KR20230064229A - Methane oxidation catalyst regeneration device and regeneration method - Google Patents

Methane oxidation catalyst regeneration device and regeneration method Download PDF

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KR20230064229A
KR20230064229A KR1020210149595A KR20210149595A KR20230064229A KR 20230064229 A KR20230064229 A KR 20230064229A KR 1020210149595 A KR1020210149595 A KR 1020210149595A KR 20210149595 A KR20210149595 A KR 20210149595A KR 20230064229 A KR20230064229 A KR 20230064229A
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methane
methane oxidation
oxidation catalyst
regeneration gas
reactor
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KR102623977B1 (en
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이정주
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에이치디현대중공업 주식회사
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    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • 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
    • F01N9/00—Electrical control of exhaust gas treating 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
    • F01N2410/00—By-passing, at least partially, exhaust from inlet to outlet of apparatus, to atmosphere or to other device
    • 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
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1453—Sprayers or atomisers; Arrangement thereof in the exhaust apparatus
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
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Abstract

The present invention relates to a methane-oxidizing catalyst regeneration device for oxidizing methane and a method thereof, which may regenerate the entire methane-oxidizing catalyst within a reactor or selectively regenerate a partial methane oxidation catalyst in reducing PdO formed at the methane-oxidizing catalyst by injecting regenerative gas into the reactor in a state in which the reactor equipped with the methane-oxidizing catalyst is closed. To this end, the methane-oxidizing catalyst regeneration device according to the present invention comprises: a reactor equipped with a methane-oxidizing catalyst; a regenerative gas supply line which supplies regenerative gas to the reactor; and a regenerative gas branching pipe which is branched from the regenerative gas supply line to be extended upstream from the methane-oxidizing catalyst in the reactor, and sprays regenerative gas towards the methane-oxidizing catalyst. Therefore, the regenerative gas sprayed from the regenerative gas branching pipe may reduce PdO formed at the methane-oxidizing catalyst. The methane-oxidizing catalyst regeneration method includes the following steps of: closing the reactor equipped with the methane-oxidizing catalyst; and reducing the PdO by injecting the regenerative gas upstream from the methane-oxidizing catalyst.

Description

메탄산화촉매 재생장치 및 재생방법{Methane oxidation catalyst regeneration device and regeneration method}Methane oxidation catalyst regeneration device and regeneration method

본 발명은 메탄을 산화시키는 메탄산화촉매의 재생장치 및 그 방법에 관한 것으로, 특히 메탄산화촉매가 장착된 반응기를 폐쇄한 상태에서 재생가스를 반응기에 주입하여 메탄산화촉매에 형성된 PdO를 환원시킴에 있어 반응기 내부의 전체 메탄산화촉매를 재생하거나 또는 일부 메탄산화촉매를 선택하여 재생할 수 있게 구성한 것이다.The present invention relates to an apparatus and method for regenerating a methane oxidation catalyst that oxidizes methane. In particular, in a state where the reactor equipped with the methane oxidation catalyst is closed, regeneration gas is injected into the reactor to reduce PdO formed in the methane oxidation catalyst. It is configured to regenerate all the methane oxidation catalysts inside the reactor or select and regenerate some methane oxidation catalysts.

천연가스 연료는 기존 연료에 비하여 이산화탄소, 황산화물, 질소산화물, 미립자물질(PM: Particulate Matter) 등 대기오염물질 및 지구온난화가스의 배출량이 매우 적어 친환경 연료로 주목 받고 있다. 이런 장점 때문에 선박 및 자동차 등에 있어서 천연가스를 연료로 하는 엔진의 사용이 증가하는 추세이다.Compared to conventional fuels, natural gas fuel is attracting attention as an eco-friendly fuel because it emits very little air pollutants such as carbon dioxide, sulfur oxides, nitrogen oxides, and particulate matter (PM) and global warming gases. Because of these advantages, the use of engines using natural gas as fuel is increasing in ships and automobiles.

그런데 천연가스는 메탄을 주성분으로 포함하며, 메탄은 강력한 탄소-수소 결합을 갖고 있어서 상당히 안정한 상태로 존재하기 때문에, 엔진에서 완전히 소모되지 않고 배출될 경우 배기가스 온도 조건에서는 자연적으로 산화되지 않아 미처리된 상태로 대기 중에 그대로 배출된다.However, natural gas contains methane as its main component, and since methane has a strong carbon-hydrogen bond and exists in a fairly stable state, when it is discharged without being completely consumed by the engine, it is not naturally oxidized under exhaust gas temperature conditions, so it is untreated. It is emitted as it is into the atmosphere.

한편, 메탄(CH4)은 동등한 양의 이산화탄소(CO2)에 비해 28 ~ 86배 더 높은 지구온난화물질이다. 지구 온난화의 문제를 해결하기 위해서는 배기가스에서 배출되는 메탄의 양을 줄여야 하며, 최근 국제해사기구(IMO) 및 유럽연합(EU) 등에서 GHG(지구온난화가스, Green House gases) 배출 저감을 위한 규제강화에 따라 이산화탄소(CO2) 등 GHG 배출규제 및 탄소세가 거론되고 있으며, 메탄이 대기 중으로 배출되지 않는 기술이 요구되고 있다.On the other hand, methane (CH4) is a global warming substance that is 28 to 86 times more likely than an equivalent amount of carbon dioxide (CO2). In order to solve the problem of global warming, the amount of methane emitted from exhaust gas must be reduced. Accordingly, GHG emission regulations such as carbon dioxide (CO2) and a carbon tax are being discussed, and a technology that does not emit methane into the atmosphere is required.

이와 같은 요구에 따라 환경 오염에 주요한 원인으로 작용하는 이중연료엔진(DF Engine) 등의 배기가스를 효율적으로 정화하기 위하여, 특히 배기가스에 다량으로 포함된 메탄을 효율적으로 제거하는 방법에 대한 다양한 연구가 진행 중에 있다.In accordance with such a demand, various studies on methods for efficiently removing methane contained in a large amount of exhaust gas in order to efficiently purify exhaust gas such as dual fuel engines (DF Engine), which act as a major cause of environmental pollution, is in progress

메탄을 효율적으로 제거하는 하나의 방법으로, 메탄을 산화시키는 데에 촉매를 이용하는 기술이 개발되고 있다.As one method of efficiently removing methane, a technology using a catalyst to oxidize methane is being developed.

최근에는 귀금속을 알루미나 등의 산화물 담체에 담지한 것으로, 팔라듐이나 백금을 알루미나에 담지한 촉매가 널리 알려지고 있으며, 압축천연가스 엔진을 장착한 선박 및 자동차 등에서 연비 성능을 향상시키기 위해 연료 희박 분위기(Lean-burn)에서 엔진을 작동할 경우 배기가스에 포함된 메탄을 정화하기 위해 팔라듐과 백금이 혼합된 산화촉매(Oxidation Catalyst)를 이용하는 기술이 개발되고 있다.Recently, catalysts in which noble metals are supported on oxide carriers such as alumina, and palladium or platinum supported on alumina are widely known, and fuel lean atmospheres ( A technology using an oxidation catalyst mixed with palladium and platinum is being developed to purify methane contained in exhaust gas when the engine is operated in lean-burn.

하지만, 팔라듐의 경우에는 촉매 상에 산소가 흡착되면 PdO(Palladium Oxidation)이 발생하게 되고, PdO에 의해 메탄의 산화성능이 저하된다.However, in the case of palladium, when oxygen is adsorbed on the catalyst, PdO (Palladium Oxidation) is generated, and methane oxidation performance is reduced by PdO.

따라서 팔라듐 기반 메탄산화촉매를 이용하여 메탄을 제거하기 위해서는 메탄산화촉매에 발생하는 PdO을 환원시키는 촉매재생의 기술 개발이 시급한 상태이며, 특히 엔진이 연료 희박 분위기(Lean-burn) 상태로 운전될 경우, 과잉 상태의 산소가 메탄산화촉매와 반응하여 PdO의 발생이 현저하게 증가되는 문제점이 있다.Therefore, in order to remove methane using a palladium-based methane oxidation catalyst, it is urgent to develop a catalyst regeneration technology that reduces PdO generated in the methane oxidation catalyst, especially when the engine is operated in a lean-burn condition. However, there is a problem in that excessive oxygen reacts with the methane oxidation catalyst and significantly increases the generation of PdO.

대한민국 등록특허 제10-1909303호Republic of Korea Patent No. 10-1909303 대한민국 공개특허 제10-2016-0112179호Republic of Korea Patent Publication No. 10-2016-0112179 대한민국 등록특허 제10-1598390호Republic of Korea Patent No. 10-1598390

본 발명은 앞에서 설명한 바와 같은 종래 기술의 문제점을 해결하기 위하여 발명된 것으로서, 메탄산화촉매가 장착된 반응기를 폐쇄한 상태에서 재생가스를 반응기에 주입하여 메탄산화촉매에 형성된 PdO를 환원시킴에 있어 반응기 내부의 전체 메탄산화촉매를 재생하거나 또는 일부 메탄산화촉매를 선택하여 재생할 수 있는 메탄산화촉매 재생장치 및 재생방법을 제공하는 데 그 목적이 있다.The present invention was invented to solve the problems of the prior art as described above, and in reducing PdO formed in the methane oxidation catalyst by injecting regeneration gas into the reactor in a state where the reactor equipped with the methane oxidation catalyst is closed, the reactor An object of the present invention is to provide an apparatus and method for regenerating a methane oxidation catalyst capable of regenerating all internal methane oxidation catalysts or selectively regenerating some methane oxidation catalysts.

상기와 같은 목적을 달성하기 위한 본 발명에 따른 메탄산화촉매 재생장치는 메탄산화촉매가 장착된 반응기와, 반응기로 재생가스를 공급하는 재생가스 공급라인과, 재생가스 공급라인에서 분기되어 반응기 내부의 메탄산화촉매의 상류 측으로 연장되며 메탄산화촉매를 향해 재생가스를 분사하는 재생가스 분기관을 포함하며, 재생가스 분기관에서 분사된 재생가스에 의해 PdO를 환원시키는 것을 기술적 특징으로 한다.Methane oxidation catalyst regeneration apparatus according to the present invention for achieving the above object is branched from a reactor equipped with a methane oxidation catalyst, a regeneration gas supply line for supplying regeneration gas to the reactor, and a regeneration gas supply line, A regeneration gas branch pipe extending upstream of the methane oxidation catalyst and injecting a regeneration gas toward the methane oxidation catalyst is technically characterized in that PdO is reduced by the regeneration gas injected from the regeneration gas branch pipe.

또한, 본 발명의 바람직한 실시예에 따르면, 반응기의 내부에는 복수의 메탄산화촉매가 배기가스의 진행방향을 따라 간격을 두고 배치되며, 각 메탄산화촉매 마다 재생가스 분기관이 각각 연장되어 위치한다.In addition, according to a preferred embodiment of the present invention, a plurality of methane oxidation catalysts are disposed at intervals along the flow direction of the exhaust gas inside the reactor, and a regeneration gas branch pipe is extended for each methane oxidation catalyst.

또한, 본 발명의 바람직한 실시예에 따르면, 재생가스 분기관에는 밸브가 장착되어 재생가스 공급라인에서 재생가스 분기관으로 재생가스의 공급을 제어한다.In addition, according to a preferred embodiment of the present invention, a valve is mounted on the regeneration gas branch pipe to control the supply of regeneration gas from the regeneration gas supply line to the regeneration gas branch pipe.

또한, 본 발명의 바람직한 실시예에 따르면, 재생가스 공급라인에는 밸브가 장착되어 재생가스 공급라인으로 재생가스의 공급을 제어한다.In addition, according to a preferred embodiment of the present invention, a valve is mounted on the regeneration gas supply line to control the supply of the regeneration gas to the regeneration gas supply line.

상기와 같은 목적을 달성하기 위한 본 발명에 따른 메탄산화촉매 재생방법은 메탄산화촉매가 장착된 반응기를 폐쇄하는 단계와, 메탄산화촉매의 상류 쪽에 재생가스를 주입하여 PdO를 환원하는 단계를 포함하는 것을 기술적 특징으로 한다.A method for regenerating a methane oxidation catalyst according to the present invention for achieving the above object includes closing a reactor equipped with a methane oxidation catalyst and reducing PdO by injecting a regeneration gas upstream of the methane oxidation catalyst. as a technical feature.

또한, 본 발명의 바람직한 실시예에 따르면, 반응기의 내부에 장착된 복수의 메탄산화촉매 중 일부의 메탄산화촉매에만 재생가스를 공급하여 메탄산화촉매의 재생을 선택적으로 수행하는 단계를 더 포함한다.In addition, according to a preferred embodiment of the present invention, the step of selectively performing the regeneration of the methane oxidation catalyst by supplying a regeneration gas to only some of the methane oxidation catalysts among the plurality of methane oxidation catalysts installed inside the reactor.

또한, 본 발명의 바람직한 실시예에 따르면, 반응기의 내부에 장착된 복수의 메탄산화촉매 각각에 재생가스를 공급하여 전체 메탄산화촉매를 재생하는 단계를 더 포함한다.Further, according to a preferred embodiment of the present invention, the step of regenerating the entire methane oxidation catalyst by supplying a regeneration gas to each of the plurality of methane oxidation catalysts mounted inside the reactor is further included.

앞서 설명한 바와 같이, 본 발명에 따른 메탄산화촉매 재생장치 및 재생방법은 반응기 내부에 재생가스를 주입하여 메탄산화촉매에 발생한 PdO를 환원시켜 메탄 산화성능을 향상시켜 대기 중으로 배출되는 메탄을 최소화할 수 있게 구성한 것으로서, 재생가스의 주입으로 메탄산화촉매를 환원시킬 수 있는 구조적으로 간단하면서 재생 효과가 크다는 장점이 있다.As described above, the methane oxidation catalyst regeneration apparatus and regeneration method according to the present invention reduce PdO generated in the methane oxidation catalyst by injecting regeneration gas into the reactor to improve methane oxidation performance, thereby minimizing methane discharged into the atmosphere. It has the advantage of being structurally simple and having a great regeneration effect that can reduce the methane oxidation catalyst by injecting regeneration gas.

또한 본 발명에 따른 메탄산화촉매 재생장치 및 재생방법은 반응기 내부에 장착된 메탄산화촉매들 전체를 한꺼번에 재생하거나 PdO가 심하게 발생한 메탄산화촉매를 선택적으로 재생할 수 있게 구성함으로써, 메탄산화촉매 재생효율성을 증대시킬 수 있다는 장점이 있다.In addition, the methane oxidation catalyst regeneration apparatus and method according to the present invention regenerate all the methane oxidation catalysts installed inside the reactor at once or selectively regenerate the methane oxidation catalyst in which PdO is severely generated, thereby improving the methane oxidation catalyst regeneration efficiency. It has the advantage of increasing it.

도 1은 본 발명의 한 예에 따른 메탄산화촉매 반응기를 나타낸 단면도이고,
도 2는 도 1에 도시된 메탄산화촉매를 향해 재생가스를 분사하는 관계를 나타낸 개념도이다.
도 3은 본 발명의 다른 예에 따른 메탄산화촉매 반응기를 나타낸 단면도이고,
도 4는 도 1에 도시된 메탄산화촉매를 향해 재생가스를 분사하는 관계를 나타낸 개념도이다.1 is a cross-sectional view showing a methane oxidation catalyst reactor according to an example of the present invention;
FIG. 2 is a conceptual diagram illustrating a relationship in which a regeneration gas is injected toward the methane oxidation catalyst shown in FIG. 1 .
3 is a cross-sectional view showing a methane oxidation catalyst reactor according to another example of the present invention;
FIG. 4 is a conceptual diagram showing a relationship in which regeneration gas is injected toward the methane oxidation catalyst shown in FIG. 1 .

아래에서는 본 발명에 따른 메탄산화촉매 재생장치 및 재생방법의 양호한 실시예를 첨부한 도면을 참조로 하여 상세히 설명한다.Hereinafter, a preferred embodiment of a methane oxidation catalyst regeneration apparatus and regeneration method according to the present invention will be described in detail with reference to the accompanying drawings.

도면에서, 도 1은 본 발명의 한 예에 따른 메탄산화촉매 반응기를 나타낸 단면도이고, 도 2는 도 1에 도시된 메탄산화촉매를 향해 재생가스를 분사하는 관계를 나타낸 개념도이다. 그리고 도 3은 본 발명의 다른 예에 따른 메탄산화촉매 반응기를 나타낸 단면도이고, 도 4는 도 1에 도시된 메탄산화촉매를 향해 재생가스를 분사하는 관계를 나타낸 개념도이다.In the drawings, FIG. 1 is a cross-sectional view showing a methane oxidation catalyst reactor according to an example of the present invention, and FIG. 2 is a conceptual diagram showing a relationship in which a regeneration gas is injected toward the methane oxidation catalyst shown in FIG. 1 . 3 is a cross-sectional view showing a methane oxidation catalyst reactor according to another example of the present invention, and FIG. 4 is a conceptual diagram showing a relationship in which a regeneration gas is injected toward the methane oxidation catalyst shown in FIG. 1 .

도 1 및 도 2에 도시된 바와 같이, 엔진(10)에서 연장된 선단 배기관(11F)은 반응기(110)에 연결되고, 반응기(110)에서 연장된 후단 배기관(11B)은 대기 중 또는 이코노마이저로 연장된다.As shown in FIGS. 1 and 2, the front exhaust pipe 11F extending from the engine 10 is connected to the reactor 110, and the rear exhaust pipe 11B extending from the reactor 110 is discharged to the atmosphere or to the economizer. is extended

따라서 엔진(10)에서 발생한 배기가스는 선단 배기관(11F)을 따라 반응기(110) 내부로 유입된다.Accordingly, the exhaust gas generated from the engine 10 is introduced into the reactor 110 along the front end exhaust pipe 11F.

반응기(110)는 그 하단에 선단 배기관(11F)이 연결되는 유입구(111)가 형성되고, 반응기(110)의 상단에는 후단 배기관(11B)이 연결되는 배출구(113)가 형성되며, 유입구(111)에는 입구 밸브(111V)가 그리고 배출구(113)에는 출구 밸브(113V)가 장착된다. In the reactor 110, an inlet 111 to which the front end exhaust pipe 11F is connected is formed at the bottom thereof, and an outlet 113 to which the rear end exhaust pipe 11B is connected is formed at the top of the reactor 110, and the inlet 111 ) is equipped with an inlet valve (111V) and an outlet valve (113V) is attached to the outlet (113).

이와 같이 구성된 반응기(110)에 있어서, 입구 밸브(111V)와 출구 밸브(113V)를 폐쇄하면 반응기(110) 내부가 폐쇄되고, 입구 밸브(111V)와 출구 밸브(113V)를 개방하면 엔진(10)에서 발생한 배기가스가 선단 배기관(11F)을 따라 반응기(110)로 유입된 후 후단 배기관(11B)을 따라 반응기(110) 외부로 배기된다.In the reactor 110 configured as described above, when the inlet valve 111V and the outlet valve 113V are closed, the inside of the reactor 110 is closed, and when the inlet valve 111V and the outlet valve 113V are opened, the engine 10 The exhaust gas generated in ) is introduced into the reactor 110 along the front end exhaust pipe 11F and then exhausted to the outside of the reactor 110 along the rear end exhaust pipe 11B.

한편, 반응기(110)의 내부에는 메탄산화촉매(Methane Oxidation Catalyst : MOC)(120)가 장착된다. 그 일 예로서 복수의 메탄산화촉매(120)가 배기가스의 유동방향을 따라 간격을 두고 반응기(110) 내부에 장착됨에 따라 유입구(111)로 유입된 배기가스가 배출구(113) 쪽으로 유동하면서 복수의 메탄산화촉매(120)를 순차적으로 통과하게 된다.Meanwhile, a methane oxidation catalyst (MOC) 120 is installed inside the reactor 110 . As an example, as the plurality of methane oxidation catalysts 120 are installed inside the reactor 110 at intervals along the flow direction of the exhaust gas, the exhaust gas introduced into the inlet 111 flows toward the outlet 113 while the plurality It passes through the methane oxidation catalyst 120 in sequence.

메탄산화촉매(120)는 팔라듐(Pd) 기반 촉매로서, 배기가스의 메탄(CH4)을 아래의 화학식 반응을 통해 물과 이산화탄소(CO2)로 산화시킨다.The methane oxidation catalyst 120 is a palladium (Pd)-based catalyst, and oxidizes methane (CH4) in exhaust gas to water and carbon dioxide (CO2) through the following chemical reaction.

Figure pat00001
Figure pat00001

따라서 반응기(110)로 유입된 메탄은 메탄산화촉매(120)를 통과하면서 상기 화학식 1과 같이 물과 이산화탄소로 산화된 후 후단 배기관(11B)을 통해 배기된다. Therefore, methane introduced into the reactor 110 is oxidized to water and carbon dioxide as shown in Chemical Formula 1 while passing through the methane oxidation catalyst 120 and then exhausted through the downstream exhaust pipe 11B.

메탄은 이산화탄소보다 28배가 강한 지구온난화가스물질로서, 메탄을 산화시켜 이산화탄소를 배기함에 따라 메탄 배출에 비해 지구온난화를 감소시킬 수 있다.Methane is a global warming gas substance that is 28 times stronger than carbon dioxide, and as methane is oxidized to emit carbon dioxide, global warming can be reduced compared to methane emissions.

한편, 메탄이 산화되는 중에 메탄산화촉매(120) 또한 산화되어 촉매 표면에 산화물질인 PdO가 형성된다. 촉매 표면에 산화물질인 PdO가 형성되면 메탄과의 접촉이 차단되어 촉매반응 즉 메탄의 산화 효율이 저하된다.Meanwhile, while methane is oxidized, the methane oxidation catalyst 120 is also oxidized, and PdO, an oxidizing substance, is formed on the surface of the catalyst. When PdO, an oxidizing substance, is formed on the surface of the catalyst, the contact with methane is blocked and the catalytic reaction, that is, the efficiency of methane oxidation is lowered.

본 발명은 메탄산화촉매(120)에 산화물질인 PdO가 형성되었을 경우 발생하는 메탄의 산화성능 저하를 다시 향상시킬 수 있도록 메탄산화촉매(120)를 재생하는 것에 그 목적이 있으며, 목적을 구현하기 위해서 반응기(110)에 재생가스를 주입한다.An object of the present invention is to regenerate the methane oxidation catalyst 120 so as to improve the oxidation performance of methane generated when PdO, an oxidizing agent, is formed in the methane oxidation catalyst 120. For this purpose, the regeneration gas is injected into the reactor 110.

재생가스를 반응기(110)에 주입하여 메탄산화촉매(120)를 재생하기 위한 본 발명에 따른 메탄산화촉매 재생장치는, 반응기(110)의 내부로 연장되며 배기가스의 유동 방향에 있어 메탄산화촉매(120)의 상류에 위치하여 메탄산화촉매(120)로 재생가스를 분사하는 재생가스 분기관(131)들과, 반응기(110) 내부에 장착된 복수의 메탄산화촉매(120)들 중에 재생하고자 하는 메탄산화촉매(120)를 선택하여 재생할 수 있도록 재생가스 분기관(131) 각각에 장착된 밸브(131V)들과, 반응기(110) 외부에 위치하며 재생가스 분기관(131)들이 연결된 재생가스 공급라인(130)을 포함한다.The methane oxidation catalyst regeneration device according to the present invention for regenerating the methane oxidation catalyst 120 by injecting the regeneration gas into the reactor 110 extends into the reactor 110 and in the flow direction of the exhaust gas, the methane oxidation catalyst Regeneration gas branch pipes 131 located upstream of the methane oxidation catalyst 120 to inject regeneration gas into the methane oxidation catalyst 120, and a plurality of methane oxidation catalysts 120 installed inside the reactor 110. Valves 131V mounted on each of the regeneration gas manifolds 131 to select and regenerate the methane oxidation catalyst 120 that is located outside the reactor 110 and connected to the regeneration gas manifolds 131 A supply line 130 is included.

이와 같이 구성된 메탄산화촉매 재생장치에 있어서, 재생가스 공급라인(130)에 인가되는 압력은 폐쇄된 반응기(110) 내부의 압력보다 높게 형성함으로써, 재생가스 분기관(131)에 설치된 밸브(131V)를 개방하면 압력 차에 의해 재생가스는 재생가스 공급라인(130)과 재생가스 분기관(131)을 통해 반응기(110) 내부로 유입된다. 이때 재생가스 분기관(131)에서 분사된 재생가스는 마주하는 메탄산화촉매(120)로 유입된다.In the methane oxidation catalyst regeneration apparatus configured as described above, the pressure applied to the regeneration gas supply line 130 is formed higher than the pressure inside the closed reactor 110, so that the valve 131V installed in the regeneration gas branch pipe 131 When is opened, the regeneration gas is introduced into the reactor 110 through the regeneration gas supply line 130 and the regeneration gas branch pipe 131 due to the pressure difference. At this time, the regeneration gas injected from the regeneration gas branch pipe 131 flows into the methane oxidation catalyst 120 facing each other.

한편, 재생가스는 PdO를 환원할 수 있는 N2, H2, HC 중 어느 한 종류의 가스 또는 특정 혼합비로 혼합된 가스로 구성할 수 있으며, 재생가스는 메탄산화촉매(120)에 발생된 PdO를 환원시켜 메탄산화촉매(120)를 재생한다.On the other hand, the regeneration gas can be composed of any one of N2, H2, and HC capable of reducing PdO, or a gas mixed at a specific mixing ratio, and the regeneration gas reduces PdO generated in the methane oxidation catalyst 120 to regenerate the methane oxidation catalyst 120.

이와 같이 메탄산화촉매(120)에서 PdO를 환원시키는 재생작업을 통해 메탄산화촉매(120)는 재생되고, 이후 입구 밸브(111V)와 출구 밸브(113V)를 개방하여 배기가스의 메탄이 반응기(110) 내부로 유입되면 화학식 1의 반응식과 같이 메탄의 산화 성능이 향상된다.As such, the methane oxidation catalyst 120 is regenerated through the regeneration operation of reducing PdO in the methane oxidation catalyst 120, and then the inlet valve 111V and the outlet valve 113V are opened so that the methane of the exhaust gas is discharged from the reactor 110 ) When introduced into the interior, the oxidation performance of methane is improved as shown in the reaction formula (1).

한편, 앞서 설명한 메탄산화촉매 재생장치는 반응기(110)의 내부에 설치된 메탄산화촉매(120)들 중 도 2에 보이듯이 일부 메탄산화촉매를 재생하거나 전체 메탄산화촉매를 재생할 수 있도록 재생가스 분기관(131)에 밸브(131V)를 설치하였으나, 도 3 및 도 4에 도시된 바와 같이 반응기(110)의 내부에 설치된 전체 메탄산화촉매(120)들을 일괄적으로 재생하도록 구성할 수 있다.Meanwhile, as shown in FIG. 2 among the methane oxidation catalysts 120 installed inside the reactor 110, the methane oxidation catalyst regeneration apparatus described above includes a regeneration gas branch pipe to regenerate some of the methane oxidation catalysts or to regenerate the entire methane oxidation catalyst. Although the valve 131V is installed in the valve 131, as shown in FIGS. 3 and 4, the entire methane oxidation catalyst 120 installed inside the reactor 110 may be collectively regenerated.

이 경우에는 도 3에 보이듯이, 재생가스 분기관(131)은 재생가스 공급라인(130)에서 분기되며, 재생가스 공급라인(130)에 밸브(130V)를 설치한다.In this case, as shown in FIG. 3, the regeneration gas branch pipe 131 is branched from the regeneration gas supply line 130, and a valve 130V is installed in the regeneration gas supply line 130.

따라서 재생가스 공급라인(130)에 설치된 밸브(130V)를 개방하면 재생가스는 재생가스 공급라인(130)과 분기된 재생가스 분기관(131)을 통해 반응기(110)로 유입되며, 각 메탄산화촉매(120)와 대응하여 상류 쪽에 위치한 재생가스 분기관(131)을 통해 분사된 재생가스는 각 메탄산화촉매(120)로 유입되어 반응기(110) 내부의 전체 메탄산화촉매(120)를 한꺼번에 재생할 수 있게 구성할 수도 있다.Therefore, when the valve 130V installed in the regeneration gas supply line 130 is opened, the regeneration gas flows into the reactor 110 through the regeneration gas supply line 130 and the regeneration gas branch pipe 131 branched off, and each methane oxidation The regeneration gas injected through the regeneration gas branch pipe 131 located upstream in correspondence with the catalyst 120 flows into each methane oxidation catalyst 120 and regenerates all the methane oxidation catalysts 120 inside the reactor 110 at once. It can also be configured to be .

10 : 엔진
11F, 11B : 배기관
110 : 반응기
111 : 유입구
111V : 입구 밸브
113 : 배출구
113V : 출구 밸브
120 : 메탄산화촉매(MOC)
130 : 재생가스 공급라인
130V : 밸브
131 : 재생가스 분기관
131V : 밸브10 : engine
11F, 11B: exhaust pipe
110: reactor
111: inlet
111V: inlet valve
113: outlet
113V: Outlet valve
120: methane oxidation catalyst (MOC)
130: regeneration gas supply line
130V: Valve
131: regeneration gas branch pipe
131V: Valve

Claims (7)

메탄산화촉매가 장착된 반응기와,
반응기로 재생가스를 공급하는 재생가스 공급라인과,
재생가스 공급라인에서 분기되어 반응기 내부의 메탄산화촉매의 상류 측으로 연장되며 메탄산화촉매를 향해 재생가스를 분사하는 재생가스 분기관을 포함하며,
재생가스 분기관에서 분사된 재생가스는 메탄산화촉매에 형성된 PdO를 환원시키는 것을 특징으로 하는 메탄산화촉매 재생장치.
A reactor equipped with a methane oxidation catalyst;
A regeneration gas supply line for supplying regeneration gas to the reactor;
A regeneration gas branch pipe branching from the regeneration gas supply line and extending upstream of the methane oxidation catalyst inside the reactor and injecting the regeneration gas toward the methane oxidation catalyst,
The regeneration gas injected from the regeneration gas branch pipe reduces the PdO formed in the methane oxidation catalyst.
 제1항에 있어서,
반응기의 내부에는 복수의 메탄산화촉매가 배기가스의 진행방향을 따라 간격을 두고 배치되며, 각 메탄산화촉매 마다 재생가스 분기관이 각각 연장되어 위치하는 것을 특징으로 하는 메탄산화촉매 재생장치.
According to claim 1,
Inside the reactor, a plurality of methane oxidation catalysts are disposed at intervals along the traveling direction of exhaust gas, and a regeneration gas branch pipe is extended for each methane oxidation catalyst.
 제1항 또는 제2항에 있어서,
재생가스 분기관에는 밸브가 장착되어 재생가스 공급라인에서 재생가스 분기관으로 재생가스의 공급을 제어하는 것을 특징으로 하는 메탄산화촉매 재생장치.
According to claim 1 or 2,
A methane oxidation catalyst regeneration apparatus, characterized in that a valve is mounted on the regeneration gas branch pipe to control the supply of regeneration gas from the regeneration gas supply line to the regeneration gas branch pipe.
 제1항 또는 제2항에 있어서,
재생가스 공급라인에는 밸브가 장착되어 재생가스 공급라인으로 재생가스의 공급을 제어하는 것을 특징으로 하는 메탄산화촉매 재생장치.
According to claim 1 or 2,
A methane oxidation catalyst regeneration apparatus, characterized in that a valve is mounted on the regeneration gas supply line to control the supply of regeneration gas to the regeneration gas supply line.
 메탄산화촉매에 형성된 PdO를 환원시켜 메탄산화촉매를 재생하는 방법으로서,
메탄산화촉매가 장착된 반응기를 폐쇄하는 단계와,
메탄산화촉매의 상류 쪽에 재생가스를 주입하여 PdO를 환원하는 단계를 포함하는 것을 특징으로 하는 메탄산화촉매 재생방법.
A method of regenerating a methane oxidation catalyst by reducing PdO formed in the methane oxidation catalyst,
Closing the reactor equipped with the methane oxidation catalyst;
A method for regenerating a methane oxidation catalyst comprising the step of reducing PdO by injecting a regeneration gas upstream of the methane oxidation catalyst.
 제5항에 있어서,
반응기의 내부에 장착된 복수의 메탄산화촉매 중 일부의 메탄산화촉매에만 재생가스를 공급하여 메탄산화촉매의 재생을 선택적으로 수행하는 단계를 더 포함하는 것을 특징으로 하는 메탄산화촉매 재생방법.
According to claim 5,
The methane oxidation catalyst regeneration method further comprising the step of selectively performing regeneration of the methane oxidation catalyst by supplying a regeneration gas to only some of the methane oxidation catalysts among the plurality of methane oxidation catalysts installed inside the reactor.
 제5항에 있어서,
반응기의 내부에 장착된 복수의 메탄산화촉매 각각에 재생가스를 공급하여 전체 메탄산화촉매를 재생하는 단계를 더 포함하는 것을 특징으로 하는 메탄산화촉매 재생방법.According to claim 5,
A method for regenerating the methane oxidation catalyst, further comprising regenerating the entire methane oxidation catalyst by supplying a regeneration gas to each of the plurality of methane oxidation catalysts mounted inside the reactor.
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