KR102273996B1 - Nitrogen oxide reduction agent comprising rrea containing fine bubbles - Google Patents

Nitrogen oxide reduction agent comprising rrea containing fine bubbles Download PDF

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KR102273996B1
KR102273996B1 KR1020150107986A KR20150107986A KR102273996B1 KR 102273996 B1 KR102273996 B1 KR 102273996B1 KR 1020150107986 A KR1020150107986 A KR 1020150107986A KR 20150107986 A KR20150107986 A KR 20150107986A KR 102273996 B1 KR102273996 B1 KR 102273996B1
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urea
nitrogen oxide
reducing agent
present
nitrogen
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KR1020150107986A
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Korean (ko)
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KR20170015680A (en
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김종민
오승훈
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중앙대학교 산학협력단
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    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • 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 미세버블 함유 요소수를 포함하는 질소산화물 환원제에 관한 것이다.The present invention relates to a nitrogen oxide reducing agent comprising microbubble-containing urea water.

Description

미세버블 함유 요소수를 포함하는 질소산화물 환원제{Nitrogen oxide reduction agent comprising rrea containing fine bubbles}Nitrogen oxide reduction agent comprising rrea containing fine bubbles

본 발명은 UREA-SCR 시스템에서 사용되는 요소수 질소환원제에 관한 것이다.The present invention relates to a urea water nitrogen reducing agent used in the UREA-SCR system.

유럽에서는 Adblue라는 이름으로 통일되어 공급되고 있으며, 또한 국제적으로 요소수 용액이라는 뜻으로 사용되는 용어로 AUS(Aqueous Urea Solution)가 있다. 기본적으로 Urea는 사전적인 의미로는 요소를 뜻하지만 자동차에서는 요소수 자동차 촉매제라는 의미로 사용되고 있다. 요소와 물로 주로 이루어진 우레아는 자동차 질소산화물을 저감시키기 위한 장치(SCR)에 사용되는 액상 화학물질이다. 요소수는 온도에 따라 어는 점의 변화가 매우 큰데, 요소수 농도가 32.5% 일 때 어는점이 -11℃로 가장 낮기 때문에 표준을 정할 때 자동차용 요소수는 32.5%로 정하고 있다. In Europe, it is uniformly supplied under the name of Adblue, and there is AUS (Aqueous Urea Solution) as a term used internationally to mean urea solution. Basically, Urea means urea in the dictionary meaning, but in automobiles, it is used in the meaning of urea water as an automobile catalyst. Urea, which consists mainly of urea and water, is a liquid chemical used in automotive nitrogen oxide reduction systems (SCRs). The number of urea has a very large change in freezing point depending on the temperature. When the concentration of urea is 32.5%, the freezing point is -11℃, which is the lowest. Therefore, when setting the standard, the number of urea for automobiles is set at 32.5%.

유로4와 유로5등 유럽환경기준 도입에 따라 친환경적인 자동차의 보급과 편리한 사용을 위해 표준화된 환원제로 쓰이고 있는 우레아 요소수는 자동차 SCR 엔진의 촉매장치에 뿌려져 온도에 따라 자동으로 분사되어 질소산화물 배출시 산화물을 질소로 환원해 주는 역할을 한다.In accordance with the introduction of European environmental standards such as Euro 4 and Euro 5, urea urea water, which is used as a standardized reducing agent for the supply and convenient use of eco-friendly automobiles, is sprayed on the catalyst device of the automobile SCR engine and automatically sprayed according to the temperature to emit nitrogen oxides. It serves to reduce oxides to nitrogen.

Urea SCR 시스템은 우레아 분사시스템, 촉매, 믹서, 센서 등으로 구성되는데, 촉매의 담채는 세라믹의 벌집모양 담채가 주로 쓰인다. SCR 촉매전단에 우레아를 배출가스 중에 균일하게 분산시키기 위하여 믹서를 사용하며 유레아 분사량을 제어하기 위해 SCR장치 입구와 출구에 질소산화물 센서를 장착하여 사용한다. Urea SCR system is composed of urea injection system, catalyst, mixer, sensor, etc. The catalyst support is mainly ceramic honeycomb support. A mixer is used to uniformly disperse urea in the exhaust gas in front of the SCR catalyst, and nitrogen oxide sensors are installed at the inlet and outlet of the SCR device to control the amount of urea injection.

유레아를 사용하면 연소활동이 원활히 이루어지기 때문에 자동차 엔진의 성능을 향상시키고 이로 인해 연비가 약 6% 상승되어 결과적으로 CO2가 5~6% 줄어들고, 요소수를 통한 질소산화물 저감효과에 대해서는 온도에 따라 저감효과가 다르게 나타난다.The urea since the combustion activity smoothly performed in the temperature for improving the performance of an automobile engine and which because of the fuel consumption is increased about 6% as a result CO 2 is 5-6% less, reducing the nitrogen oxides by the number of elements effects The reduction effect is different depending on the

국내 한 연구원 연구결과에 의하면 자동차 온도 감지 센서로 우레아가 온도에 따라 자동적으로 분사되는데, 초기에 시동을 걸어 자동차 온도가 200℃ 정도 올라갔을 때 우레아 분사로 인한 질소산화물 저감은 50~60%정도이며, 자동차 온도가 300℃ 정도 됐을 때 분사되는 우레아 질소산화물 저감 효과는 90%까지 달한다. 이에 따르면 우레아는 공기 중의 질소가 산소가 만난 질소산화물을 우레아 요소수를 통해 무해한 상태의 원래의 질소로 환원시켜 주는 역할을 하는데, 이 같은 요소수 반응을 일으키려면 촉매제가 필요하기 때문에 벌집 모양의 촉매장치에 요소수를 분사시켜, 원활한 질소 환원 반응을 일으키도록 하는 기술적인 시스템이 필요하며, 이 시스템을 우레아 SCR 이라고 한다. According to the research result of a research institute in Korea, urea is automatically injected according to the temperature by the car temperature sensor. When the temperature of the car rises by 200℃ after starting the engine at the beginning, the reduction of nitrogen oxide due to urea injection is about 50 to 60%. , the reduction effect of urea nitrogen oxides sprayed when the car temperature reaches 300℃ reaches up to 90%. According to this, urea plays a role in reducing nitrogen oxides in the air, which is met by oxygen, to original nitrogen in a harmless state through urea urea water. Since a catalyst is required to cause such a urea water reaction, a honeycomb catalyst A technical system is required to cause a smooth nitrogen reduction reaction by injecting urea water into the device, and this system is called urea SCR.

이러한 촉매장치는 배기관에 장착되어 있어야 하며 요소수를 자동차용으로 쓰려면 중금속 등의 불순물 정제 과정이 필수적이기 때문에 단순히 요소를 물에 타서 엔진에 뿌리는 것으로는 질소산화물 저감에 전혀 효과가 없다. 또한, 불법 촉매제 제조를 막기 위해서는 엄격한 유레아 품질 기준 마련이 필요하다. 자동차용 질소산화물 저감기술로는 Urea SCR 외에도 HC-SCR, LNT등의 기술이 개발되고 있으나, Urea SCR 기술은 다른 후처리 기술에 비해 촉매반응 온도 대역이 넓고, 내구성이 우수하다는 장점이 있으며 약 60~80% 수준의 높은 질소산화물 정화효율을 얻을 수 있어 가장 활발히 연구되고 있다.Such a catalyst device must be installed in the exhaust pipe, and since the purification process of impurities such as heavy metals is essential to use urea water for automobiles, simply adding urea to water and spraying it on the engine is not effective at all in reducing nitrogen oxides. In addition, strict urea quality standards are required to prevent illegal catalyst manufacturing. In addition to Urea SCR, HC-SCR and LNT technologies are being developed as nitrogen oxide reduction technologies for automobiles. However, compared to other post-treatment technologies, Urea SCR technology has a wider catalytic reaction temperature range and superior durability. It is being studied most actively because it can obtain a high nitrogen oxide purification efficiency of ~80%.

본 발명은 요소수에 의한 Urea-SCR 시스템에서 배기 가스 내의 질소산화물 환원제로서, 현존하는 요소수에 비해 놓은 효율의 환원제를 제공함을 목적으로 한다.An object of the present invention is to provide a reducing agent with high efficiency compared to existing urea water as a nitrogen oxide reducing agent in exhaust gas in a Urea-SCR system using urea water.

본 발명은 미세버블 함유 요소수를 포함하는 질소산화물 환원제를 제공한다.The present invention provides a nitrogen oxide reducing agent comprising urea water containing microbubbles.

본 발명의 질소산화물 환원제는, Urea-SCR 시스템에서 사용될 수 있다. The nitrogen oxide reducing agent of the present invention may be used in the Urea-SCR system.

본 발명의 요소수는 증류수 및 요소(CO(NH2)2)의 혼합물이다.The urea water of the present invention is a mixture of distilled water and urea (CO(NH 2 ) 2 ).

상기 미세버블은 수소 또는 공기를 포함함을 특징으로 한다. 공기를 포함하는 미세버블 함유 요소수는 이러한 미세버블을 포함하지 않는 요소수에 비해 배기가스 내의 질소화합물의 환원 효율이 극대화된다. 특히 수소를 포함하는 경우 버블 내의 수소가 촉매반응에 의해 유리화되어 배기가스 내의 질소화합물과 화학반응을 통해 질소와 물을 생성할 수 있어, 이의 환원 효율을 더욱 극대화할 수 있다.The microbubbles are characterized in that they contain hydrogen or air. The urea water containing microbubbles including air maximizes the reduction efficiency of nitrogen compounds in the exhaust gas compared to the urea water containing no such microbubbles. In particular, when hydrogen is included, hydrogen in the bubble is liberated by a catalytic reaction to generate nitrogen and water through a chemical reaction with nitrogen compounds in the exhaust gas, thereby further maximizing the reduction efficiency.

본 발명의 미세버블은 이의 직경이 약 1㎚ 내지 약 1,000㎛일 수 있으나, 이에 제한되지 않을 수 있다. 미세버블이 떠오르지 않고 요수소 내에 오래 유지될 수 있을 정도의 작은 크기이면 되지 이의 크기에 제한되지 않는다. 특히 1㎛ 미만의 나노사이크의 미세버블은 요소수 내에 떠오르지 않고 오래 지속되어 미세버블 함유 요소수로서 역할할 수 있다.The microbubbles of the present invention may have a diameter of about 1 nm to about 1,000 μm, but may not be limited thereto. It should be of a size small enough that microbubbles do not float and can be maintained for a long time in urea, but the size is not limited thereto. In particular, nano-sized microbubbles of less than 1 μm do not float in the urea water and last for a long time, and thus can serve as the urea water containing microbubbles.

다른 측면으로서, 본 발명은 배기 가스라인에 공급하여 질소산화물을 제거하는 Urea-SCR 시스템을 제공하며, 상기 시스템은, 본 발명의 질소산화물 환원제를 포함하는 환원제공급부; 및 상기 질소산화물 환원제를 무화시켜 상기 배기 가스라인에 공급되도록 구성된 분무장치를 포함한다.As another aspect, the present invention provides a Urea-SCR system for removing nitrogen oxide by supplying it to an exhaust gas line, the system comprising: a reducing agent supply unit containing the nitrogen oxide reducing agent of the present invention; and a spraying device configured to atomize the nitrogen oxide reducing agent and supply it to the exhaust gas line.

본 발명은 Urea-SCR 시스템에서 사용될 수 있는 미세버블을 포함하는 요소수를 제공하여, 현존하는 환원제에 비해 월등한 환원 반응 촉진의 하여 우수한 질소산화물 감소 효과를 제공한다.The present invention provides the urea water containing microbubbles that can be used in the Urea-SCR system, and provides an excellent effect of reducing nitrogen oxides by promoting a reduction reaction superior to that of existing reducing agents.

이하, 본 발명의 실시예에 대해 상세히 설명한다. 본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는바, 특정 실시예들을 예시하고 본문에 상세하게 설명하고자 한다. 그러나 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. Hereinafter, embodiments of the present invention will be described in detail. Since the present invention may have various changes and may have various forms, specific embodiments will be illustrated and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

본 출원에서 사용한 용어는 단지 특정한 실시 예를 설명하기 위해 사용된 것으로서 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terms used in the present application are used only to describe specific embodiments and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, step, operation, component, part, or combination thereof described in the specification is present, and includes one or more other features or steps. , it should be understood that it does not preclude the possibility of the existence or addition of , operation, components, parts, or combinations thereof.

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. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.
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 this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

본 발명은 미세버블 함유 요소수를 포함하는 질소산화물 환원제를 제공한다. 본 발명의 미세버블 함유 요소수는 마이크로 또는 나노 사이즈의 직경의 버블이 요소수 내에 분산되어 있는 요소수를 의미하며, 상기 버블은 기체를 함유하고 있고, 상기 버블의 크기는 충분히 작아서 요소수 내에 오랜 시간 지속되어 있는 상태를 제공한다. 여기서 오랜 시간이란 수일 또는 수개월의 시간일 수 있고 이 시간에 한정되는 것이 아니라 제조된 요소수가 SCR 시스템에 투입되기 전까지의 통상의 보관 기간일 수 있을 것이다. 1 ㎛ 미만의 나노 사이즈의 경우 기체 함유 미세버블이 요수수 내에 오랜 기간 부유하지 않고 지속될 수 있다.The present invention provides a nitrogen oxide reducing agent comprising urea water containing microbubbles. The number of urea containing microbubbles of the present invention means the number of urea in which micro- or nano-sized diameter bubbles are dispersed in the urea water, the bubble contains gas, and the size of the bubble is sufficiently small that it has a long time in the urea water. Provides a state that lasts time. Here, the long time may be a time of several days or several months, and is not limited to this time, but may be a normal storage period until the manufactured urea water is put into the SCR system. In the case of a nano size of less than 1 μm, gas-containing microbubbles may persist for a long period of time without floating in water.

미세버블 함유 요소수 제조방법은 다양한 방법으로 제조될 수 있으며, 특정 제조 방법에 한정되는 것은 아니나, 본 발명자의 특허인 국제특허출원 번호 PCT/KR2013/010476가 참조될 수 있으며, 이는 본원에 참조로서 통합된다.The method for manufacturing urea water containing microbubbles can be prepared by various methods, and is not limited to a specific manufacturing method, but International Patent Application No. PCT/KR2013/010476, which is a patent of the present inventor, may be referred to, which is incorporated herein by reference. are integrated

본 발명은 배기 가스라인에 공급하여 질소산화물을 제거하는 Urea-SCR 시스템을 제공하며, 상기 시스템은, 본 발명의 질소산화물 환원제를 포함하는 환원제공급부; 및 상기 질소산화물 환원제를 무화시켜 상기 배기 가스라인에 공급되도록 구성된 분무장치를 포함한다.The present invention provides a Urea-SCR system for removing nitrogen oxide by supplying it to an exhaust gas line, the system comprising: a reducing agent supply unit containing the nitrogen oxide reducing agent of the present invention; and a spraying device configured to atomize the nitrogen oxide reducing agent and supply it to the exhaust gas line.

Claims (7)

증류수 및 요소(CO(NH2)2)의 혼합물인 요소수, 및
상기 요소수 내에 함유된 수소를 포함하는 가스를 포함하는 1000nm 이하의 크기의 미세버블을 포함하는, Urea-SCR 시스템용 질소산화물 환원제.urea water, which is a mixture of distilled water and urea (CO(NH 2 ) 2 ), and
A nitrogen oxide reducing agent for the Urea-SCR system, comprising microbubbles with a size of 1000 nm or less containing a gas containing hydrogen contained in the urea water. 삭제delete 삭제delete 삭제delete 제1항에 있어서,
상기 미세버블은 추가로 공기를 포함하는,
질소산화물 환원제.According to claim 1,
The microbubbles further include air,
Nitrogen oxide reducing agent. 삭제delete 배기 가스라인에 공급하여 질소산화물을 제거하는 Urea-SCR 시스템으로서,
상기 시스템은, 제1항의 질소산화물 환원제를 포함하는 환원제공급부; 및
상기 질소산화물 환원제를 무화시켜 상기 배기 가스라인에 공급되도록 구성된 분무장치를 포함하는,
Urea-SCR 시스템.As a Urea-SCR system that removes nitrogen oxides by supplying it to an exhaust gas line,
The system comprises: a reducing agent supply unit comprising the nitrogen oxide reducing agent of claim 1; and
Comprising a spraying device configured to atomize the nitrogen oxide reducing agent and supply it to the exhaust gas line,
Urea-SCR system.
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JP2010511493A (en) 2006-11-30 2010-04-15 ゼネラル・エレクトリック・カンパニイ Multi-bed selective catalytic reduction system and method for reducing nitrogen oxide emissions
JP2014037788A (en) 2012-08-13 2014-02-27 Isuzu Motors Ltd Exhaust gas post-processing device and internal combustion engine mounted with the same

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JP2010511493A (en) 2006-11-30 2010-04-15 ゼネラル・エレクトリック・カンパニイ Multi-bed selective catalytic reduction system and method for reducing nitrogen oxide emissions
JP2010077902A (en) * 2008-09-26 2010-04-08 Ud Trucks Corp Engine exhaust emission control device
JP2014037788A (en) 2012-08-13 2014-02-27 Isuzu Motors Ltd Exhaust gas post-processing device and internal combustion engine mounted with the same

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