WO2013089319A1 - Exhaust reducer for inhibiting discharge of white smoke from diesel engine - Google Patents

Exhaust reducer for inhibiting discharge of white smoke from diesel engine Download PDF

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Publication number
WO2013089319A1
WO2013089319A1 PCT/KR2012/001833 KR2012001833W WO2013089319A1 WO 2013089319 A1 WO2013089319 A1 WO 2013089319A1 KR 2012001833 W KR2012001833 W KR 2012001833W WO 2013089319 A1 WO2013089319 A1 WO 2013089319A1
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Prior art keywords
white smoke
diesel
smoke
doc
diesel engine
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PCT/KR2012/001833
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French (fr)
Korean (ko)
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한현식
이태우
하재어
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희성촉매 주식회사
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Publication of WO2013089319A1 publication Critical patent/WO2013089319A1/en

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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
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • 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
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—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
    • 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
    • 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
    • F01N3/24—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 constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • 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
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction

Definitions

  • the present invention relates to a smoke reduction device in which a noble metal content range is specified in a catalyst composition applied to diesel oxidation catalyst (DOC) and diesel particulate filter (DPF) catalysts to reduce white smoke generated in a diesel engine. It is about.
  • DOC diesel oxidation catalyst
  • DPF diesel particulate filter
  • Diesel engine exhaust products are mixtures of exhaust gases such as carbon monoxide ("CO"), hydrocarbons (“HC”) and nitrogen oxides (“NOx”) and condensates (soot) which constitute particulate matter. Soot in the exhaust product is solid or liquid particles contained in the gas produced through engine combustion or pyrolysis. Visible components are black smoke, blue smoke, yellow smoke and white smoke. There may be several complex sources of white smoke emissions, but white smoke itself consists of condensate or liquid fuel or sulfide components in the exhaust gas.
  • a housing installed to have a predetermined volume of space in the middle of an exhaust port to remove sulfides and moisture in the exhaust port; A plurality of positive electrode plates disposed inside the housing; A plurality of negative electrode rods spaced apart from each other at a predetermined distance with respect to the plurality of positive electrode plates; A high voltage generator converting power supplied from the outside into a high voltage DC voltage to conduct electricity between the positive electrode plate and the negative electrode rod; A driving state detection unit detecting a driving state of the vehicle; A control unit which controls the operation of the high voltage generation unit according to the driving state of the vehicle detected by the driving state detection unit; A removal apparatus including a drain passage provided to discharge condensate generated in the housing to the outside according to the operation of the high voltage generator is described.
  • the apparatus and method for controlling white smoke emission of a diesel vehicle disclosed in Korean Patent Laid-Open Publication No. 2004-0049334, when the diesel engine-mounted vehicle is left idle for a long time from the driving stop state, the engine is automatically turned off through the fuel cutoff control.
  • a method of controlling white smoke generation including a process of turning on and turning off an ignition on contact to an off contact when a predetermined time elapses after engine start.
  • the conventional approach to suppressing the white smoke has been to mechanically or electronically change the white smoke emission path of the white smoke emitted from the engine, which is not properly treated in the case of diesel engines using high sulfur fuels, and the exhaust gas treatment. There was a problem that the overall efficiency of the system is reduced.
  • the present invention is to suppress white smoke emission from a catalytic point of view. That is, the present invention relates to a device and a method for suppressing white smoke emission by adjusting a noble metal component of a catalyst composition applied to a smoke reduction device.
  • the present invention relates to a soot reduction device comprising a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) mounted on a rear end of a diesel engine, wherein the platinum / palladium weight ratio (Pt / Pd) of the diesel oxidation catalyst composition applied to the DOC.
  • DOC diesel oxidation catalyst
  • DPF diesel particulate filter
  • Is 0 ⁇ Pt / Pd ⁇ 1 relates to a smoke reduction device for suppressing the diesel exhaust smoke emissions.
  • the present invention is characterized in that only the palladium is contained as a noble metal component of the diesel particulate filter catalyst composition.
  • the ratio of the noble metal component of the diesel oxidation catalyst composition according to the present invention is limited to a predetermined ratio according to the present invention, the white smoke emission generated during the initial start-up of the diesel engine is particularly reduced.
  • 1 is a photograph of white smoke emission of a DOC and DPF equipped diesel engine vehicle.
  • Figure 2 is a photograph of the white smoke emission experiment apparatus.
  • WS white smoke
  • Figure 4 is a graph showing the relationship between the measurement results and the optical smoke smoke measurement.
  • 5 is a graph showing the results of the measurement of the light transmission soot of the normal fuel and high sulfur fuel.
  • the term "soot reduction device” means a diesel oxidation catalyst and a diesel particulate filter (DPF or CSF).
  • Diesel oxidation catalysts are oxidation catalysts comprising platinum group metals, base metals, and combinations thereof, which are catalysts for oxidizing and converting some of the unburned hydrocarbons (HC) and carbon monoxide (CO) and particulate matter into carbon dioxide and water. Is generally used coated on various monolith substrates. A diesel particulate filter is used continuously after the diesel oxidation catalyst.
  • Diesel particulate filter which is usually implemented as a ceramic wall flow filter, is coated with a catalyst component containing a platinum group metal component to remove particulate matter and force regeneration thereof.
  • platinum group metal is used interchangeably with “noble metal component” and means platinum and palladium.
  • Commercially available DOCs and DPFs consist of a number of precious metal components, including platinum and palladium.
  • FIG. 1 is a photograph of the white smoke emission experiment apparatus.
  • a smoke reduction device equipped with DOC and DPF is arranged at the rear end of the diesel engine, and the rear end of the smoke reduction device is connected with a muffler, and a light transmission smoke detector is installed at the rear of the muffler.
  • the light soot meter results are measured in% impermeability.
  • 3 is a graph showing white smoke (WS) emission at each measurement point temperature zone.
  • FIG. 4 is a graph showing the results of the measurement of the optical smoke detector and visual recognition of smoke.
  • 5 is a graph showing the results of the measurement of the light transmission type of the normal fuel and the high sulfur fuel, the normal fuel is less than 35% of the impermeability before and after the 200 °C muffler, the result of using the high sulfur fuel muffler rear temperature 200 °C The permeability reached 55% before and after, and the normal fuel did not emit visible white smoke, but the intrinsic sulfur fuel was observed to emit white smoke, and thus the white smoke emission standard established by the present inventors was determined to be appropriate.
  • the present inventors paid particular attention to the precious metal component among the catalyst components applied to the smoke reduction apparatus. It was determined that the main component of white lead is sulfide and the component that determines white lead production is due to the oxidizing power of oxidation catalyst component, especially precious metal component, especially platinum and palladium component.
  • Catalyst compositions coated as slurries in the DOC and DPF constituting the soot reduction device are known in the art and generally comprise a platinum group metal and base metal base composition.
  • a catalyst composition that can typically be used in DOC and DPFs contains a platinum group component (eg, platinum, palladium or rhodium component) dispersed on a high surface area refractory oxide support (eg ⁇ -alumina).
  • Suitable platinum group metal components are platinum and palladium.
  • the noble metal content including platinum and palladium loaded in the DOC, is about 20 g / ft 3 to 200 g / ft 3 , containing Pt alone or some Pd to obtain the best oxidation activity, usually Pt / Pd
  • the weight ratio is one or more. That is, the Pt: Pd ratio is about 10: 1 to 4: 1.
  • DPF or CSF
  • DOC also contains oxidizing catalyst components, and Pt alone or part of Pd is contained to obtain proper activity. Is more than 1
  • DOC and CSF catalyst compositions were prepared by adjusting the platinum and palladium component ratios contained in DOC and CSF by methods known in the art.
  • the prepared catalyst composition was slurried and coated on a conventional monolithic filter for DOC and a filter for CSF to assemble a smoke reduction device, and white smoke was measured by a light transmission type smoke analyzer according to the experimental apparatus shown in FIG. 1.
  • Table 1 summarizes the precious metal component ratios and the measured impermeability in each DOC and CSF prepared according to the examples.
  • FIGS. 6 and 7 are oxidation catalyst components applied in existing soot reduction apparatus, and the impermeability was observed at 35% or more to produce a visually recognized white lead, which was judged to be inadequate due to the white smoke.

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  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

The present invention is for inhibiting the discharge of white smoke from a catalytic perspective. The present invention relates to a composition for inhibiting the discharge of white smoke by adjusting the precious metal ingredients of a catalyst composition which is applied to an exhaust reducer. The present invention relates to a catalyst composition for an exhaust reducer for inhibiting the discharge of white smoke, which is mounted on a rear end of a diesel engine, comprising a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) or catalyzed soot filter (CSF) catalyst, wherein the weight ratio of platinum/palladium of the diesel oxidation catalyst is (Pt/Pd)dl 0 < Pd/Pt < 1. When the ratio of the precious metal ingredients of the diesel oxidation catalyst is limited to a specific ratio according to the present invention, the discharging of white smoke that is generated during the initial starting of a diesel engine, especially in the winter, can be significantly reduced.

Description

디젤엔진 백연 방출 억제를 위한 매연저감장치Soot Reduction Device for Suppressing Diesel Engine White Lead
본 발명은 디젤엔진에서 발생되는 백연 (white smoke)을 억제하기 위하여 매연저감장치인 디젤 산화 촉매 (DOC) 및 디젤 미립자 필터 (DPF) 촉매에 적용되는 촉매조성물에 귀금속 함량 범위가 특정되는 매연저감장치에 관한 것이다.The present invention relates to a smoke reduction device in which a noble metal content range is specified in a catalyst composition applied to diesel oxidation catalyst (DOC) and diesel particulate filter (DPF) catalysts to reduce white smoke generated in a diesel engine. It is about.
고유한 연료 경제성 및 저속에서의 높은 토크 장점을 가지는 압축 점화 디젤엔진은 연료가 매우 희박한 조건인 높은 공기 대 연료 (A/F) 비율로 운전되므로 디젤엔진은 기체상 탄화수소 및 일산화탄소의 배출은 매우 낮지만, 질소산화물 (NOx) 및 미립자는 비교적 높게 배출된다. 디젤엔진 배기생성물은 일산화탄소 ("CO"), 탄화수소 ("HC") 및 질소산화물 ("NOx")과 같은 배출가스 및 미립자 물질을 구성하는 응축물질 (매연)의 혼합물이다. 배기생성물 중 매연은 엔진 연소 또는 열분해 과정을 통해 생성된 가스 중에 포함되어 있는 고체 또는 액체 입자로서 눈에 보이는 부유 성분으로 흑색매연, 청색매연, 황색매연 및 백연 (white smoke)로 대별된다. 백연 배출에는 여러 가지 복합적인 원인이 있을 수 있으나, 백연 자체는 배기가스 내의 응축수 또는 액상연료 또는 황화물 성분들로 이루어진다.Compressed ignition diesel engines, which have inherent fuel economy and high torque advantages at low speeds, operate at a high air to fuel (A / F) ratio, where fuel is very sparse, so diesel engines have very low emissions of gaseous hydrocarbons and carbon monoxide. However, nitrogen oxides (NOx) and particulates are discharged relatively high. Diesel engine exhaust products are mixtures of exhaust gases such as carbon monoxide ("CO"), hydrocarbons ("HC") and nitrogen oxides ("NOx") and condensates (soot) which constitute particulate matter. Soot in the exhaust product is solid or liquid particles contained in the gas produced through engine combustion or pyrolysis. Visible components are black smoke, blue smoke, yellow smoke and white smoke. There may be several complex sources of white smoke emissions, but white smoke itself consists of condensate or liquid fuel or sulfide components in the exhaust gas.
백연 방출을 억제하기 위한 다양한 방법들 및 장치들이 개시되어 있다. 예를들면, 대한민국 특허 제0792951호의 디젤엔진의 백연 제거장치에 의하면, 배기구 내 황화물 및 수분을 제거하기 위하여 배기구로의 도중에 소정 용적의 공간을 가지도록 설치된 하우징과; 상기 하우징의 내부에 배치된 다수의 양전극판; 상기 다수의 양전극판에 대해 각각 일정 거리를 두고 이격되게 배치된 다수의 음전극봉; 외부로부터 제공되는 전원을 고압의 직류전압으로 변환하여 상기 양전극판과 상기 음전극봉 사이로 통전시키는 고전압 발생부; 차량의 주행상태를 검출하는 주행상태 검출부; 상기 주행상태 검출부로부터 검출되는 차량의 주행상태에 따라 상기 고전압 발생부의 작동을 제어하는 제어부 및; 상기 고전압 발생부의 작동에 따라 상기 하우징 내에 발생된 응축수를 외부로 배출시키도록 설치된 드레인 통로를 포함하는 제거장치가 기술된다. 또한, 대한민국 특허공개 제2004-0049334호인 디젤 차량의 백연 배출 제어장치 및 방법에 의하면, 디젤 엔진 장착 차량이 주행 정지 상태에서 장시간 공회전 상태로 방치되는 경우 연료 차단 제어를 통해 엔진의 시동을 자동 오프 시켜 백연 발생을 제어하는 것으로, 시동 온 상태에서 검출되는 차량의 각 상태 정보가 정지 상태로 장시간 공회전 중인지를 판단하는 과정과, 상기에서 정지 상태의 장시간 공회전인 것으로 판단되면 연료 차단을 통해 엔진 시동을 오프 시키는 과정과, 엔진 시동 후 일정 시간이 경과되면 점화 온 접점을 오프 접점으로 절환시키는 과정을 포함하는 백연 발생 제어방법이 개시된다.Various methods and devices for suppressing white smoke release are disclosed. For example, according to the apparatus for removing white smoke of a diesel engine of Korean Patent No. 0792951, a housing installed to have a predetermined volume of space in the middle of an exhaust port to remove sulfides and moisture in the exhaust port; A plurality of positive electrode plates disposed inside the housing; A plurality of negative electrode rods spaced apart from each other at a predetermined distance with respect to the plurality of positive electrode plates; A high voltage generator converting power supplied from the outside into a high voltage DC voltage to conduct electricity between the positive electrode plate and the negative electrode rod; A driving state detection unit detecting a driving state of the vehicle; A control unit which controls the operation of the high voltage generation unit according to the driving state of the vehicle detected by the driving state detection unit; A removal apparatus including a drain passage provided to discharge condensate generated in the housing to the outside according to the operation of the high voltage generator is described. In addition, according to the apparatus and method for controlling white smoke emission of a diesel vehicle disclosed in Korean Patent Laid-Open Publication No. 2004-0049334, when the diesel engine-mounted vehicle is left idle for a long time from the driving stop state, the engine is automatically turned off through the fuel cutoff control. By controlling the generation of smoke, the process of determining whether each state information of the vehicle detected in the start-up state is idle for a long time in the stop state, and if it is determined that the idle time is in the idle state for a long time, the engine is turned off by shutting off the fuel. Disclosed is a method of controlling white smoke generation including a process of turning on and turning off an ignition on contact to an off contact when a predetermined time elapses after engine start.
그러나, 종래 백연 억제 관련 접근 방법은 엔진에서 배출되는 백연을 기구적 또는 전자적으로 백연 배출 경로를 변경하는 것이었으나, 이는 고유황 연료가 사용되는 디젤엔진의 경우 적절하게 처리되지 못할 뿐 아니라 배기가스 처리시스템 전체 효율이 떨어지는 문제점이 있었다.However, the conventional approach to suppressing the white smoke has been to mechanically or electronically change the white smoke emission path of the white smoke emitted from the engine, which is not properly treated in the case of diesel engines using high sulfur fuels, and the exhaust gas treatment. There was a problem that the overall efficiency of the system is reduced.
본 발명은 촉매적인 관점에서 백연 방출을 억제하기 위한 것이다. 즉 매연저감장치에 적용되는 촉매조성물의 귀금속 성분을 조절하여 백연 배출을 억제하는 장치 및 방법에 관한 것이다.The present invention is to suppress white smoke emission from a catalytic point of view. That is, the present invention relates to a device and a method for suppressing white smoke emission by adjusting a noble metal component of a catalyst composition applied to a smoke reduction device.
본 발명은 디젤엔진 후단에 장착되는 디젤산화촉매 (DOC) 및 디젤미립자필터 (DPF)로 구성되는 매연저감장치에 있어서, DOC에 적용되는 디젤산화촉매조성물의 백금/팔라듐 중량 비율 (Pt/Pd)은 0 < Pt/Pd < 1인 것을 특징으로 하는, 디젤엔진 백연 방출 억제를 위한 매연저감장치에 관한 것이다. 비-제한적으로 본 발명은, 디젤미립자필터촉매조성물의 귀금속 성분으로는 팔라듐 만이 함유되는 것을 특징으로 한다.The present invention relates to a soot reduction device comprising a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) mounted on a rear end of a diesel engine, wherein the platinum / palladium weight ratio (Pt / Pd) of the diesel oxidation catalyst composition applied to the DOC. Is 0 <Pt / Pd <1, relates to a smoke reduction device for suppressing the diesel exhaust smoke emissions. Non-limitingly, the present invention is characterized in that only the palladium is contained as a noble metal component of the diesel particulate filter catalyst composition.
본 발명에 의한 디젤산화촉매조성물 귀금속 성분 비율이 본 발명에 의한 소정 비율로 국한되면 디젤엔진 초기 시동 시 특히 겨울철에 발생되는 백연 배출이 현저하게 감소된다.When the ratio of the noble metal component of the diesel oxidation catalyst composition according to the present invention is limited to a predetermined ratio according to the present invention, the white smoke emission generated during the initial start-up of the diesel engine is particularly reduced.
도 1은 DOC 및 DPF 장착 디젤엔진 차량의 백연 배출 사진이다.1 is a photograph of white smoke emission of a DOC and DPF equipped diesel engine vehicle.
도 2는 백연 배출 실험 장치 사진이다.Figure 2 is a photograph of the white smoke emission experiment apparatus.
도 3은 각 측정 지점 온도 구역에서의 백연 (WS) 배출 상태를 보이는 그래프이다.3 is a graph showing white smoke (WS) emission at each measurement point temperature zone.
도 4는 광투과식 매연측정기 측정 결과 및 시각적 백연 인식 관계를 보이는 그래프이다.Figure 4 is a graph showing the relationship between the measurement results and the optical smoke smoke measurement.
도 5는 정상 연료 및 고유황 연료의 광투과식 매연 측정 결과를 보이는 그래프이다.5 is a graph showing the results of the measurement of the light transmission soot of the normal fuel and high sulfur fuel.
도 6은 본 발명에 의한 촉매조성물이 적용된 매연저감장치에 대한 광투과식 매연측정기 측정 결과이다.6 is a measurement result of the light transmission type smoke detector for the smoke reduction device to which the catalyst composition according to the present invention is applied.
도 7은 비교 촉매조성물이 적용된 매연저감장치에 대한 광투과식 매연측정기 측정 결과이다.7 is a measurement result of the light transmission type soot measuring device for the smoke reduction device to which the comparative catalyst composition is applied.
본 발명자들은 디젤엔진 백연 배출을 억제하기 위한 시도로 매연저감장치를 이루는 유닛들의 촉매 조성, 특히 귀금속 성분을 조절하였다. 본 발명에서 “매연저감장치”라 함은 디젤산화촉매 및 디젤미립자필터 (DPF 또는 CSF)를 의미한다. 디젤산화촉매는 백금족 금속, 베이스 금속 및 이들의 조합을 포함하는 산화촉매로서, 연소되지 않은 탄화수소 (HC) 및 일산화탄소 (CO) 및 미립자 물질의 일부를 산화하여 이산화탄소 및 물로 전환시키는 촉매이며, 이러한 촉매는 일반적으로 다양한 모노리스 기재에 코팅되어 사용된다. 디젤산화촉매 후단에 연속하여 디젤미립자필터가 사용된다. 통상 세라믹 기재 필터 (wall flow filter)로 구현되는 디젤미립자필터는 미립자 물질을 제거하고 이를 강제 재생하기 위하여 백금족 금속 성분을 함유하는 촉매성분이 코팅된다. 본원에서 사용되는 용어 “백금족 금속”은 “귀금속 성분”과 상호 교환적으로 사용되며 백금 및 팔라듐을 의미한다. 상업적으로 입수되는 DOC 및 DPF에는 백금 및 팔라듐을 포함한 다수의 귀금속 성분으로 구성된다.The inventors have adjusted the catalyst composition, in particular the noble metal component, of the units making up the soot reduction device in an attempt to suppress diesel engine white smoke emissions. In the present invention, the term "soot reduction device" means a diesel oxidation catalyst and a diesel particulate filter (DPF or CSF). Diesel oxidation catalysts are oxidation catalysts comprising platinum group metals, base metals, and combinations thereof, which are catalysts for oxidizing and converting some of the unburned hydrocarbons (HC) and carbon monoxide (CO) and particulate matter into carbon dioxide and water. Is generally used coated on various monolith substrates. A diesel particulate filter is used continuously after the diesel oxidation catalyst. Diesel particulate filter, which is usually implemented as a ceramic wall flow filter, is coated with a catalyst component containing a platinum group metal component to remove particulate matter and force regeneration thereof. As used herein, the term “platinum group metal” is used interchangeably with “noble metal component” and means platinum and palladium. Commercially available DOCs and DPFs consist of a number of precious metal components, including platinum and palladium.
본 발명자들은 종래 DOC 및 DPF를 장착한 매연저감장치의 DPF 재생 과정에서 특히 겨울철에 심각한 백연이 발생하는 문제점 (도 1)을 확인하고 이를 해결하고자 촉매성분 중 귀금속 성분 비율에 주목하였다. 도 2는 백연 배출 실험 장치 사진이다. 디젤엔진 후단에 DOC 및 DPF가 장착된 매연저감장치를 배치하고 매연저감장치 후단을 머플러로 연결하며, 머플러 후단에는 광투과식 매연측정기를 설치하였다. 광투과식 매연측정기 결과는 불투과도 (%)로 측정된다. 도 3은 각 측정 지점 온도 구역에서의 백연 (WS) 배출 상태를 보이는 그래프이다. 즉, DOC 전단, CSF 전단, CSF 후단 및 머플러 후단에 장착된 온도센서에 의한 온도 및 백연 (White Smoke, WS) 배출 관계를 도시한 것이다. 본 발명자들은 백연이 가시적으로 인식되는 영역을 확인하고자 하였으며, 반복적인 실험 결과 머플러 후단 온도 영역이 100 ℃ 내지 200℃에 범위에 있고, 이때 불투과도가 35% 이상인 경우 머플러 후단에서 가시적인 백연이 배출되며 200℃ 이상이면 가시적으로 인식되는 백연이 형성되지 않는다는 사실을 확인하였다. 도 4는 광투과식 매연측정기 측정 결과 및 시각적 백연 인식 관계를 보이는 그래프이며, 이에 따르면 머플러 후단 온도가 200℃인 경우 불투과도가 35% 이내이며, 도 4에서 실험된 매연저감장치는 백연을 배출하지 않는 정상적인 매연저감장치로 인정된다. 본 발명자들이 확립한 백연 배출 기준을 재확인하기 위하여 정상연료 및 고유황연료를 대상으로 실험한 결과를 도 5에 도시하였다. 도 5는 정상 연료 및 고유황 연료의 광투과식 매연 측정 결과를 보이는 그래프이며, 정상연료는 머플러 후단 온도 200℃ 전후하여 불투과도는 35% 이내이지만, 고유황연료를 사용한 결과 머플러 후단 온도 200℃ 전후하여 불투과도는 55%에 달하고, 정상연료는 가시적으로 인식되는 백연을 배출하지 않지만 고유황연료는 백연 배출이 관찰되므로, 본 발명자들이 확립한 백연 배출 기준은 적정하다고 판단하였다.The present inventors noticed the problem of serious white smoke occurring during the DPF regeneration process of the conventional smoke reduction device equipped with DOC and DPF (FIG. 1), and paid attention to the noble metal component ratio of the catalyst component. Figure 2 is a photograph of the white smoke emission experiment apparatus. A smoke reduction device equipped with DOC and DPF is arranged at the rear end of the diesel engine, and the rear end of the smoke reduction device is connected with a muffler, and a light transmission smoke detector is installed at the rear of the muffler. The light soot meter results are measured in% impermeability. 3 is a graph showing white smoke (WS) emission at each measurement point temperature zone. That is, the temperature and white smoke (WS) emission relationship by the temperature sensor mounted in the DOC front end, CSF front end, CSF rear end and muffler rear end is shown. The present inventors attempted to identify the area where white lead is visually recognized. As a result of repeated experiments, the temperature range of the rear end of the muffler is in the range of 100 ° C. to 200 ° C., and when the opacity is 35% or more, the visible white smoke is emitted from the rear end of the muffler. And it was confirmed that the white lead is not visible if it is 200 ℃ or more. FIG. 4 is a graph showing the results of the measurement of the optical smoke detector and visual recognition of smoke. According to this, when the rear end temperature of the muffler is 200 ° C., the impermeability is within 35%, and the smoke reduction device tested in FIG. It is recognized as a normal smoke reduction device that does not. 5 shows the results of experiments on normal fuel and high sulfur fuel in order to reconfirm the emission criteria established by the present inventors. 5 is a graph showing the results of the measurement of the light transmission type of the normal fuel and the high sulfur fuel, the normal fuel is less than 35% of the impermeability before and after the 200 ℃ muffler, the result of using the high sulfur fuel muffler rear temperature 200 ℃ The permeability reached 55% before and after, and the normal fuel did not emit visible white smoke, but the intrinsic sulfur fuel was observed to emit white smoke, and thus the white smoke emission standard established by the present inventors was determined to be appropriate.
본 발명자들은 매연저감장치에 적용되는 촉매성분 중 특히 귀금속성분에 주목하였다. 이는 백연의 주성분이 황화물에 의한 것이고 백연 생성을 결정하는 성분은 산화촉매성분 특히 귀금속성분 구체적으로 백금 및 팔라듐 성분의 산화력에 기인할 것이라 판단하였다. The present inventors paid particular attention to the precious metal component among the catalyst components applied to the smoke reduction apparatus. It was determined that the main component of white lead is sulfide and the component that determines white lead production is due to the oxidizing power of oxidation catalyst component, especially precious metal component, especially platinum and palladium component.
DOC 및 DPF 촉매조성물 제조DOC and DPF catalyst composition
매연저감장치를 구성하는 DOC 및 DPF에 슬러리로서 코팅되는 촉매조성물은 본 분야에 공지되어 있고, 포괄적으로는 백금족 금속 및 베이스 금속 기재 조성물을 포함한다. 통상 DOC 및 DPF에서 사용될 수 있는 촉매조성물의 일례는 고 표면적 내화성 산화물 지지체 (예를들면, γ-알루미나) 상에 분산된 백금족 성분 (예를 들면, 백금, 팔라듐 또는 로듐 성분)을 함유한다. 적합한 백금족 금속 성분은 백금 및 팔라듐이다. DOC에 로딩되는 백금 및 팔라듐을 포함한 귀금속 함량은 약 20 g/ft3 내지 200 g/ft3이며, 최고의 산화 활성을 얻기 위하여 Pt 단독 또는 일부 Pd가 함유되며, Pd가 함유되는 경우 통상 Pt/Pd 중량 비율은 1 이상이다. 즉, Pt: Pd 비율은 약 10:1 내지 4:1이다. 한편, DOC와 함께 매연저감장치를 구현하는 DPF (또는 CSF)에도 산화촉매성분들이 포함되며, 적절한 활성을 얻기 위하여 Pt 단독 또는 일부 Pd가 함유되며, Pd가 함유되는 경우 통상 Pt/Pd 중량 비율은 1 이상이다Catalyst compositions coated as slurries in the DOC and DPF constituting the soot reduction device are known in the art and generally comprise a platinum group metal and base metal base composition. One example of a catalyst composition that can typically be used in DOC and DPFs contains a platinum group component (eg, platinum, palladium or rhodium component) dispersed on a high surface area refractory oxide support (eg γ-alumina). Suitable platinum group metal components are platinum and palladium. The noble metal content, including platinum and palladium loaded in the DOC, is about 20 g / ft 3 to 200 g / ft 3 , containing Pt alone or some Pd to obtain the best oxidation activity, usually Pt / Pd The weight ratio is one or more. That is, the Pt: Pd ratio is about 10: 1 to 4: 1. On the other hand, DPF (or CSF), which implements a smoke reduction device together with DOC, also contains oxidizing catalyst components, and Pt alone or part of Pd is contained to obtain proper activity. Is more than 1
실시예EXAMPLE
본 분야에서 공지된 방법으로 DOC 및 CSF에 함유되는 백금 및 팔라듐 성분 비율을 조정하여 DOC 및 CSF 촉매조성물을 제조하였다. 제조된 촉매조성물을 슬러리화하여 통상의 DOC용 모노리스 및 CSF용 필터에 코팅하여 매연저감장치를 조립하여 도 1에 도시된 실험 장치에 따라 광투과식 매연측정기로 백연을 측정하였다.DOC and CSF catalyst compositions were prepared by adjusting the platinum and palladium component ratios contained in DOC and CSF by methods known in the art. The prepared catalyst composition was slurried and coated on a conventional monolithic filter for DOC and a filter for CSF to assemble a smoke reduction device, and white smoke was measured by a light transmission type smoke analyzer according to the experimental apparatus shown in FIG. 1.
표 1은 실시예에 따라 준비된 각각의 DOC 및 CSF에서의 귀금속 성분 비율 및 측정된 불투과도를 정리한 것이다.Table 1 summarizes the precious metal component ratios and the measured impermeability in each DOC and CSF prepared according to the examples.
표 1
사용연료 매연저감장치 순번 DOC 귀금속 비율 (Pt/Pd) DPF 귀금속 비율 (Pt/Pd) 머플러 후단 온도 200℃에서의 불투과도 (%) 백연 억제 적합성 판단
고유황연료 대조 2/1 2/1 92% 부적합
고유황연료 비교 1 2/1 1/1 87% 부적합
고유황연료 비교 2 1/1 1/1 47% 부적합
고유황연료 실시 1 1/2 1/1 28% 적합
고유황연료 실시 2 1/2 Pd 단독 13% 적합
정상연료 기준 2/1 2/1 6% 적합
Table 1
Fuel used Soot Reduction Device DOC Precious Metals Ratio (Pt / Pd) DPF Precious Metals Ratio (Pt / Pd) Permeability at% after muffler (%) Determination of white smoke suppression suitability
High sulfur fuel contrast 2/1 2/1 92% incongruity
High sulfur fuel Comparison 1 2/1 1/1 87% incongruity
High sulfur fuel Comparison 2 1/1 1/1 47% incongruity
High sulfur fuel Conduct 1 1/2 1/1 28% fitness
High sulfur fuel Conduct 2 1/2 Pd sole 13% fitness
Normal fuel standard 2/1 2/1 6% fitness
도 6은 본 발명에 의한 촉매조성물 (표 1: 실시 2)이 적용된 매연저감장치에 대한 광투과식 매연측정기 측정 결과이며, 도 7은 비교 촉매조성물 (표 1: 비교 1)이 적용된 매연저감장치에 대한 광투과식 매연측정기 측정 결과이다. 표 1 및 도 6, 7을 참조하면, 정상연료에서는 백연이 발생되지 않았으나, 동일한 매연저감장치 조건에서 고유황연료를 사용하는 경우 백연 발생 (불투과도 92%)이 관찰되었다. 비교 1 및 비교 2는 현존 매연저감장치에서 적용되는 산화촉매성분들이며, 불투과도가 35% 이상으로 관찰되어 시각적으로 인식되는 백연이 생성되어 백연 매연으로 인하여 부적합 판정을 받았다. 그러나, DOC에서 Pt/Pd 비율이 1 미만인 경우 및 CSF에서 Pt가 배제되고 Pd만이 사용되는 경우 백연 측정 결과 놀랍게도 불투과도는 35% 이하로 관찰되며 실질적으로 육안으로 보이는 백연은 생성되지 않았다. 상기 실험에서 Pt/Pd가 0.5인 경우를 대상으로 하였으나, 본 분야의 기술자는 Pt 및 Pd 산화력에 기인하여 이러한 결과가 도출되는 것으로 판단할 것이며, 이는 Pd 성분이 Pt 성분 대비 초과 존재하는 경우, 즉 Pt/Pd < 1인 경우, 즉 0.9, 0.8, 0.7 등의 비율에서도 동일한 결과를 보일 것이라는 것은 당업자에게 자명한 것이라 할 것이다.6 is a light transmission type soot measuring instrument measurement result for the catalyst composition according to the present invention (Table 1: Example 2) is applied, Figure 7 is a smoke reduction device to which the comparative catalyst composition (Table 1: comparison 1) is applied The results of the measurement of the light transmission soot meter for. Referring to Table 1 and FIGS. 6 and 7, white smoke was not generated in the normal fuel, but white smoke was generated (92% impermeability) when high sulfur fuel was used under the same soot reduction condition. Comparative 1 and 2 are oxidation catalyst components applied in existing soot reduction apparatus, and the impermeability was observed at 35% or more to produce a visually recognized white lead, which was judged to be inadequate due to the white smoke. However, when the Pt / Pd ratio is less than 1 in DOC and when Pt is excluded in CSF and only Pd is used, the whiteness measurement surprisingly shows less than 35% opacity and no substantially visible white smoke has been produced. In the above experiment, the case where Pt / Pd is 0.5, but the person skilled in the art will determine that such a result is obtained due to Pt and Pd oxidizing power, which means that the Pd component is present in excess of the Pt component, that is, It will be apparent to those skilled in the art that Pt / Pd <1, that is, the same result will be obtained even at a ratio of 0.9, 0.8, 0.7, and the like.

Claims (2)

  1. 디젤엔진 후단에 장착되는 디젤산화촉매 (DOC) 및 디젤미립자필터 (DPF)로 구성되는 매연저감장치에 있어서, DOC에 적용되는 디젤산화촉매조성물의 백금/팔라듐 중량 비율 (Pt/Pd)은 0 < Pt/Pd < 1인 것을 특징으로 하는, 디젤엔진 백연 방출 억제를 위한 매연저감장치.In a smoke reduction device composed of a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) mounted at a rear end of a diesel engine, the platinum / palladium weight ratio (Pt / Pd) of the diesel oxidation catalyst composition applied to the DOC is 0 < Pt / Pd <1, characterized in that the smoke reduction device for suppressing the diesel exhaust smoke emissions.
  2. 제1항에 있어서, DPF에 적용되는 디젤미립자필터촉매조성물의 귀금속 성분으로는 팔라듐 만이 함유되는 것을 특징으로 하는, 디젤엔진 백연 방출 억제를 위한 매연저감장치.The apparatus of claim 1, wherein only the palladium is contained as a noble metal component of the diesel particulate filter catalyst composition applied to the DPF.
PCT/KR2012/001833 2011-12-14 2012-03-14 Exhaust reducer for inhibiting discharge of white smoke from diesel engine WO2013089319A1 (en)

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KR20020043091A (en) * 2000-12-01 2002-06-08 이계안 Closed Coupled Converter structure using metal catalystic
KR20070005406A (en) * 2005-07-06 2007-01-10 희성엥겔하드주식회사 Diesel particulate filter
KR20090023786A (en) * 2007-09-03 2009-03-06 현대자동차주식회사 Partial oxidation promoted diesel oxidation catalyst and method for manufacturing the same

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Publication number Priority date Publication date Assignee Title
KR20020043091A (en) * 2000-12-01 2002-06-08 이계안 Closed Coupled Converter structure using metal catalystic
KR20070005406A (en) * 2005-07-06 2007-01-10 희성엥겔하드주식회사 Diesel particulate filter
KR20090023786A (en) * 2007-09-03 2009-03-06 현대자동차주식회사 Partial oxidation promoted diesel oxidation catalyst and method for manufacturing the same

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