 O 3 or zeolite.

또한, 본 발명에서는 V2O5를 활성 물질로서 사용한다. 상기 활성 물질의 양은 당업자가 촉매 성능을 고려하여 적절히 선택할 수 있고, 일반적으로, 상기 활성 물질이 담지되는 지지체를 포함한 총 중량을 기준으로 0.01 내지 15 중량%의 양으로 담지된다. 활성 물질이 15 중량% 이상 담지될 경우, 응집 현상이 나타나거나 과도한 산화력으로 인하여 환원제인 암모니아를 산화시켜 질소산화물 제거 성능의 저하를 초래하는 경우도 있다.Also, in the present invention, V 2 O 5 is used as an active material. The amount of the active material can be appropriately selected by those skilled in the art in consideration of catalytic performance, and is generally supported in an amount of 0.01 to 15% by weight based on the total weight including the support on which the active material is supported. When the active material is supported in an amount of 15% by weight or more, aggregation may occur or ammonia, a reducing agent, may be oxidized due to excessive oxidizing power, resulting in deterioration in nitrogen oxide removal performance.

아울러, 본 발명에서는 상기 조촉매는 알칼리 토금속, 전이금속, 및 희토류 금속으로 이루어진 군에서 선택되는 적어도 1종의 금속을 포함할 수 있다. 구체적으로, 상기 조촉매는 MoO3, SiO2, CeO2, Sb2O3, WO3, GeO2, Nb2O3, Bi2O3, TiO2, MnO2, CuO, Ga2O3, La2O3, SmO2, Nd2O3, Gd2O3, GdxCe1-xO2-x, SmxCe1-xO2-x, La2-xSrxGa3Ox, 및 (ErO1.5)x(BiO1.5)1-x로 이루어진 군에서 선택되는 적어도 1종일 수 있다. 상기 조촉매의 종류 및 함량은 온도 대역, 배기가스 조성 등의 요구되는 조건에 따라 적절히 선택될 수 있다. 상기 조촉매의 함량은 일반적으로 총 중량을 기준으로 0.01 중량% 이상 50 중량% 이하로 첨가할 수 있다.In addition, in the present invention, the cocatalyst may include at least one metal selected from the group consisting of alkaline earth metals, transition metals, and rare earth metals. Specifically, the cocatalyst is MoO 3 , SiO 2 , CeO 2 , Sb 2 O 3 , WO 3 , GeO 2 , Nb 2 O 3 , Bi 2 O 3 , TiO 2 , MnO 2 , CuO, Ga 2 O 3 , La 2 O 3 , SmO 2 , Nd 2 O 3 , Gd 2 O 3 , Gd x Ce 1-x O 2-x , Sm x Ce 1-x O 2-x , La 2-x Sr x Ga 3 O x , and (ErO 1.5 ) x (BiO 1.5 ) 1-x . The type and content of the cocatalyst may be appropriately selected according to required conditions such as temperature range and exhaust gas composition. The content of the cocatalyst may be generally added in an amount of 0.01% by weight or more and 50% by weight or less based on the total weight.

본 발명의 일 양태에 따르면, V2O5/TiO2 촉매 분말을 조촉매 전구체 분말과 물리적으로 혼합하는 단계를 포함하는 조촉매가 도핑된 V2O5/TiO2계 SCR 촉매의 제조 방법이 제공된다. 상기 방법은 TiO2 지지체를 V2O5 용액으로 함침 처리후 건조시켜 V2O5/TiO2 촉매 분말을 얻는 단계를 추가로 포함할 수 있다. According to one aspect of the present invention, a method for preparing a V 2 O 5 /TiO 2 based SCR catalyst doped with a cocatalyst, comprising physically mixing V 2 O 5 /TiO 2 catalyst powder with cocatalyst precursor powder, Provided. The method may further include a step of impregnating the TiO 2 support with a V 2 O 5 solution and then drying to obtain a V 2 O 5 /TiO 2 catalyst powder.

이에, 본 발명의 일 구현예에 따르면, 본 발명의 제조 방법은 (a) TiO2 지지체를 V2O5 용액으로 함침 처리후 건조시켜 V2O5/TiO2 촉매 분말을 얻는 단계 및 (b) V2O5/TiO2 촉매 분말을 조촉매 전구체 분말과 물리적으로 혼합하는 단계를 포함할 수 있다.Accordingly, according to one embodiment of the present invention, the manufacturing method of the present invention includes the steps of (a) impregnating a TiO 2 support with a V 2 O 5 solution and drying it to obtain a V 2 O 5 /TiO 2 catalyst powder; and (b) ) physically mixing the V 2 O 5 /TiO 2 catalyst powder with the cocatalyst precursor powder.

상기 (a) 단계에서 건조는 소성일 수 있다. 구체적으로, 상기 (a) 단계에서 상기 함침 처리후, 지지체에 남아 있는 바나듐 전구체 물질을 제거하기 위해 300℃ 이상, 구체적으로 400℃ 내지 600℃에서 소성할 수 있다. 상기 소성 온도가 600℃를 초과할 경우, 티타니아의 상(phase) 변화로 인하여 내구성 저하가 있을 수도 있다.Drying in step (a) may be sintering. Specifically, after the impregnation treatment in step (a), the support may be calcined at 300° C. or higher, specifically at 400° C. to 600° C. to remove the vanadium precursor material remaining on the support. When the firing temperature exceeds 600° C., durability may be deteriorated due to phase change of titania.

추가로, 상기 (b) 단계 이후에 (c) 소성하는 단계를 추가로 더 포함할 수 있다. 상기 소성도 300℃ 이상, 구체적으로 400℃ 내지 600℃에서 수행될 수 있다.Additionally, after the step (b), a step of (c) firing may be further included. The firing may also be carried out at 300 ° C or higher, specifically 400 ° C to 600 ° C.

본 발명의 제조 방법은 촉매 분말을 조촉매 전구체 분말과 물리적으로 혼합하여 조촉매를 도핑하는 것을 특징으로 한다. 여기서 물리적 혼합이란 소정의 압력 인가 하에 물질을 혼합하는 임의의 혼합 방식을 의미할 수 있으며, 증발법이나 함침법과 같은 화학적 혼합에 대한 상대적 의미로 사용될 수 있다. 구체적으로 상기 물리적 혼합은 가압하의 혼합, 또는 밀링(milling)일 수 있으며, 더 구체적으로는 상기 밀링은 볼(ball) 밀링일 수 있다. 상기 물리적 혼합은 예를 들어 소정의 rpm 하에서 1시간 이상 수행될 수 있다. 본 발명에서는 통상의 함침법과 같은 화학적 도핑이 아니라 물리적 혼합에 의해 외부로부터의 물리적인 조촉매 도핑에 의함으로써 촉매 성능의 향상을 얻을 수 있었다. 상기 촉매 성능의 향상은 구체적으로 저온에서의 SCR 활성, 예를 들어 저온에서의 높은 NOx 전환율 및 H2O와 SO2에 대한 저항성일 수 있다.The manufacturing method of the present invention is characterized by doping the cocatalyst by physically mixing the catalyst powder with the cocatalyst precursor powder. Here, physical mixing may refer to any mixing method in which materials are mixed under a predetermined pressure, and may be used in a relative sense to chemical mixing such as an evaporation method or an impregnation method. Specifically, the physical mixing may be mixing under pressure or milling, and more specifically, the milling may be ball milling. The physical mixing may be performed, for example, for 1 hour or more under a predetermined rpm. In the present invention, improvement in catalytic performance could be obtained by physical cocatalyst doping from the outside through physical mixing rather than chemical doping as in the conventional impregnation method. The improvement of the catalytic performance may be specifically SCR activity at low temperature, for example, high NOx conversion rate at low temperature and resistance to H 2 O and SO 2 .

이와 같이 저온에서 활성이 우수한 SCR 촉매를 사용함으로써 자동차의 콜드 스타트(cold start)에 따른 초기 NOx 배출에 대응할 수 있고, 산업체에서의 이용시 촉매 가열에 필요한 에너지 소비를 크게 감소시킬 수 있으며, 발전소의 FGD 후단과 같은 저온 영역이나 선박용 CP-SCR (After turbo-charger)용으로도 적용될 수가 있다는 이점이 있다.By using the SCR catalyst, which has excellent activity at low temperatures, it is possible to respond to the initial NOx emission due to the cold start of automobiles, greatly reduce the energy consumption required for heating the catalyst when used in industries, and FGD of power plants. There is an advantage that it can be applied to low-temperature areas such as the rear end or for CP-SCR (After turbo-charger) for ships.

또한, SCR 촉매는 200℃ 이하 저온 영역에서는 환원제로 사용하는 암모니아, 물이 황산화물, 질소산화물과 반응하여 ABS (ammonium bisulfate), AN (ammonium nitrate)를 형성하여 촉매 활성점을 막거나 후단 설비를 부식시키는 문제가 있고, 이에 따라 저온 영역에서 황산화물에 대한 내구성을 가질 것이 필요한데, 본 발명에 따르면 황화물에 대해 높은 흡착 성능을 보이는 조촉매를 물리적 혼합에 의해 손쉽게 도핑할 수 있으므로 ABS 에 대한 촉매의 저항성을 손쉽게 증가시킬 수 있다는 이점이 있다.In addition, the SCR catalyst forms ABS (ammonium bisulfate) and AN (ammonium nitrate) by reacting ammonia and water used as a reducing agent with sulfur oxides and nitrogen oxides in the low-temperature region below 200 ° C. There is a problem of corrosion, and accordingly, it is necessary to have durability against sulfur oxides in a low temperature region. According to the present invention, since a cocatalyst showing high adsorption performance for sulfides can be easily doped by physical mixing, the catalyst for ABS It has the advantage that resistance can be easily increased.

본 발명의 또다른 일 양태에 따르면, 본 발명의 전술한 제조 방법에 의해 제조된, 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매와 함께, SOx의 선택적 흡착용 촉매, ABS(Ammonium Bisulfate) 분해용 촉매, 및 SO3로의 SO2 산화용 촉매로 이루어진 군에서 선택되는 적어도 1종의 촉매를 포함하는 배가스 정화용 촉매가 제공될 수 있다.According to another aspect of the present invention, a catalyst for selective adsorption of SOx , ABS ( An exhaust gas purifying catalyst including at least one catalyst selected from the group consisting of a catalyst for decomposition of Ammonium Bisulfate) and a catalyst for oxidation of SO 2 into SO 3 may be provided.

상기 배가스 정화용 촉매는 도 1에 도시된 바와 같이 다양한 기능을 가진 촉매들을 혼합하거나 또는 이러한 다양한 기능을 가진 촉매들의 계층적 구조(layered structure)를 형성시켜 구성할 수 있으며, 이러한 다양한 형태의 구조를 통해 저온 활성이나 황화물에 대한 저항성 등과 같은 촉매 활성을 증가시킬 수 있다. 도 1에서 Function 1은 SCR 촉매, Function 2는 SOx의 선택적 흡착용 촉매, Function 3은 ABS(Ammonium Bisulfate) 분해용 촉매, Function 4는 SO3로의 SO2 산화용 촉매이다.As shown in FIG. 1, the exhaust gas purification catalyst can be configured by mixing catalysts having various functions or forming a layered structure of catalysts having various functions. It can increase catalytic activity, such as low-temperature activity or resistance to sulphides. In FIG. 1, Function 1 is an SCR catalyst, Function 2 is a catalyst for selective adsorption of SOx, Function 3 is a catalyst for decomposing aluminum bisulfate (ABS), and Function 4 is a catalyst for oxidation of SO 2 to SO 3 .

본 발명의 일 구현예에 따르면, 본 발명의 배가스 정화용 촉매는 도 1의 (a)에 도시된 바와 같이, SCR 촉매 (Function 1, 적색) 와 SOx의 선택적 흡착용 촉매 (Function 2, 청색)를 함께 혼합하고 압출하여 형성된 촉매층을 포함할 수 있다.According to one embodiment of the present invention, the exhaust gas purification catalyst of the present invention, as shown in (a) of FIG. and a catalyst layer formed by mixing and extruding together.

또한, 본 발명의 다른 일 구현예에 따르면, 본 발명의 배가스 정화용 촉매는 도 1의 (b)에 도시된 바와 같이, SCR 촉매를 압출하여 형성된 제1 촉매층 (Function 1, 적색)이 있고, SOx의 선택적 흡착용 촉매를 압출하여 형성된 제2 촉매층 (Function 2, 청색)이 상기 제1 촉매층 상에 있는 계층적 구조를 가질 수 있다.In addition, according to another embodiment of the present invention, the exhaust gas purification catalyst of the present invention has a first catalyst layer (Function 1, red) formed by extruding the SCR catalyst, as shown in FIG. 1 (b), and SOx A second catalyst layer (Function 2, blue) formed by extruding a catalyst for selective adsorption may have a hierarchical structure on the first catalyst layer.

또한, 본 발명의 또다른 일 구현예에 따르면, 본 발명의 배가스 정화용 촉매는 도 1의 (c)에 도시된 바와 같이, SCR 촉매 (Function 1, 적색) 와 SOx의 선택적 흡착용 촉매 (Function 2, 청색)를 함께 혼합하고 압출하여 형성된 제1 촉매층을 포함하고, ABS(Ammonium Bisulfate) 분해용 촉매를 압출하여 형성된 제2 촉매층 (Function 3, 회색)이 상기 제1 촉매층 상에 있는 계층적 구조를 가질 수 있다. In addition, according to another embodiment of the present invention, the exhaust gas purification catalyst of the present invention, as shown in (c) of FIG. , blue) and a first catalyst layer formed by mixing and extruding a catalyst for decomposition of ABS (Ammonium Bisulfate), and a second catalyst layer (Function 3, gray) formed by extruding a catalyst for decomposition of ABS (Ammonium Bisulfate) has a hierarchical structure on the first catalyst layer. can have

또한, 본 발명의 또다른 일 구현예에 따르면, 본 발명의 배가스 정화용 촉매는 도 1의 (d)에 도시된 바와 같이, SCR 촉매 (Function 1, 적색) 와 SOx의 선택적 흡착용 촉매 (Function 2, 청색)를 함께 혼합하고 압출하여 형성된 제1 촉매층을 포함하고, ABS(Ammonium Bisulfate) 분해용 촉매를 압출하여 형성된 제2 촉매층 (Function 3, 회색) 및 SO3로의 SO2 산화용 촉매를 압출하여 형성된 제3 촉매층 (Function 4, 녹색)이 상기 제1 촉매층 상에 병렬로 형성된 계층적 구조를 가질 수 있다.In addition, according to another embodiment of the present invention, the exhaust gas purification catalyst of the present invention, as shown in (d) of FIG. , blue) together, and a second catalyst layer (Function 3, gray) formed by extruding a catalyst for decomposition of ABS (Ammonium Bisulfate) and a catalyst for oxidation of SO 2 to SO 3 by extruding The formed third catalyst layer (Function 4, green) may have a hierarchical structure formed in parallel on the first catalyst layer.

상기 SOx의 선택적 흡착용 촉매, ABS 분해용 촉매, 및 SO3로의 SO2 산화용 촉매의 종류는 특별히 제한되지 않으며, 본 기술이 속하는 분야에 공지된 임의의 것을 통상의 기술자가 적절히 선택하여 사용할 수 있다. 구체적으로, 상기 촉매들은 알칼리 토금속, 전이금속, 및 희토류 금속으로 이루어진 군에서 선택되는 적어도 1종의 금속을 포함하는 것일 수 있다. 예를 들어, 상기 촉매들은 금속-도핑된 제올라이트, MoO3, SiO2, CeO2, Sb2O3, WO3, GeO2, Nb2O3, Bi2O3, TiO2, MnO2, CuO, Ga2O3, La2O3, SmO2, Nd2O3, Gd2O3, GdxCe1-xO2-x, SmxCe1-xO2-x, La2-xSrxGa3Ox, 및 (ErO1.5)x(BiO1.5)1-x로 이루어진 군에서 선택된 것일 수 있다.The types of the catalyst for selective adsorption of SOx, the catalyst for decomposing ABS, and the catalyst for oxidation of SO 2 to SO 3 are not particularly limited, and any known in the art to which the present technology belongs can be appropriately selected and used by a person skilled in the art. have. Specifically, the catalysts may include at least one metal selected from the group consisting of alkaline earth metals, transition metals, and rare earth metals. For example, the catalysts are metal-doped zeolites, MoO 3 , SiO 2 , CeO 2 , Sb 2 O 3 , WO 3 , GeO 2 , Nb 2 O 3 , Bi 2 O 3 , TiO 2 , MnO 2 , CuO , Ga 2 O 3 , La 2 O 3 , SmO 2 , Nd 2 O 3 , Gd 2 O 3 , Gd x Ce 1-x O 2-x , Sm x Ce 1-x O 2-x , La 2-x It may be selected from the group consisting of Sr x Ga 3 O x , and (ErO 1.5 ) x (BiO 1.5 ) 1-x .

이하에서는 본 발명의 실시예를 참조하여 발명을 더욱 구체적으로 설명하겠다. 실시예는 발명의 설명을 위해 제시되는 것이므로, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to embodiments of the present invention. Since the examples are presented for explanation of the invention, the present invention is not limited thereto.

{실시예] 본 발명에 따른 SCR 촉매 (SCR F1-Ce-Ex)의 제조{Example] Preparation of SCR catalyst (SCR F1-Ce-Ex) according to the present invention

NH4VO3 를 60oC 증류수에 용해 후 Ti를 용액에 첨가하였다. 혼합용액은 회전 진공 증발기를 사용하여 65oC에서 진공 상태, 50 rpm으로 물을 제거 후 건조하고, 400oC 에서 공기 분위기로 4시간 소성하였다. 제조된 V2O5/TiO2 분말과 Ce 전구체 분말을 막자 사발을 사용하여 30 분 동안 물리적 혼합하여 준비하였다. 그 후 샘플을 400oC에서 공기 분위기로 2시간 소성하여 Ce가 외부 도핑된 V2O5/TiO2 촉매 (이하, SCR F1-Ce-Ex)를 제조하였다.After dissolving NH 4 VO 3 in distilled water at 60 ° C, Ti was added to the solution. The mixed solution was dried after removing water at 50 rpm in a vacuum at 65 ° C using a rotary vacuum evaporator, and then calcined at 400 ° C in an air atmosphere for 4 hours. The prepared V 2 O 5 /TiO 2 powder and the Ce precursor powder were physically mixed for 30 minutes using a mortar and pestle. Thereafter, the sample was calcined at 400 ° C. in an air atmosphere for 2 hours to prepare a Ce externally doped V 2 O 5 /TiO 2 catalyst (hereinafter referred to as SCR F1-Ce-Ex).

[비교예] 화학적 혼합에 의해 조촉매를 도핑한 SCR F1-Ce-In의 제조[Comparative Example] Preparation of SCR F1-Ce-In doped with a cocatalyst by chemical mixing

NH4VO3 를 60oC 증류수에 용해 후 Ti를 용액에 첨가하였다. 혼합용액은 회전 진공 증발기를 사용하여 65oC에서 진공 상태, 50 rpm으로 물을 제거 후 건조하고, 400oC 에서 공기 분위기로 4시간 소성하였다. 그 후 V2O5/TiO2 분말을 Ce 전구체 용액에 첨가하여 90 분 동안 습식 함침법으로 혼합하였다 혼합용액은 회전 진공 증발기를 사용하여 65oC에서 진공 상태, 50 rpm으로 물을 제거 후 건조하고, 400oC 에서 공기 분위기로 2시간 소성하여, Ce가 내부 도핑된 V2O5/TiO2 촉매 (이하, SCR F1-Ce-In)를 제조하였다.After dissolving NH 4 VO 3 in distilled water at 60 ° C, Ti was added to the solution. The mixed solution was dried after removing water at 50 rpm in a vacuum at 65 ° C using a rotary vacuum evaporator, and then calcined at 400 ° C in an air atmosphere for 4 hours. Then, V 2 O 5 /TiO 2 powder was added to the Ce precursor solution and mixed by wet impregnation for 90 minutes. The mixed solution was dried after removing water at 50 rpm in a vacuum state at 65 o C using a rotary vacuum evaporator. and calcined at 400 ° C for 2 hours in an air atmosphere to prepare a Ce internally doped V 2 O 5 /TiO 2 catalyst (hereinafter referred to as SCR F1-Ce-In).

[실험예 1] 180 [Experimental Example 1] 180 oo C에서 HC to H 22 O 및 SOO and SO 22 영향성 평가 impact assessment

조촉매가 도핑되지 않은 SCR F1, 비교예에서 제조한 SCR F1-Ce-In, 및 실시예에서 제조한 SCR F1-Ce-Ex의 NOx 전환율을 그래프로 나타내어 도 2에 도시하였다. Figure 2 shows the NOx conversion rates of SCR F1 not doped with a cocatalyst, SCR F1-Ce-In prepared in Comparative Example, and SCR F1-Ce-Ex prepared in Example.

도 2은 180oC에서 촉매에 대한 H2O 및 SO2의 영향성을 확인하였다. 먼저 180oC에서 500 ppm NO, 500 ppm NH3, 3vol% O2, 6vol% H2O, 60,000 hr-1의 조건으로 wet 조건에서의 영향성을 1시간 동안 확인하였고(분홍색 구간) 그 후 500 ppm NO, 500 ppm NH3, 3vol% O2, 60,000 hr-1 조건으로 변경하여 건조 조건에서 초기 활성을 회복되는지 1시간 동안 확인하였다(노란색 구간). 그 후 500 ppm NO, 500 ppm NH3, 3vol% O2, 60,000 hr-1 조건에서 100 ppm SO2을 추가하여 Dry+SO2 조건에서 1시간 동안 촉매 활성을 확인하였고(연두색 구간) 1시간 후 Dry+SO2 조건에서 6vol% H2O을 추가하여 Wet+SO2 촉매 활성을 1시간 확인 한 뒤(하늘색 구간) 500 ppm NO, 500 ppm NH3, 3vol% O2, 60,000 hr-1 건조조건으로 변경하여 초기 활성을 회복하는지 30 분 동안 확인하였다(회색 구간).Figure 2 confirmed the effect of H 2 O and SO 2 on the catalyst at 180 ° C. First, at 180 o C, 500 ppm NO, 500 ppm NH 3 , 3 vol% O 2 , 6 vol% H 2 O, and 60,000 hr -1 were used to confirm the effect under wet conditions for 1 hour (pink section). 500 ppm NO, 500 ppm NH 3 , 3vol% O 2 , 60,000 hr -1 conditions were changed to confirm whether the initial activity was recovered in dry conditions for 1 hour (yellow section). After that, 100 ppm SO 2 was added at 500 ppm NO, 500 ppm NH 3 , 3 vol% O 2 , and 60,000 hr -1 to confirm the catalytic activity for 1 hour under Dry+SO 2 conditions (light green section), and after 1 hour After checking the Wet+SO 2 catalyst activity for 1 hour by adding 6vol% H 2 O under Dry+SO 2 condition (light blue section), 500 ppm NO, 500 ppm NH 3 , 3vol% O 2 , 60,000 hr -1 dry conditions It was checked for 30 minutes to recover the initial activity by changing to (grey section).

도 2에서 알 수 있는 바와 같이, 본 발명에 따른 SCR F1-Ce-Ex가 H2O나 SO2에 따른 영향에 관계없이 다른 두 촉매에 비하여 전체 시간에 걸쳐 더 높은 활성을 나타내었다.As can be seen in FIG. 2, the SCR F1-Ce-Ex according to the present invention showed higher activity over the entire time compared to the other two catalysts regardless of the effect of H 2 O or SO 2 .

[실험예 2] 저온에서의 촉매 활성 평가[Experimental Example 2] Evaluation of catalytic activity at low temperature

도 3는 온도에 따른 SCR 촉매의 NOx 전환율을 나타내는 그래프이다. 160oC에서부터 300oC까지 온도 범위에서 확인하였다. 500 ppm NO, 500 ppm NH3, 3vol% O2, 60,000 hr-1 의 조건에서 NOx 전환율을 확인하였다. 도 3에서 알 수 있듯이, 본 발명에 따른 SCR F1-Ce-Ex가 SCR F1-Ce-In 에 비하여 저온에서 더 높은 활성을 나타내었다.3 is a graph showing the NOx conversion rate of the SCR catalyst according to temperature. It was confirmed in the temperature range from 160 o C to 300 o C. NOx conversion rate was confirmed under conditions of 500 ppm NO, 500 ppm NH 3 , 3 vol% O 2 , and 60,000 hr -1 . As can be seen in FIG. 3, SCR F1-Ce-Ex according to the present invention showed higher activity at low temperature than SCR F1-Ce-In.

상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the present invention described in the claims below. You will understand that you can.

Claims (10)

V2O5/TiO2 촉매 분말을 조촉매 전구체 분말과 물리적으로 혼합하는 단계를 포함하고,
TiO2 지지체를 V2O5 용액으로 함침 처리 후 건조시켜 V2O5/TiO2 촉매 분말을 얻는 단계를 추가로 포함되고,
상기 V2O5/TiO2 촉매 분말을 얻는 단계는 65℃ 내지 400℃의 온도에서 건조 뒤 소성하는 단계를 포함하고,
상기 건조 뒤 소성한 후 물리적으로 혼합하는 시간은 4시간 내지 6.5시간이고,
상기 소성온도는 600℃ 미만이고, 및
상기 V2O5인 활성물질은 상기 활성 물질이 담지되는 TiO2 지지체를 포함한 총 중량을 기준으로 0.01 내지 15중량%의 양으로 담지되는 것을 특징으로 하는,
조촉매가 외부 도핑(external doping)된 V2O5/TiO2계 SCR 촉매의 제조 방법.physically mixing the V 2 O 5 /TiO 2 catalyst powder with the cocatalyst precursor powder;
Further comprising the step of impregnating the TiO 2 support with a V 2 O 5 solution and then drying to obtain a V 2 O 5 /TiO 2 catalyst powder;
The step of obtaining the V 2 O 5 /TiO 2 catalyst powder includes drying and calcining at a temperature of 65 ° C to 400 ° C,
After the drying and firing, the physical mixing time is 4 hours to 6.5 hours,
The firing temperature is less than 600 ° C, and
Characterized in that the active material of V 2 O 5 is supported in an amount of 0.01 to 15% by weight based on the total weight including the TiO 2 support on which the active material is supported.
Method for preparing a V 2 O 5 /TiO 2 based SCR catalyst externally doped with a cocatalyst. 제1항에 있어서,
상기 물리적 혼합이 가압 하의 혼합 또는 밀링(milling)에 의해 수행되는 것을 특징으로 하는 제조 방법.According to claim 1,
A manufacturing method, characterized in that the physical mixing is performed by mixing or milling under pressure. 삭제delete 제1항에 있어서,
상기 조촉매는 알칼리 토금속, 전이금속, 및 희토류 금속으로 이루어진 군에서 선택되는 적어도 1종의 금속을 포함하는 것을 특징으로 하는 제조 방법.According to claim 1,
The method of claim 1, wherein the cocatalyst comprises at least one metal selected from the group consisting of alkaline earth metals, transition metals, and rare earth metals. 제4항에 있어서,
상기 조촉매는 MoO3, SiO2, CeO2, Sb2O3, WO3, GeO2, Nb2O3, Bi2O3, TiO2, MnO2, CuO, Ga2O3, La2O3, SmO2, Nd2O3, Gd2O3, GdxCe1-xO2-x, SmxCe1-xO2-x, La2-xSrxGa3Ox, 및 (ErO1.5)x(BiO1.5)1-x로 이루어진 군에서 선택되는 적어도 1종인 것을 특징으로 하는 제조 방법.According to claim 4,
The cocatalyst is MoO 3 , SiO 2 , CeO 2 , Sb 2 O 3 , WO 3 , GeO 2 , Nb 2 O 3 , Bi 2 O 3 , TiO 2 , MnO 2 , CuO, Ga 2 O 3 , La 2 O 3 , SmO 2 , Nd 2 O 3 , Gd 2 O 3 , Gd x Ce 1-x O 2-x , Sm x Ce 1-x O 2-x , La 2-x Sr x Ga 3 O x , and ( A manufacturing method characterized in that at least one selected from the group consisting of ErO 1.5 ) x (BiO 1.5 ) 1-x . 제1항에 기재된 방법에 의해 제조된 것을 특징으로 하고,
상기 V2O5인 활성물질은 상기 활성 물질이 담지되는 지지체인 TiO2를 포함한 총 중량을 기준으로 0.01 내지 15중량%의 양으로 담지되는 것을 특징으로 하는,
조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매.It is characterized in that it is produced by the method according to claim 1,
Characterized in that the active material of V 2 O 5 is supported in an amount of 0.01 to 15% by weight based on the total weight including TiO 2 which is a support on which the active material is supported.
A V 2 O 5 /TiO 2 based SCR catalyst externally doped with a cocatalyst. 제1항에 기재된 방법에 의해 제조된 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매와 함께, SOx의 선택적 흡착용 촉매, ABS(Ammonium Bisulfate) 분해용 촉매, 및 SO3로의 SO2 산화용 촉매로 이루어진 군에서 선택되는 적어도 1종의 촉매를 포함하는 배가스 정화용 촉매.A catalyst for selective adsorption of SOx, a catalyst for decomposition of ABS (Ammonium Bisulfate), and SO into SO 3 together with a V 2 O 5 /TiO 2 based SCR catalyst externally doped with the cocatalyst prepared by the method according to claim 1 2 Catalyst for purification of exhaust gas comprising at least one catalyst selected from the group consisting of catalysts for oxidation. 제7항에 있어서, 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매와 SOx의 선택적 흡착용 촉매를 함께 혼합하고 압출하여 형성된 촉매층을 포함하는 것을 특징으로 하는 배가스 정화용 촉매.The catalyst for purification of exhaust gas according to claim 7, characterized in that it comprises a catalyst layer formed by mixing and extruding a V 2 O 5 /TiO 2 -based SCR catalyst externally doped with the cocatalyst and a catalyst for selective adsorption of SOx. 제7항에 있어서, 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매를 압출하여 형성된 제1 촉매층, 및 상기 제1 촉매층 상에 SOx의 선택적 흡착용 촉매를 압출하여 형성된 제2 촉매층을 포함하는 것을 특징으로 하는 배가스 정화용 촉매.The method of claim 7, wherein the first catalyst layer is formed by extruding a V 2 O 5 /TiO 2 -based SCR catalyst externally doped with a cocatalyst, and the second catalyst layer is formed by extruding a catalyst for selective adsorption of SOx on the first catalyst layer. Catalyst for purification of flue gas, characterized in that it comprises a. 제7항에 있어서, 조촉매가 외부 도핑된 V2O5/TiO2계 SCR 촉매와 SOx의 선택적 흡착용 촉매를 함께 혼합하고 압출하여 형성된 제1 촉매층을 포함하고, 상기 제1 촉매층 상에 ABS(Ammonium Bisulfate) 분해용 촉매를 압출하여 형성된 제2 촉매층 또는 상기 제1 촉매층 상에 ABS(Ammonium Bisulfate) 분해용 촉매를 압출하여 형성된 제2 촉매층 및 SO3로의 SO2 산화용 촉매를 압출하여 형성된 제3 촉매층이 병렬로 형성된 것을 특징으로 하는 배가스 정화용 촉매.The method of claim 7, wherein the cocatalyst comprises a first catalyst layer formed by mixing and extruding a V 2 O 5 /TiO 2 based SCR catalyst externally doped with a catalyst for selective adsorption of SOx, and ABS on the first catalyst layer. A second catalyst layer formed by extruding a catalyst for decomposition of (Ammonium Bisulfate) or a second catalyst layer formed by extruding a catalyst for decomposition of ABS (Ammonium Bisulfate) on the first catalyst layer and a second catalyst layer formed by extruding a catalyst for oxidation of SO 2 to SO 3 A catalyst for purifying exhaust gas, characterized in that three catalyst layers are formed in parallel.
KR1020200181354A 2020-12-22 2020-12-22 SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas KR102476636B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020200181354A KR102476636B1 (en) 2020-12-22 2020-12-22 SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020200181354A KR102476636B1 (en) 2020-12-22 2020-12-22 SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas

Publications (2)

Publication Number Publication Date
KR20220090300A KR20220090300A (en) 2022-06-29
KR102476636B1 true KR102476636B1 (en) 2022-12-12

Family

ID=82269986

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020200181354A KR102476636B1 (en) 2020-12-22 2020-12-22 SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas

Country Status (1)

Country Link
KR (1) KR102476636B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116351410B (en) * 2023-03-20 2024-04-16 浙江工业大学之江学院 Solid acid catalyst loaded with ternary metal oxides of titanium, vanadium and cerium, and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101102714B1 (en) * 2011-06-27 2012-01-05 한국전력기술 주식회사 Method for preparing a catalyst for removal of nitrogen oxides using dry ball-milling
KR101629483B1 (en) 2015-02-27 2016-06-13 주식회사 에코프로 Vanadium-based denitration catalyst and preparing method of the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR970010332A (en) * 1995-08-08 1997-03-27 한승준 Car cigarette ignition
US9101877B2 (en) * 2012-02-13 2015-08-11 Siemens Energy, Inc. Selective catalytic reduction system and process for control of NOx emissions in a sulfur-containing gas stream
CN111201075B (en) * 2017-10-12 2023-02-03 巴斯夫公司 Combined NOx absorber and SCR catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101102714B1 (en) * 2011-06-27 2012-01-05 한국전력기술 주식회사 Method for preparing a catalyst for removal of nitrogen oxides using dry ball-milling
KR101629483B1 (en) 2015-02-27 2016-06-13 주식회사 에코프로 Vanadium-based denitration catalyst and preparing method of the same

Also Published As

Publication number Publication date
KR20220090300A (en) 2022-06-29

Similar Documents

Publication Publication Date Title
US10385750B2 (en) Denitration catalyst and method for producing the same
KR101121184B1 (en) Exhaust gas catalyst
EP1685891A1 (en) Method for catalytically reducing nitrogen oxide and catalyst therefor
CN101972652B (en) Preparation method of compound SCR catalyst with zero-valent mercury conversion function
KR101670075B1 (en) Manufacturing Method of De-NOx Catalyst for Selective Catalytic Reduction
AU2007302446A1 (en) Alkali resistant catalyst
CN101468314B (en) Catalyst for low-temperature denitration of flue gas and preparation method thereof
KR102476636B1 (en) SCR Catalysts Having Improved Low Temperature Performance, Method for Preparing the Same, and Catalysts for Purifying Exhaust Gas
CA2764132C (en) Mercury oxidation catalyst and method for producing the same
TWI555569B (en) A method for purifying exhaust gas containing metallic mercury, an oxidation catalyst for metallic mercury in exhaust gas, and a method of manufacturing the same
CN111111647A (en) Niobite type manganese-niobium-based SCR denitration catalyst and preparation method thereof
US11371406B2 (en) Low-temperature de-NOx catalyst for treatment of exhaust gas from stationary source and method of manufacturing same
EP1360006B1 (en) Method for preparing a catalyst for selective catalytic reduction of nitrogen oxides
CA2427081C (en) Catalyst compound for purifying exhaust gas, catalyst comprising the compound, and processes for producing them
KR20210069181A (en) DE-NOx CATALYST HAVING STORAGE EFFICIENCY OF NITROGER OXIDE AND METHOD OF PREPARING THE SAME
KR102292551B1 (en) Scr catalyst with enhanced stability for surfur components
EP3075437B1 (en) Exhaust gas treatment system
KR100473080B1 (en) Method for Improving NOx Removal Efficiency from Flue Gas and Reducing Consumption of Ammonia and Emission of Nitrogen Dioxide Using Modified Natural Manganese Ores
KR102634719B1 (en) Selective catalytic reduction comprising surface treatment layer and method of preparing the same
KR102558168B1 (en) Catalyst for ammonia oxidation, and method for producing the same
KR20230057068A (en) Catalyst with wide range of reaction temperature for NOx removal in flexible operation of coal-fired power plants and its manufacturing method
KR20230133559A (en) SCR catalyst using single-step hexagonal boron nitride with improved thermal stability and method for synthesizing the same
KR20230123097A (en) Denitrification catalyst and method of the same
CN106964377B (en) SCR catalyst for diesel vehicle tail gas denitration and preparation method thereof
KR20220110061A (en) Corrugated catalyst system

Legal Events

Date Code Title Description
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant