WO2014178635A1 - Catalyst for preventing diesel engine from discharging white smoke - Google Patents

Catalyst for preventing diesel engine from discharging white smoke Download PDF

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WO2014178635A1
WO2014178635A1 PCT/KR2014/003825 KR2014003825W WO2014178635A1 WO 2014178635 A1 WO2014178635 A1 WO 2014178635A1 KR 2014003825 W KR2014003825 W KR 2014003825W WO 2014178635 A1 WO2014178635 A1 WO 2014178635A1
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diesel
dpf
doc
smoke
reduction device
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PCT/KR2014/003825
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French (fr)
Korean (ko)
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조형문
이태우
김은석
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희성촉매 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
    • F01N3/02—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
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/068—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/072—Iron group metals or copper
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • 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
    • F01N3/103—Oxidation catalysts for HC and CO only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2042—Barium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/502—Beta zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/908—O2-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/915—Catalyst supported on particulate filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
    • 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
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/16—Oxygen

Definitions

  • the present invention relates to a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) catalyst used in a soot reduction device to suppress white smoke generated in a diesel engine, and more particularly, to minimize sulfate adsorption.
  • DOC diesel oxidation catalyst
  • DPF diesel particulate filter
  • the present invention relates to a DOC catalyst and a DPF catalyst capable of delaying sulfate desorption and a smoke reduction device to which they are assembled.
  • Diesel engines have low emissions of hydrocarbons and carbon monoxide, but relatively high emissions of nitrogen oxides (NOx) and particulates (soot).
  • Soot in diesel exhaust products is solid or liquid particles contained in the gas produced through engine combustion or pyrolysis, and is a visible floating component, and is classified into black smoke, blue smoke, yellow smoke and white smoke.
  • white smoke emissions 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.
  • the applicant has disclosed a smoke reduction device for suppressing the emission of white smoke in a diesel engine through the Republic of Korea Patent Application No. 2011-134404 (2011.12.14), according to the diesel oxidation catalyst (DOC) and diesel particulate filter mounted to the rear end of the diesel engine
  • DOC diesel oxidation catalyst
  • the platinum / palladium weight ratio (Pt / Pd) of the diesel oxidation catalyst composition applied to the DOC is 0 ⁇ Pt / Pd ⁇ 1, which suppresses the diesel engine white smoke emission.
  • the smoke abatement system was found to significantly reduce white smoke emissions during the initial start-up of diesel engines, especially in winter.
  • the inventors of the present invention believe that the fundamental cause of the generation of white smoke is a sulfate component adsorbed to DOC of the soot reduction device, and when the adsorbed sulfate is desorbed during the regeneration of the DPF module, the final discharge temperature is 250 ° C. to 300 ° C. or less. It was confirmed that it aggregated and visualized as white lead particles. Therefore, it was confirmed that the addition of the components capable of inhibiting the respective steps of the reaction mechanism to the DOC and DPF catalyst components of the soot reduction device can substantially block the generation of white smoke.
  • the present invention relates to a soot reduction device comprising a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) mounted at a rear end of a diesel engine, wherein the precious metal support of the diesel oxidation catalyst composition applied to the DOC is an acid zeolite, and the OSC is applied to the DPF.
  • the present invention relates to a soot reduction apparatus for suppressing a diesel engine white smoke emission.
  • the DPF according to the present invention may further include a zeolite ion-exchanged with copper or iron.
  • Acidic zeolite of the diesel oxidation catalyst composition according to the present invention inhibits the adsorption of sulphate, and the OSC component coated on the DPF delays the release of sulphate, thereby significantly reducing the white smoke emission during the initial start-up of the diesel engine. .
  • 1 is a photograph of white smoke emission of a DOC and DPF equipped diesel engine vehicle.
  • FIG. 2 measures the impermeability and release SO2 concentrations of Assembly Example 1 and Assembly Comparative Example 1.
  • FIG. 3 measures the impermeability and release SO2 concentrations of Assembly Example 2 and Assembly Comparative Example 2.
  • Example 4 is a measure of the impermeability of Example 3 and Assembly Comparative Example 1.
  • 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.
  • the 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.
  • the inventors of the present invention have identified a problem (FIG. 1) in which severe white smoke occurs especially in winter during the DPF regeneration process of the smoke reduction device equipped with the DOC and the DPF (FIG. 1), and studied the mechanism of white smoke generation. According to various experiments of the present inventors, white lead occurs by the following mechanisms.
  • the present inventors have focused on suppressing such a mechanism.
  • the DOC catalyst support is selected as an acidic substance to suppress sulfate adsorption
  • the DPF coating component is selected as a basic substance to delay desorption of the sulfate.
  • a method of further delaying sulfate desorption was studied by adding a sulfate trap component to the DPF coating component.
  • the light transmission type soot measuring device applied in the present invention is the same as in the applicant's prior application (Patent Application No. 2011-134404), which is incorporated herein by reference in its entirety.
  • the inventors of the present invention attempted to suppress the generation of white smoke by appropriately selecting a support or an additional component supporting the precious metal component rather than paying attention to the precious metal content among the catalyst components applied to the smoke reduction device.
  • 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 1 or more. That is, the Pt: Pd ratio is about 10: 1 to 4: 1.
  • DOC support in the present invention is characterized in that the above-mentioned alumina acid zeolite is applied.
  • Such acidic zeolites can inhibit the sulfate adsorption reaction mentioned above.
  • Natural or synthetic zeolites may be applied, and representative zeolites include, but are not limited to, beta-zeolites (BEA).
  • BEA beta-zeolites
  • the zeolites according to the invention are applied to DOC modules after they have been made into a slurry by supporting Pt and Pd noble metal components in the same manner as procedures using alumina supports.
  • DPF which implements a soot reduction device together with DOC
  • DPF catalyst component in the present invention further includes an OSC (oxygen storage component) including ceria, zirconia and / or alkaline earth metal oxides.
  • Representative alkaline earth metal oxides may include barium oxide.
  • adding ceria and / or zirconia and / or barium oxide content corresponding to the noble metal content to the DPF catalyst component may delay sulfate desorption during the DPF regeneration process, resulting in a reaction against the reaction mechanism. It can be suppressed.
  • the DPF catalyst component may further include an ion exchanged zeolite.
  • the amount of the added OSC component and the same amount of Cu-Zeolite may be included, and the acid sulphate desorption may be further delayed due to the basicity of Cu-Zeolite.
  • 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, coated on a conventional DOC monolith and CSF filter, and a smoke reduction device was assembled, and white smoke was measured by a light transmission smoke analyzer.
  • Pt-Pd-impregnated zeolite mixed with platinum and palladium by weight in 2: 1 ratio was prepared using chloroplatinic acid and palladium nitrate in BEA powder, and dispersed in water to produce slurry Pt and Pd.
  • Supported zeolite support was prepared and ball milling so that about 90% of the particle size was 8-10 um.
  • 'implementation DOC' is referred to as 'implementation DOC'.
  • Gamma alumina powder was used as a support in the DOC preparation example. Hereinafter referred to as 'comparison DOC'.
  • Pt-Pd-impregnated activated alumina containing 1.5 parts by weight of platinum and palladium is prepared using chloroplatinic acid and palladium nitrate in gamma alumina powder, and the content corresponds to the precious metal component content.
  • the mixture was mixed with ceria (CeO2) and dispersed in water to prepare a DPF catalyst support having Pt and Pd in the form of slurry, and about 95% was ball milled to have a particle size of 8-10 ⁇ m.
  • the ball milled slurry was coated on a cordierite honeycomb, dried at 150 ° C. to 160 ° C. for about 15 minutes, and calcined at 530 ° C. to 550 ° C.
  • Example 1 DPF Catalyst Composition Preparation Ceria was excluded from Example 1. Hereinafter referred to as 'comparison DPF'.
  • Table 1 summarizes the elements of the soot reduction apparatuses in which each DOC and DPF manufactured according to the above embodiment was coated on each carrier and assembled therewith.
  • Soot Reduction Test Conditions Passed fuel containing 14 g of sulfur, operated for 20 minutes, carried out on a Euro-5 standard vehicle.
  • FIG. 2 is a measure of impermeability and release SO 2 concentration as a function of time of assembly Example 1 and assembly comparative example 1.
  • FIG. 2 is a measure of impermeability and release SO 2 concentration as a function of time of assembly Example 1 and assembly comparative example 1.
  • Example 1 and Comparative Example 1 apply the same DPF, and only the DOC catalyst support is modified.
  • the DOC configuration according to the present invention inevitably requires a DPF module capable of delaying SO 2 component emissions.
  • Figure 3 measures the impermeability and release SO2 concentrations as a function of time of assembly example 2 and assembly comparative example 2. That is, the same DOC component is applied, and the DPF coating component further includes ceria, an oxygen storage material.
  • Example 2 the SO 2 component discharge was greatly delayed, and thus the desorption reaction mechanism was progressed in the direction of suppression, thereby confirming that ultimately, the opacity, that is, the incandescent emission, was reduced. These results may be due to the delayed SO 2 desorption by ceria present in the DPF.
  • FIG. 4 measures the impermeability of Assembly Example 3 and Comparative Comparative Example 1.
  • the composition according to the present invention is applied and compared with a conventional soot reduction device.
  • the coating component further includes an ion exchange zeolite.
  • the DPF module has significantly reduced opacity. This opacity also shows an effect of reducing the opacity even when compared with the smoke reduction device of Example 1. This is considered to be an effect caused by delayed SO 3 desorption due to the adsorptivity of the ion exchange zeolite.

Abstract

The present invention relates to a diesel oxidation catalyst (DOC) and a diesel fine particulate filter (DPF) used in a smoke reduction system for preventing a diesel engine from generating white smoke, and more particularly to a DOC catalyst for minimizing the adsorption of a sulfate and a DPF catalyst for delaying the detachment of a sulfate. The present invention discloses a smoke reduction system mounted at the rear end of a diesel engine comprising a diesel oxidation catalyst (DOC) and a diesel fine particulate filter (DPF), wherein the precious metal support of a diesel oxidation catalyst composition applied to DOC is an acidic zeolite, and a diesel fine particulate filter composition applied to DPF includes an OSC (Oxygen Storage Component).

Description

디젤엔진 백연 방출 억제를 위한 촉매Catalysts for Suppressing Diesel Engine White Lead
본 발명은 디젤엔진에서 발생되는 백연 (white smoke)을 억제하기 위하여 매연저감장치에 사용되는 디젤산화촉매 (DOC) 및 디젤미립자 필터 (DPF) 촉매에 관한 것이며, 더욱 상세하게는 황산염 흡착을 최소화할 수 있는 DOC 촉매 및 황산염 탈착을 지연할 수 있는 DPF 촉매 및 이들이 조립되는 매연저감장치에 관한 것이다.The present invention relates to a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) catalyst used in a soot reduction device to suppress white smoke generated in a diesel engine, and more particularly, to minimize sulfate adsorption. The present invention relates to a DOC catalyst and a DPF catalyst capable of delaying sulfate desorption and a smoke reduction device to which they are assembled.
디젤엔진은 탄화수소 및 일산화탄소의 배출은 낮지만, 상대적으로 질소산화물 (NOx) 및 미립자 (매연) 배출은 높다. 디젤 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.Diesel engines have low emissions of hydrocarbons and carbon monoxide, but relatively high emissions of nitrogen oxides (NOx) and particulates (soot). Soot in diesel exhaust products is solid or liquid particles contained in the gas produced through engine combustion or pyrolysis, and is a visible floating component, and is classified into 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.
본 출원인은 대한민국 특허출원 제2011-134404호 (2011.12.14)을 통하여 디젤엔진 백연 방출 억제를 위한 매연저감장치를 개시하였고, 이에 따르면 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 매연저감장치는 디젤엔진 초기 시동 시 특히 겨울철에 발생되는 백연 배출이 현저하게 감소하게 된다는 것을 확인하였다.The applicant has disclosed a smoke reduction device for suppressing the emission of white smoke in a diesel engine through the Republic of Korea Patent Application No. 2011-134404 (2011.12.14), according to the diesel oxidation catalyst (DOC) and diesel particulate filter mounted to the rear end of the diesel engine In the smoke reduction device composed of (DPF), the platinum / palladium weight ratio (Pt / Pd) of the diesel oxidation catalyst composition applied to the DOC is 0 <Pt / Pd <1, which suppresses the diesel engine white smoke emission. The smoke abatement system was found to significantly reduce white smoke emissions during the initial start-up of diesel engines, especially in winter.
본 발명자에 의한 상기 선출원은 매연저감장치에서 DOC에 적용되는 귀금속 함량을 조절 내지 특정하여 백연 발생을 억제하고자 하는 것이었으나, 본 발명자는 백연 발생 원인을 이해하고 이에 기초한 새로운 촉매의 개발의 필요성에 따라, 백연 발생의 메카니즘을 규명하고 이러한 반응기작 이해에 따라 근본적으로 백연 발생을 차단할 수 있는 접근법에 도달하게 되었다.The prior application by the present inventors was intended to suppress the generation of white smoke by adjusting or specifying the noble metal content applied to the DOC in the smoke reduction device, but the present inventors understand the cause of the generation of white smoke and according to the necessity of developing a new catalyst based thereon As a result, the mechanism of white lead generation has been elucidated and the understanding of this mechanism has led to an approach that can fundamentally block white lead generation.
본 발명자는, 백연 발생의 근본적인 원인이, 매연저감장치의 DOC에 흡착되는 황산염 성분이며, 이러한 흡착 황산염이 DPF 모듈 재생과정에서 탈착되면서, 최종 배출온도가 250℃ 내지 300℃ 이하인 경우 물 분자들과 응집되어 백연 입자로 가시화된다는 것을 확인하였다. 따라서 이러한 반응 메카니즘의 각각의 단계들을 억제할 수 있는 성분들을 매연저감장치의 DOC 및 DPF 촉매성분에 추가함으로써 실질적으로 백연 발생을 차단할 수 있음을 확인하였다. The inventors of the present invention believe that the fundamental cause of the generation of white smoke is a sulfate component adsorbed to DOC of the soot reduction device, and when the adsorbed sulfate is desorbed during the regeneration of the DPF module, the final discharge temperature is 250 ° C. to 300 ° C. or less. It was confirmed that it aggregated and visualized as white lead particles. Therefore, it was confirmed that the addition of the components capable of inhibiting the respective steps of the reaction mechanism to the DOC and DPF catalyst components of the soot reduction device can substantially block the generation of white smoke.
본 발명은 디젤엔진 후단에 장착되는 디젤산화촉매 (DOC) 및 디젤미립자필터 (DPF)로 구성되는 매연저감장치에 있어서, DOC에 적용되는 디젤산화촉매조성물의 귀금속 지지체는 산성 제올라이트이며, DPF에는 OSC (산소저장성분)이 포함되는, 디젤엔진 백연 방출 억제를 위한 매연저감장치에 관한 것이다. 또한 본 발명에 의한 DPF에는 구리 또는 철로 이온교환된 제올라이트를 더욱 포함할 수 있다.The present invention relates to a soot reduction device comprising a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) mounted at a rear end of a diesel engine, wherein the precious metal support of the diesel oxidation catalyst composition applied to the DOC is an acid zeolite, and the OSC is applied to the DPF. (Oxygen storage component), the present invention relates to a soot reduction apparatus for suppressing a diesel engine white smoke emission. In addition, the DPF according to the present invention may further include a zeolite ion-exchanged with copper or iron.
본 발명에 의한 디젤산화촉매조성물의 산성 제올라이트는 황산염의 흡착을 억제하고, DPF에 코팅되는 OSC 성분은 황산염 방출을 지연시킴으로써 디젤엔진 초기 시동 시 특히 겨울철에 발생되는 백연 배출이 현저하게 감소시킬 수 있다.Acidic zeolite of the diesel oxidation catalyst composition according to the present invention inhibits the adsorption of sulphate, and the OSC component coated on the DPF delays the release of sulphate, thereby significantly reducing the white smoke emission during the initial start-up of the diesel engine. .
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 조립 실시예 1 및 조립 비교예 1의 불투과성 및 방출 SO2 농도를 측정한 것이다.FIG. 2 measures the impermeability and release SO2 concentrations of Assembly Example 1 and Assembly Comparative Example 1. FIG.
도 3은 조립 실시예 2 및 조립 비교예 2의 불투과성 및 방출 SO2 농도를 측정한 것이다.FIG. 3 measures the impermeability and release SO2 concentrations of Assembly Example 2 and Assembly Comparative Example 2. FIG.
도 4는 조립 실시예 3 및 조립 비교예 1의 불투과성을 측정한 것이다.4 is a measure of the impermeability of Example 3 and Assembly Comparative Example 1.
본 발명자들은 디젤엔진 백연 배출을 억제하기 위한 시도로 매연저감장치를 이루는 유닛들의 촉매 조성을 개발하였다. 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 developed the catalyst composition 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. The 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 백연 발생 메카니즘을 연구하였다. 본 발명자들의 다양한 실험에 의하면, 백연은 다음과 같은 기작들로 발생한다. The inventors of the present invention have identified a problem (FIG. 1) in which severe white smoke occurs especially in winter during the DPF regeneration process of the smoke reduction device equipped with the DOC and the DPF (FIG. 1), and studied the mechanism of white smoke generation. According to various experiments of the present inventors, white lead occurs by the following mechanisms.
1) 디젤엔진에서 배출되는 이산화황은 DOC에서 황산염 (SO3)으로 산화된다:1) Sulfur dioxide emitted from diesel engines is oxidized to sulfate (SO 3 ) in DOC:
2SO2 + O2 → 2SO3 2SO 2 + O 2 → 2SO 3
2) 생성된 황산염은 DOC 표면에 흡착된다:2) The sulfate produced is adsorbed onto the DOC surface:
SO3 + M → M-SO3 SO 3 + M → M-SO 3
3) 흡착된 황산염은 DPF 재생 과정에서 황산염 및 이산화황으로 탈착된다:3) The adsorbed sulphate desorbs to sulphate and sulfur dioxide during DPF regeneration:
M-SO3 → M + xSO2 + ySO3 M-SO 3 → M + xSO 2 + ySO 3
4) 황산염은 배출온도가 250 내지 300℃ 이하일 때 물과 응집되어 백연 형태로 방출된다.4) Sulfate aggregates with water and is released in the form of white lead when the discharge temperature is below 250 ~ 300 ℃.
본 발명자는 이러한 메카니즘을 억제하는 방안에 주목하였다. 구체적으로는, DOC 촉매 지지체를 산성 물질로 선택하여 황산염 흡착을 억제하는 것이고, DPF 코팅성분을 염기성 물질로 선택하여 황산염의 탈착을 지연시키는 것이다. 더불어 DPF 코팅성분에 황산염 트랩 (trap) 성분을 추가하여 황산염 탈착을 더욱 지연시키는 방법을 연구하였다.The present inventors have focused on suppressing such a mechanism. Specifically, the DOC catalyst support is selected as an acidic substance to suppress sulfate adsorption, and the DPF coating component is selected as a basic substance to delay desorption of the sulfate. In addition, a method of further delaying sulfate desorption was studied by adding a sulfate trap component to the DPF coating component.
본 발명은 상기 전략에 따라 구현된 것이며, 이하 상술한다.The present invention has been implemented according to the above strategy, and will be described in detail below.
먼저, 본 발명에서 적용되는 광투과식 매연측정기는 본 출원인의 선행출원 (특허출원 제2011-134404호)에서와 동일하며, 상기 선행출원은 본원에서 참고로 전체가 포함된다. 본 발명자들은 매연저감장치에 적용되는 촉매성분 중 특히 귀금속함량에 주목하기보다는 상기 귀금속 성분을 지지하는 지지체 또는 추가 성분을 적절하게 선택하여 상기 백연 발생 반응 메카니즘 진행을 방해하여 백연 발생을 억제하고자 하였다.First, the light transmission type soot measuring device applied in the present invention is the same as in the applicant's prior application (Patent Application No. 2011-134404), which is incorporated herein by reference in its entirety. The inventors of the present invention attempted to suppress the generation of white smoke by appropriately selecting a support or an additional component supporting the precious metal component rather than paying attention to the precious metal content among the catalyst components applied to the smoke reduction device.
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. 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. 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 1 or more. That is, the Pt: Pd ratio is about 10: 1 to 4: 1.
본 발명에서의 DOC 지지체는 상기된 알루미나가 아닌 산성 제올라이트가 적용되는 것을 특징으로 한다. 이러한 산성 제올라이트는 상기 언급된 황산염 흡착 반응을 억제할 수 있다. 천연 또는 합성제올라이트가 적용될 수 있으며 대표적인 제올라이트로는 베타-제올라이트 (BEA)가 적용될 수 있으나, 이에 국한되지 않는다. 본 발명에 의한 제올라이트는 알루미나 지지체를 사용하는 절차와 동일한 방식으로 Pt 및 Pd 귀금속 성분을 지지하여 슬러리로 제조된 후 DOC 모듈에 적용된다.DOC support in the present invention is characterized in that the above-mentioned alumina acid zeolite is applied. Such acidic zeolites can inhibit the sulfate adsorption reaction mentioned above. Natural or synthetic zeolites may be applied, and representative zeolites include, but are not limited to, beta-zeolites (BEA). The zeolites according to the invention are applied to DOC modules after they have been made into a slurry by supporting Pt and Pd noble metal components in the same manner as procedures using alumina supports.
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 이상이다. 본 발명에서의 DPF 촉매성분에는 세리아, 지르코니아 및/또는 알칼리토금속산화물을 포함한 OSC (산소저장성분)이 더욱 포함된다. 대표적인 알칼리토금속산화물로는 바륨산화물을 예시할 수 있다. 본 발명에 의하면 귀금속 함량에 상당하는 세리아 및/또는 지르코니아 및/또는 바륨산화물 함량을 DPF 촉매성분에 추가하면 DPF 재생 과정에서 황산염 탈착이 지연되어 상기 반응 메카니즘에 역행하는 결과를 얻을 수 있어 백연 발생을 억제할 수 있는 것이다. On the other hand, DPF (or CSF), which implements a soot reduction device together with DOC, also contains oxidizing catalyst components, and Pt alone or some Pds are contained in order to obtain appropriate activity, and when Pd is contained, the Pt / Pd weight ratio is usually 1 or more. The DPF catalyst component in the present invention further includes an OSC (oxygen storage component) including ceria, zirconia and / or alkaline earth metal oxides. Representative alkaline earth metal oxides may include barium oxide. According to the present invention, adding ceria and / or zirconia and / or barium oxide content corresponding to the noble metal content to the DPF catalyst component may delay sulfate desorption during the DPF regeneration process, resulting in a reaction against the reaction mechanism. It can be suppressed.
또한 DPF 촉매성분에는 이온교환된 제올라이트를 더욱 포함할 수 있다. 바람직하게는 첨가되는 OSC 성분의 함량과 동량의 Cu-Zeolite가 포함될 수 있고, Cu-Zeolite 의 염기성으로 인하여 산성 황산염 탈착을 더욱 지연할 수 있는 것이다.In addition, the DPF catalyst component may further include an ion exchanged zeolite. Preferably, the amount of the added OSC component and the same amount of Cu-Zeolite may be included, and the acid sulphate desorption may be further delayed due to the basicity of Cu-Zeolite.
포괄 실시예Comprehensive Example
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 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, coated on a conventional DOC monolith and CSF filter, and a smoke reduction device was assembled, and white smoke was measured by a light transmission smoke analyzer.
DOC 촉매 조성물 제조 실시예DOC Catalyst Composition Preparation Examples
BEA 파우더에 클로로플라티닉산 및 팔라듐나이트레이트 (palladium nitrate) 를 이용하여 백금 및 팔라듐 중량부가 2:1 비율로 혼합된 Pt-Pd가 함침된 제올라이트를 제조하여 수중에 분산시켜 슬러리 상태의 Pt 및 Pd가 담지된 제올라이트 지지체를 제조하고 약 90% 정도가 입자크기 8-10um가 되도록 볼밀링을 하였다. 상기 볼밀링 처리된 슬러리를 코오디어라이트 하니콤에 코팅하여 150℃ 내지 160℃ 에서 약 10분간 건조한 후, 530℃ ~ 550℃에서 약 40분간 소성하여 Pt-Pd/BEA DOC 촉매(총 백금:팔라듐 = 2/1)를 완성하였다. 이하 '실시 DOC'라고 칭한다.Pt-Pd-impregnated zeolite mixed with platinum and palladium by weight in 2: 1 ratio was prepared using chloroplatinic acid and palladium nitrate in BEA powder, and dispersed in water to produce slurry Pt and Pd. Supported zeolite support was prepared and ball milling so that about 90% of the particle size was 8-10 um. The ball milled slurry was coated on cordierite honeycomb, dried at 150 ° C. to 160 ° C. for about 10 minutes, and calcined at 530 ° C. to 550 ° C. for about 40 minutes to form a Pt-Pd / BEA DOC catalyst (total platinum: palladium). = 2/1). Hereinafter referred to as 'implementation DOC'.
DOC 촉매 조성물 비교예DOC Catalyst Composition Comparative Example
상기 DOC 제조 실시예에서 지지체로 감마 알루미나 파우더를 사용하였다. 이하 '비교 DOC'라고 칭한다.Gamma alumina powder was used as a support in the DOC preparation example. Hereinafter referred to as 'comparison DOC'.
DPF 촉매 조성물 제조 실시예 1DPF Catalyst Composition Preparation Example 1
감마 알루미나 파우더에 클로로플라티닉산 및 팔라듐나이트레이트 (palladium nitrate) 를 이용하여 백금 및 팔라듐 중량부가 1.5:1 비율로 혼합된 Pt-Pd가 함침된 활성알루미나를 제조하고, 귀금속 성분 함량에 상당하는 함량의 세리아 (CeO2)와 혼합하여 수중에 분산시켜 슬러리 상태의 Pt 및 Pd가 담지된 DPF 촉매 지지체를 제조하고 약 95% 정도가 입자크기 8-10um가 되도록 볼밀링을 하였다. 상기 볼밀링 처리된 슬러리를 코오디어라이트 하니콤에 코팅하여 150℃~160℃에서 약 15분간 건조한 후, 530℃~550℃에서 약 40분간 소성하여 Pt-Pd/Al2O3-CeO2 DPF 촉매(총 백금:팔라듐 = 1.5/1: 귀금속 (Pt+Pd)/CeO2 중량비= 1/1)를 완성하였다. 이하 '실시 DPF 1'라고 칭한다.Pt-Pd-impregnated activated alumina containing 1.5 parts by weight of platinum and palladium is prepared using chloroplatinic acid and palladium nitrate in gamma alumina powder, and the content corresponds to the precious metal component content. The mixture was mixed with ceria (CeO2) and dispersed in water to prepare a DPF catalyst support having Pt and Pd in the form of slurry, and about 95% was ball milled to have a particle size of 8-10 μm. The ball milled slurry was coated on a cordierite honeycomb, dried at 150 ° C. to 160 ° C. for about 15 minutes, and calcined at 530 ° C. to 550 ° C. for about 40 minutes to form a Pt-Pd / Al 2 O 3 -CeO 2 DPF catalyst (total platinum : Palladium = 1.5 / 1: Precious metal (Pt + Pd) / CeO 2 weight ratio = 1/1) was completed. Hereinafter referred to as 'implemented DPF 1'.
DPF 촉매 조성물 제조 실시예 2DPF Catalyst Composition Preparation Example 2
상기 DPF 촉매 조성물 제조 실시예 1과 같이 진행하되, 슬러리 제조시에 Cu-ZSM5 성분을 세리아 함량과 동량으로 첨가한 슬러리를 이용하여 Pt-Pd/Al2O3-CeO2-Cu-ZSM5 DPF 촉매(총 백금:팔라듐 = 1.5/1: 귀금속 (Pt+Pd)/CeO2 중량비= 1/1 : 귀금속 (Pt+Pd)/Cu-ZSM 중량비 = 1:1)를 완성하였다. 이하 '실시 DPF 2'라고 칭한다.Proceed as in Example 1 to prepare the DPF catalyst composition, Pt-Pd / Al 2 O 3 -CeO 2 -Cu-ZSM5 DPF catalyst (total platinum: Palladium = 1.5 / 1: precious metal (Pt + Pd) / CeO2 weight ratio = 1/1: precious metal (Pt + Pd) / Cu-ZSM weight ratio = 1: 1). Hereinafter referred to as 'implemented DPF 2'.
DPF 촉매 조성물 비교예DPF Catalyst Composition Comparative Example
DPF 촉매 조성물 제조 실시예 1에서 세리아 성분을 제외하였다. 이하 '비교 DPF'라고 칭한다.DPF Catalyst Composition Preparation Ceria was excluded from Example 1. Hereinafter referred to as 'comparison DPF'.
표 1은 상기 실시예에 따라 제조된 각각의 DOC 및 DPF를 각각의 캐리어에 코팅하고 이들을 조립한 매연저감장치들의 요소들을 요약한 것이다. Table 1 summarizes the elements of the soot reduction apparatuses in which each DOC and DPF manufactured according to the above embodiment was coated on each carrier and assembled therewith.
표 1
실시 DOC 실시 DPF 1 실시 DPF 2 비교 DOC 비교 DPF
조립 실시예 1 ◎ ◎
조립 실시예 2 ◎ ◎
조립 실시예 3 ◎ ◎
조립 비교예 1 ◎ ◎
조립 비교예 2 ◎ ◎
Table 1
Conduct DOC Real DPF 1 Real DPF 2 Compare DOC Compare DPF
Assembly Example 1 ◎ ◎
Assembly Example 2 ◎ ◎
Assembly Example 3 ◎ ◎
Assembly Comparative Example 1 ◎ ◎
Assembly Comparative Example 2 ◎ ◎
매연저감 실험조건: 14g의 황을 포함한 연료를 통과, 20분 가동, 유로-5 기준 차량에서 실시.Soot Reduction Test Conditions: Passed fuel containing 14 g of sulfur, operated for 20 minutes, carried out on a Euro-5 standard vehicle.
결과result
1. 도 2는 조립 실시예 1 및 조립 비교예 1의 경시 함수로써 불투과성 및 방출 SO2 농도를 측정한 것이다.1. FIG. 2 is a measure of impermeability and release SO 2 concentration as a function of time of assembly Example 1 and assembly comparative example 1. FIG.
실시예 1 및 비교예 1은 동일한 DPF를 적용한 것이고, DOC 촉매 지지체만이 변경된 것이다. 도 2에서 확인되는 바와 같이, 지지체로 산성 제올라이트가 적용되는 경우 불투과도는 약간 억제되지만 SO2 성분 지연 효과는 달성되지 않는다. 따라서 본 발명에 의한 DOC 구성은 필연적으로 SO2 성분 배출을 지연시킬 수 있는 DPF 모듈을 필요로 한다.Example 1 and Comparative Example 1 apply the same DPF, and only the DOC catalyst support is modified. As can be seen in FIG. 2, when acidic zeolite is applied as a support, the opacity is slightly suppressed but the SO 2 component delay effect is not achieved. Therefore, the DOC configuration according to the present invention inevitably requires a DPF module capable of delaying SO 2 component emissions.
2. 도 3은 조립 실시예 2 및 조립 비교예 2의 경시 함수로써 불투과성 및 방출 SO2 농도를 측정한 것이다. 즉 동일한 DOC 성분을 적용하고 DPF 코팅성분에 산소저장물질인 세리아를 더욱 포함한 것이다.2. Figure 3 measures the impermeability and release SO2 concentrations as a function of time of assembly example 2 and assembly comparative example 2. That is, the same DOC component is applied, and the DPF coating component further includes ceria, an oxygen storage material.
실시예 2에서 SO2 성분 배출은 크게 지연되어 상기 탈착 반응 메카니즘이 억제되는 방향으로 진행되어 궁극적으로 불투과도, 즉 백열 방출이 감소되었음을 확인할 수 있다. 이러한 결과는 DPF 중에 존재하는 세리아에 의한 SO2 탈착 지연으로 인한 것으로 판단된다.In Example 2, the SO 2 component discharge was greatly delayed, and thus the desorption reaction mechanism was progressed in the direction of suppression, thereby confirming that ultimately, the opacity, that is, the incandescent emission, was reduced. These results may be due to the delayed SO 2 desorption by ceria present in the DPF.
3. 도 4는 조립 실시예 3 및 조립 비교예 1의 불투과도를 측정한 것이다. 즉 DOC 촉매성분 및 DPF 코팅성분에 있어서, 본 발명에 의한 구성들을 적용하여 종래 매연저감장치와 비교한 것이다.비교예 1과 비교할 때, 세리아에 추가하여 이온교환 제올라이트가 더욱 포함된 코팅성분을 가지는 DPF 모듈은 불투과도를 상당히 낮추었다. 이러한 불투과도는 실시예 1의 매연저감장치와 비교할 때에도 불투과도 저감 효과를 보인다. 이는 이온교환 제올라이트의 흡착성에 기인하여 SO3 탈착이 지연되어 유발되는 효과라고 판단된다.3. FIG. 4 measures the impermeability of Assembly Example 3 and Comparative Comparative Example 1. FIG. That is, in the DOC catalyst component and the DPF coating component, the composition according to the present invention is applied and compared with a conventional soot reduction device. Compared with Comparative Example 1, in addition to ceria, the coating component further includes an ion exchange zeolite. The DPF module has significantly reduced opacity. This opacity also shows an effect of reducing the opacity even when compared with the smoke reduction device of Example 1. This is considered to be an effect caused by delayed SO 3 desorption due to the adsorptivity of the ion exchange zeolite.

Claims (8)

  1. 디젤엔진 후단에 장착되는 디젤산화촉매 (DOC) 및 디젤미립자필터 (DPF)로 구성되는 매연저감장치에 있어서, DOC에 적용되는 디젤산화촉매조성물의 귀금속 지지체는 산성 제올라이트이며, DPF에 적용되는 디젤미립자필터촉매조성물에는 OSC (산소저장성분)이 포함되는 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 precious metal support of the diesel oxidation catalyst composition applied to the DOC is an acid zeolite, and diesel particulates applied to the DPF. The catalyst catalyst composition is characterized in that the OSC (oxygen storage component), characterized in that the smoke reduction device for suppressing the exhaust emission of diesel engine.
  2. 제1항에 있어서, 산성 제올라이트는 베타 제올라이트 (BEA)이며, OSC는 세리아 또는 지르코니아 또는 바륨산화물인 것을 특징으로 하는, 디젤엔진 백연 방출 억제를 위한 매연저감장치.The apparatus of claim 1, wherein the acidic zeolite is beta zeolite (BEA), and the OSC is ceria or zirconia or barium oxide.
  3. 제1항 또는 제2항에 있어서, DPF에 적용되는 디젤미립자필터촉매조성물에는 구리 또는 철로 이온교환된 제올라이트를 더욱 포함하는, 디젤엔진 백연 방출 억제를 위한 매연저감장치.The particulate matter reduction apparatus for suppressing the emission of white smoke in a diesel engine according to claim 1 or 2, wherein the diesel particulate filter catalyst composition applied to the DPF further comprises a zeolite ion-exchanged with copper or iron.
  4. 제1항 또는 제2항에 있어서, DOC에 적용되는 디젤산화촉매조성물의 백금/팔라듐 중량 비율 (Pt/Pd)은 0 < Pt/Pd < 1인 것을 특징으로 하는, 디젤엔진 백연 방출 억제를 위한 매연저감장치.The platinum / palladium weight ratio (Pt / Pd) of the diesel oxidation catalyst composition applied to the DOC is 0 <Pt / Pd <1, according to claim 1 or 2, Soot reduction device.
  5. 제1항 또는 제2항에 있어서, DPF에 적용되는 디젤미립자필터촉매조성물의 귀금속 성분으로는 팔라듐만이 함유되는 것을 특징으로 하는, 디젤엔진 백연 방출 억제를 위한 매연저감장치.The smoke reduction device for suppressing the emission of white smoke in a diesel engine according to claim 1 or 2, wherein only the palladium is contained as a noble metal component of the diesel particulate filter catalyst composition applied to the DPF.
  6. 디젤엔진 후단에 장착되는 디젤산화촉매 (DOC) 및 디젤미립자필터 (DPF)로 구성되는 매연저감장치를 이용하여 매연을 저감시키는 방법에 있어서, DOC에서 황산염의 흡착을 억제시키는 단계 및 DPF에서 황산염 방출을 지연시키는 단계를 포함하는 것을 특징으로 하는, 디젤엔진 후단에 장착되는 디젤산화촉매 (DOC) 및 디젤미립자필터 (DPF)로 구성되는 매연저감장치를 이용하여 매연을 저감시키는 방법.A method for reducing soot by using a soot 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 method comprising: inhibiting the adsorption of sulfate in DOC and sulphate release in DPF Reducing the smoke using a smoke reduction device consisting of a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) mounted to the rear end of the diesel engine, characterized in that it comprises the step of delaying.
  7. 제7항에 있어서, 황산염 흡착 억제는 산성 제올라이트에 의해 이루어지고, 황산염 방출 지연은 산소저장성분에 의해 이루어지는 것을 특징으로 하는, 디젤엔진 후단에 장착되는 디젤산화촉매 (DOC) 및 디젤미립자필터 (DPF)로 구성되는 매연저감장치를 이용하여 매연을 저감시키는 방법.8. The diesel oxidation catalyst (DOC) and diesel particulate filter (DPF) mounted to the rear end of a diesel engine according to claim 7, wherein the sulfate adsorption suppression is made by acidic zeolite and the sulfate release delay is made by oxygen storage component. A method of reducing smoke using a smoke reduction device composed of).
  8. 제8항에 있어서, 상기 산소저장성분은 세리아 또는 지르코니아 또는 알칼리토금속산화물인 것을 특징으로 하는, 디젤엔진 후단에 장착되는 디젤산화촉매 (DOC) 및 디젤미립자필터 (DPF)로 구성되는 매연저감장치를 이용하여 매연을 저감시키는 방법.According to claim 8, wherein the oxygen storage component is characterized in that the ceria, zirconia or alkaline earth metal oxide, the particulate smoke reduction device consisting of a diesel oxidation catalyst (DOC) and a diesel particulate filter (DPF) mounted to the rear end of the diesel engine. To reduce soot.
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