KR101241420B1 - Palladium-rhodium based automotive catalyst containing rare earth element having improved heat resistance - Google Patents

Palladium-rhodium based automotive catalyst containing rare earth element having improved heat resistance Download PDF

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KR101241420B1
KR101241420B1 KR1020100130845A KR20100130845A KR101241420B1 KR 101241420 B1 KR101241420 B1 KR 101241420B1 KR 1020100130845 A KR1020100130845 A KR 1020100130845A KR 20100130845 A KR20100130845 A KR 20100130845A KR 101241420 B1 KR101241420 B1 KR 101241420B1
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여권구
차문순
박병일
이경민
김해리
임원미
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    • 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
    • B01J23/54—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
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    • 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
    • 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
    • B01J37/0244—Coatings comprising several layers

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Abstract

본 발명은 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매에 관한 것으로, 더욱 상세하게는 담체, 전술한 담체의 외표면에 형성되며, 팔라듐이 함유되는 제1코팅층 및 전술한 제1코팅층의 외표면에 형성되며, 로듐이 함유되는 제2코팅층을 포함하여 이루어진다.
본 발명에 따른 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매는 조촉매로 종래에 사용되던 세륨, 지르코늄 이외에 란타늄, 네오듐 및 이트륨이 더 첨가되어 반응성 및 열적 내구성이 향상된다.The present invention relates to a catalyst for palladium-rhodium-based automobiles containing rare earth metals with improved heat resistance, and more particularly, a first coating layer containing palladium and a first coating layer formed on the outer surface of the carrier and the aforementioned carrier. It is formed on the outer surface of the coating layer, and comprises a second coating layer containing rhodium.
Palladium-rhodium-based automotive catalyst containing the rare earth metal according to the present invention has improved heat resistance, and in addition to cerium and zirconium, which are conventionally used as cocatalysts, lanthanum, neodium and yttrium are added to improve reactivity and thermal durability.

Description

희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매 {PALLADIUM-RHODIUM BASED AUTOMOTIVE CATALYST CONTAINING RARE EARTH ELEMENT HAVING IMPROVED HEAT RESISTANCE}Palladium-rhodium-based automotive catalysts containing rare earth metals with improved heat resistance {PALLADIUM-RHODIUM BASED AUTOMOTIVE CATALYST CONTAINING RARE EARTH ELEMENT HAVING IMPROVED HEAT RESISTANCE}

본 발명은 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매에 관한 것으로, 더욱 상세하게는 담체, 전술한 담체의 외표면에 형성되며, 팔라듐이 함유되는 제1코팅층 및 전술한 제1코팅층의 외표면에 형성되며, 로듐이 함유되는 제2코팅층으로 이루어진다.
The present invention relates to a catalyst for palladium-rhodium-based automobiles containing rare earth metals with improved heat resistance, and more particularly, a first coating layer containing palladium and a first coating layer formed on the outer surface of the carrier and the aforementioned carrier. It is formed on the outer surface of the coating layer, and consists of a second coating layer containing rhodium.

본 발명은 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매에 관한 것으로, 더욱 상세하게는 담체, 전술한 담체의 외표면에 형성되며, 팔라듐이 함유되는 제1코팅층 및 전술한 제1코팅층의 외표면에 형성되며, 로듐이 함유되는 제2코팅층으로 이루어진다.The present invention relates to a catalyst for palladium-rhodium-based automobiles containing rare earth metals with improved heat resistance, and more particularly, a first coating layer containing palladium and a first coating layer formed on the outer surface of the carrier and the aforementioned carrier. It is formed on the outer surface of the coating layer, and consists of a second coating layer containing rhodium.

일반적으로 자동차의 연료로는 원유를 정제하는 과정에서 얻어지는 가솔린 및 디젤이 가장 널리 사용되는데, 이러한 가솔린 및 디젤의 경우는 환경오염을 유발하는 탄소를 다량 함유한 배기가스를 배출하고 있다.In general, gasoline and diesel obtained in the process of refining crude oil are most widely used as fuels for automobiles. In the case of gasoline and diesel, exhaust gas containing a large amount of carbon causing environmental pollution is emitted.

이러한 배기가스를 정화하기 위해 백금, 팔라듐 또는 로듐등의 귀금속류가 함유된 촉매가 활발히 연구되고 있으며, 이러한 귀금속류가 함유된 촉매는 내열, 내구성 및 촉매의 성능을 향상시키기 위해 많은 첨가물들이 첨가되어지고 있다.Catalysts containing precious metals such as platinum, palladium or rhodium have been actively studied to purify these exhaust gases, and many additives have been added to catalysts containing such precious metals to improve heat resistance, durability and catalyst performance. .

내연기관의 배출가스에 대한 방출기준이 각국 정부에 의해 정해져 있으며 또한 이에 대한 모니터링도 그 기준이 정해져 있는데, 배출가스에 대한 모니터링 기준을 만족시키기 위하여 사용되는 기술이 조촉매제의 산소저장능력을 이용하는 것이다. 그러나 종래의 자동차 촉매는 산소저장능력이 있는 세리아 또는 세리아 복합산화물만을 주로 사용하기 때문에, 세리아나 세리아 복합산화물들의 산소저장능력이 자동차 배기가스 중 탄화수소의 산화반응력을 저하시켜 탄화수소의 정화능을 감소시키는 문제점이 있었다.Emission standards for internal combustion engines are set by governments, and monitoring standards are set. The technology used to satisfy the monitoring standards for emissions is to use the oxygen storage capacity of the promoter. . However, since the conventional automotive catalyst mainly uses only ceria or ceria composite oxides having oxygen storage capacity, the oxygen storage capacity of ceria or ceria composite oxides reduces the oxidation reaction of hydrocarbons in automobile exhaust gas, thereby reducing the hydrocarbon purification ability. There was a problem.

또한, 최근에는 배기가스에 대한 규제가 강화됨에 따라, 종래에 사용되던 자동차용 촉매에 사용되던 조촉매를 개량하여 종래에 사용되던 촉매보다 월등한 정화효율을 나타내면서 전술한 문제점이 발생하지 않는 자동차 배기가스를 정화시키는 촉매의 제조가 요구되고 있다.
In addition, in recent years, as regulations on exhaust gases have been tightened, automobile exhaust gas which does not have the above-mentioned problems while exhibiting superior purification efficiency than conventional catalysts by improving the promoter used in the conventional catalysts for automobiles There is a need for the production of catalysts for purifying gases.

본 발명의 목적은 제1코팅층에 팔라듐을 첨가하고, 제2코팅층에 로듐을 첨가한 비대층구조로 형성되어 열질량의 감소되고, 정화효율이 향상된 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매를 제공하는 것이다.An object of the present invention is a palladium-rhodium-based system having a rare earth metal having a large-layer structure in which palladium is added to the first coating layer and rhodium is added to the second coating layer, thereby reducing the thermal mass and improving the purification efficiency. It is to provide a catalyst for automobiles.

본 발명의 목적은 조촉매로서 란타늄, 네오듐 및 이트륨이 더 첨가되어 반응성 및 내열성이 향상된 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매를 제공하는 것이다.
An object of the present invention is to provide a palladium-rhodium-based automotive catalyst having improved heat resistance by containing a rare earth metal having further added lanthanum, neodium and yttrium as cocatalysts to improve reactivity and heat resistance.

본 발명의 목적은 담체, 상기 담체의 외표면에 형성되며, 팔라듐이 함유되는 제1코팅층 및 상기 제1코팅층의 외표면에 형성되며, 로듐이 함유되는 제2코팅층을 포함하는 것을 특징으로 하는 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매를 제공함에 의해 달성된다.An object of the present invention is a rare earth formed on a carrier, an outer surface of the carrier, a first coating layer containing palladium and a second coating layer formed on the outer surface of the first coating layer, and containing rhodium. It is achieved by providing a catalyst for a palladium-rhodium-based automobile containing metals and improving heat resistance.

본 발명의 바람직한 특징에 따르면, 상기 제1코팅층은 산화알루미늄, 산화스트론듐, 조촉매혼합물 및 팔라듐을 포함하는 것으로 한다.According to a preferred feature of the present invention, the first coating layer comprises aluminum oxide, strontium oxide, a promoter mixture and palladium.

본 발명의 더 바람직한 특징에 따르면, 상기 제1코팅층은 산화알루미늄 55 내지 57 중량부, 산화스트론듐 5 내지 10 중량부, 조촉매혼합물 30 내지 40 중량부 및 팔라듐 1.5 내지 2 중량부를 포함하는 것으로 한다.According to a more preferred feature of the invention, the first coating layer is to include 55 to 57 parts by weight of aluminum oxide, 5 to 10 parts by weight of strontium oxide, 30 to 40 parts by weight of the promoter mixture and 1.5 to 2 parts by weight of palladium do.

본 발명의 더욱 바람직한 특징에 따르면, 상기 조촉매 혼합물은 세륨 30 내지 65 중량부, 지르코늄 35 내지 60 중량부, 란타늄 1 내지 2 중량부, 네오듐 1 내지 2 중량부 및 이트륨 1 내지 2 중량부로 이루어지는 것으로 한다.According to a more preferred feature of the invention, the promoter mixture is composed of 30 to 65 parts by weight of cerium, 35 to 60 parts by weight of zirconium, 1 to 2 parts by weight of lanthanum, 1 to 2 parts by weight of neodium and 1 to 2 parts by weight of yttrium Shall be.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 제2코팅층은 산화알루미늄, 조촉매혼합물 및 로듐을 포함하는 것으로 한다.According to a still further preferred feature of the invention, the second coating layer is to comprise aluminum oxide, a promoter mixture and rhodium.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 제2코팅층은 산화알루미늄 54 내지 56 중량부, 조촉매혼합물 43 내지 45 중량부 및 로듐 0.1 내지 0.5 중량부를 포함하는 것으로 한다.According to a still more preferred feature of the present invention, the second coating layer is 54 to 56 parts by weight of aluminum oxide, 43 to 45 parts by weight of the promoter mixture and 0.1 to 0.5 parts by weight of rhodium.

본 발명의 더욱 더 바람직한 특징에 따르면, 상기 조촉매혼합물은 세륨 30 내지 65 중량부, 지르코늄 35 내지 60 중량부, 란타늄 1 내지 2 중량부, 네오듐 1 내지 2 중량부 및 이트륨 1 내지 2 중량부로 이루어지는 것으로 한다.
According to a further preferred feature of the invention, the promoter mixture is 30 to 65 parts by weight of cerium, 35 to 60 parts by weight of zirconium, 1 to 2 parts by weight of lanthanum, 1 to 2 parts by weight of neodium and 1 to 2 parts by weight of yttrium Shall be made.

본 발명에 따른 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매는 제1코팅층에 팔라듐을 첨가하고, 제2코팅층에 로듐을 첨가한 비대층구조로 형성되어 열질량의 감소되고, 정화효율이 향상되는 탁월한 효과를 나타낸다.Palladium-rhodium-based automotive catalyst containing a rare earth metal according to the present invention having improved heat resistance is formed in an enlarged layer structure in which palladium is added to the first coating layer and rhodium is added to the second coating layer, thereby reducing thermal mass and purifying. It shows an excellent effect of improving efficiency.

또한, 조촉매로서 란타늄, 네오듐 및 이트륨이 더 첨가되어 반응성 및 내열성이 향상되는 탁월한 효과를 나타낸다.
In addition, lanthanum, neodium and yttrium are further added as cocatalysts, which shows an excellent effect of improving reactivity and heat resistance.

도 1은 본 발명의 일실시예에 따른 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매를 나타낸 부분단면도이다.
도 2는 본 발명의 다른 실시예에 따른 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매를 나타낸 부분단면도이다.
도 3은 본 발명에 사용되는 조촉매혼합물과 종래에 사용되던 조촉매혼합물을 TPR측정기로 측정하여 나타낸 그래프이다.
도 4는 본 발명의 실시예 2에 의해 제조된 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매와 비교예 2에 의해 제조된 가솔린 자동차용 촉매의 온도에 따른 일산화탄소(CO)의 전환율을 나타낸 그래프이다.
도 5는 본 발명의 실시예 2에 의해 제조된 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매와 비교예 2에 의해 제조된 가솔린 자동차용 촉매의 온도에 따른 총탄화수소(THC, Total Hydro Carbon)의 전환율을 나타낸 그래프이다.
도 6은 본 발명의 실시예 2에 의해 제조된 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매와 비교예 2에 의해 제조된 가솔린 자동차용 촉매의 온도에 따른 질소산화물(NOx)의 전환율을 나타낸 그래프이다.1 is a partial cross-sectional view showing a catalyst for a palladium-rhodium-based automobile having improved heat resistance by containing a rare earth metal according to an embodiment of the present invention.
FIG. 2 is a partial cross-sectional view showing a catalyst for a palladium-rhodium-based automobile having improved heat resistance by containing a rare earth metal according to another embodiment of the present invention.
Figure 3 is a graph showing the measurement of the promoter mixture used in the present invention and the promoter mixture used in the conventional TPR measurement.
4 is a conversion rate of carbon monoxide (CO) according to the temperature of the palladium- rhodium-based automobile catalyst containing the rare earth metal prepared by Example 2 of the present invention improved heat resistance and the catalyst for gasoline automobile prepared by Comparative Example 2 Is a graph.
5 is a total hydrocarbon (THC, Total) according to the temperature of the palladium- rhodium-based automobile catalyst containing the rare earth metal prepared by Example 2 of the present invention improved heat resistance and the catalyst for gasoline automobile prepared by Comparative Example 2 Hydrocarbon) is a graph showing the conversion rate.
6 is a diagram of nitrogen oxides (NOx) according to the temperature of a catalyst for a gasoline automobile prepared by Comparative Example 2 and a palladium-rhodium-based automobile catalyst containing the rare earth metal prepared by Example 2 of the present invention having improved heat resistance. A graph showing the conversion rate.

이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.
Hereinafter, preferred embodiments of the present invention and physical properties of the respective components will be described in detail with reference to the accompanying drawings. However, the present invention is not limited thereto, And this does not mean that the technical idea and scope of the present invention are limited.

본 발명에 따른 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매는 담체(10), 전술한 담체(10)의 외표면에 형성되며, 팔라듐이 함유되는 제1코팅층(20) 및 전술한 제1코팅층(20)의 외표면에 형성되며, 로듐이 함유되는 제2코팅층(30)으로 이루어진다.Palladium-rhodium-based automotive catalyst containing a rare earth metal according to the present invention improved heat resistance is formed on the outer surface of the carrier 10, the carrier 10, the first coating layer 20 containing palladium and the aforementioned It is formed on the outer surface of the first coating layer 20, and consists of a second coating layer 30 containing rhodium.

전술한 담체(10)는 구형 또는 허니컴 구조로 형성되며, 자동차용 촉매의 기재가 되며, 이러한 담체(10)에 제1코팅층(20) 및 제2코팅층(30)을 형성하면 되면 자동차용 촉매가 제조되는데, 담체(10)로는 자동차용 촉매에 적용할 수 있는 것이면 어떠한 것이든 가능하나, 코디어라이트로 이루어지는 것이 바람직하다.
The carrier 10 is formed in a spherical or honeycomb structure and serves as a substrate for an automobile catalyst. When the first coating layer 20 and the second coating layer 30 are formed on the carrier 10, the catalyst for automobile is formed. Although prepared, the carrier 10 may be any one as long as it can be applied to a catalyst for automobiles, but is preferably made of cordierite.

전술한 제1코팅층(20)은 전술한 담체(10)의 외표면에 형성되며, 팔라듐이 함유되는데, 산화알루미늄, 산화스트론듐, 조촉매혼합물 및 팔라듐을 포함하여 이루어지며, 산화알루미늄 55 내지 57 중량부, 산화스트론듐 5 내지 10 중량부, 조촉매혼합물 30 내지 40 중량부 및 팔라듐 1.5 내지 2 중량부를 포함하는 것이 더욱 바람직하다.The first coating layer 20 is formed on the outer surface of the carrier 10 described above, and contains palladium. The first coating layer 20 includes aluminum oxide, strontium oxide, a promoter mixture, and palladium. More preferably 57 parts by weight, 5 to 10 parts by weight of strontium oxide, 30 to 40 parts by weight of the promoter mixture and 1.5 to 2 parts by weight of palladium.

이때, 전술한 조촉매혼합물은 세륨 30 내지 65 중량부, 지르코늄 35 내지 60 중량부, 란타늄 1 내지 2 중량부, 네오듐 1 내지 2 중량부 및 이트륨 1 내지 2 중량부로 이루어지는 것이 바람직하며, 전술한 란타늄, 네오듐 및 이트륨은 전술한 제1코팅층의 반응성 및 내열성을 향상시켜 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매의 정화효율을 향상시키는 역할을 한다.At this time, the aforementioned promoter mixture is preferably composed of 30 to 65 parts by weight of cerium, 35 to 60 parts by weight of zirconium, 1 to 2 parts by weight of lanthanum, 1 to 2 parts by weight of neodium and 1 to 2 parts by weight of yttrium, Lanthanum, neodium and yttrium improve the reactivity and heat resistance of the first coating layer described above, thereby improving the purification efficiency of the palladium-rhodium-based automotive catalyst containing rare earth metals and improving heat resistance.

전술한 제1코팅층(20)은 전술한 담체(10)의 외표면에 탈이온수 100 중량부, 산화알루미늄 55 내지 57 중량부, 산화스트론듐 5 내지 10 중량부, 조촉매혼합물 30 내지 40 중량부 및 팔라듐 1.5 내지 2 중량부로 이루어지며, pH가 6.5 내지 7.5으로 조절된 혼합물을 3.0 내지 4.5㎛의 입자크기로 분쇄한 후에 도포하여 형성된다.
The first coating layer 20 is 100 parts by weight of deionized water, 55 to 57 parts by weight of aluminum oxide, 5 to 10 parts by weight of strontium oxide, 30 to 40 parts by weight of the promoter mixture on the outer surface of the carrier 10 described above. Part and 1.5 to 2 parts by weight of palladium, and a mixture having a pH adjusted to 6.5 to 7.5 is formed by pulverizing to a particle size of 3.0 to 4.5 mu m and then applying.

전술한 제2코팅층(30)은 전술한 제1코팅층(20)의 외표면에 형성되며, 로듐이 함유되는데, 산화알루미늄, 조촉매혼합물 및 로듐을 포함하여 이루어지며, 산화알루미늄 54 내지 56 중량부, 조촉매혼합물 43 내지 45 중량부 및 로듐 0.1 내지 0.5 중량부를 포함하는 것이 더욱 바람직하다. The above-described second coating layer 30 is formed on the outer surface of the above-described first coating layer 20, and contains rhodium, comprising aluminum oxide, a promoter mixture and rhodium, 54 to 56 parts by weight of aluminum oxide More preferably, 43 to 45 parts by weight of the promoter mixture and 0.1 to 0.5 parts by weight of rhodium.

이때, 전술한 조촉매혼합물은 세륨 30 내지 65 중량부, 지르코늄 35 내지 60 중량부, 란타늄 1 내지 2 중량부, 네오듐 1 내지 2 중량부 및 이트륨 1 내지 2 중량부로 이루어지는 것이 바람직하며, 전술한 란타늄, 네오듐 및 이트륨은 전술한 제2코팅층(30)의 반응성 및 내열성을 향상시켜 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매의 정화효율을 향상시키는 역할을 한다.At this time, the aforementioned promoter mixture is preferably composed of 30 to 65 parts by weight of cerium, 35 to 60 parts by weight of zirconium, 1 to 2 parts by weight of lanthanum, 1 to 2 parts by weight of neodium and 1 to 2 parts by weight of yttrium, Lanthanum, neodium and yttrium improve the reactivity and heat resistance of the above-described second coating layer 30 to improve the purification efficiency of the palladium-rhodium-based automotive catalyst containing rare earth metal and improving heat resistance.

전술한 제2코팅층(30)은 전술한 제1코팅층(20)의 외표면에 탈이온수 100 중량부, 산화알루미늄 54 내지 56 중량부, 조촉매혼합물 43 내지 45 중량부 및 로듐 0.1 내지 0.5 중량부로 이루어지며, pH가 6.0 내지 7.0으로 조절된 혼합물을 3.0 내지 4.5㎛의 입자크기로 분쇄한 후에 도포하여 형성된다.
The second coating layer 30 is 100 parts by weight of deionized water, 54 to 56 parts by weight of aluminum oxide, 43 to 45 parts by weight of the promoter mixture and 0.1 to 0.5 parts by weight of rhodium on the outer surface of the first coating layer 20 described above. It is formed by grinding the mixture adjusted to pH 6.0-7.0 to a particle size of 3.0 to 4.5㎛ and then applied.

전술한 제1코팅층(20) 및 제2코팅층(30)으로 이루어진 코팅층의 두께는 160 내지 180㎛인 것이 바람직하며, 제2코팅층(30)을 도포한 후에는 담체(10)를 80 내지 120℃의 온도로 가열하여 제1코팅층(20) 및 제2코팅층(30)에 함유된 탈이온수를 증발시키고, 탈이온수가 증발된 후에는 제1코팅층(20) 및 제2코팅층(30)이 형성된 담체(10)를 500 내지 600℃의 온도로 4 내지 5시간 소성한다.The thickness of the coating layer consisting of the first coating layer 20 and the second coating layer 30 is preferably 160 to 180 μm, and after applying the second coating layer 30, the carrier 10 is 80 to 120 ° C. The deionized water contained in the first coating layer 20 and the second coating layer 30 is evaporated by heating to a temperature of, and after the deionized water is evaporated, the carrier having the first coating layer 20 and the second coating layer 30 formed thereon. (10) is baked at a temperature of 500 to 600 ° C. for 4 to 5 hours.

전술한 소성을 통해 제1코팅층(20) 및 제2코팅층(30)에 함유되어 있던 불순물이 제거되고, 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매가 제조된다.
Through the above-described firing, impurities contained in the first coating layer 20 and the second coating layer 30 are removed, and a palladium-rhodium-based automotive catalyst including a rare earth metal having improved heat resistance is manufactured.

이하에서는 본 발명에 따른 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매의 제조방법 및 물성을 실시예를 들어 설명한다.
Hereinafter, a method for producing a palladium-rhodium-based catalyst for automobiles containing the rare earth metal according to the present invention and improved heat resistance will be described with reference to Examples.

<실시예 1>&Lt; Example 1 >

세륨 50 중량부, 지르코늄 45 중량부, 란타늄 2 중량부, 네오듐 2 중량부 및 이트륨 1 중량부를 혼합하여 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매에 첨가되는 조촉매혼합물을 제조하였다.
50 parts by weight of cerium, 45 parts by weight of zirconium, 2 parts by weight of lanthanum, 2 parts by weight of neodium, and 1 part by weight of yttrium were mixed to prepare a cocatalyst mixture added to a catalyst for a palladium-rhodium-based automobile having improved heat resistance by containing rare earth metals. It was.

<비교예 1>&Lt; Comparative Example 1 &

세륨 50 중량부, 지르코늄 49 중량부 및 란타늄 1 중량부를 혼합하여 가솔린 자동차용 촉매에 사용되고 있는 조촉매혼합물을 제조하였다.
50 parts by weight of cerium, 49 parts by weight of zirconium and 1 part by weight of lanthanum were mixed to prepare a promoter mixture used in a gasoline automobile catalyst.

<실시예 2><Example 2>

코디어라이트로 담체를 제조하고, 전술한 담체의 외표면에 탈이온수 100 중량부, 산화알루미늄 56 중량부, 7.5 중량부, 실시예 1을 통해 제조된 조촉매혼합물 35 중량부 및 팔라듐 1.75 중량부로 형성된 혼합물의 pH를 6.5 내지 7.5으로 조절하고입자크기가 3.0 내지 4.5㎛를 갖도록 분쇄한 후에 담체에 도포하여 제1코팅층을 형성하고, 전술한 제1코팅층의 외표면에 탈이온수 100 중량부, 산화알루미늄 55 중량부, 조촉매혼합물 44 중량부 및 로듐 0.25 중량부로 형성된 혼합물의 pH를 pH가 6.0 내지 7.0으로 조절하고, 입자크기가 3.0 내지 4.5㎛를 갖도록 분쇄한 후에 제1코팅층의 외표면에 도포하여 제2코팅층을 형성하고, 제2코팅층이 형성된 담체를 100℃의 온도로 가열하고, 550℃의 온도로 4시간 동안 소성하여 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매를 제조하였다.
A carrier was prepared with cordierite, and 100 parts by weight of deionized water, 56 parts by weight of aluminum oxide, 7.5 parts by weight, 35 parts by weight of the promoter mixture prepared in Example 1, and 1.75 parts by weight of palladium were prepared on the outer surface of the carrier. The pH of the formed mixture is adjusted to 6.5 to 7.5 and pulverized to have a particle size of 3.0 to 4.5 μm, and then applied to a carrier to form a first coating layer. 100 parts by weight of deionized water and oxidation on the outer surface of the first coating layer described above. The pH of the mixture formed of 55 parts by weight of aluminum, 44 parts by weight of the promoter mixture and 0.25 parts by weight of rhodium is adjusted to a pH of 6.0 to 7.0, pulverized to have a particle size of 3.0 to 4.5 μm, and then applied to the outer surface of the first coating layer. To form a second coating layer, the carrier on which the second coating layer was formed was heated to a temperature of 100 ° C., and calcined at a temperature of 550 ° C. for 4 hours to contain a rare earth metal, thereby improving heat resistance. The borrower catalyst was prepared.

<비교예 2>Comparative Example 2

실시예 2와 동일하게 진행하되 비교예 1을 통해 제조된 조촉매혼합물을 사용하여 가솔린 자동차용 촉매를 제조하였다.
Proceed in the same manner as in Example 2 but using a promoter mixture prepared in Comparative Example 1 to prepare a catalyst for a gasoline vehicle.

전술한 실시예 1 및 비교예 1을 통해 제조된 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매에 첨가되는 조촉매혼합물 및 가솔린 자동차용 촉매에 사용되고 있는 조촉매혼합물의 성능을 평가하여 아래 도 3에 나타내었다.By evaluating the performance of the promoter mixture containing the rare earth metal prepared in Example 1 and Comparative Example 1 described above and added to the palladium-rhodium-based automobile catalyst having improved heat resistance and the catalyst mixture used in the catalyst for gasoline automobile 3 is shown below.

(단, 조촉매혼합물의 성능평가는 아래에 조건으로 측정하였다.(However, the performance evaluation of the promoter mixture was measured under the following conditions.

Model : TPR, Temperature Programde ReductionModel: TPR, Temperature Programde Reduction

Detector : TCdDetector: TCd

Sample : 1000도 10시간 Oven AgingSample: 1000 degrees 10 hours Oven Aging

평가 방법Assessment Methods

가)촉매제조시 사용되는 조촉매를 샘플(0.05g)링하여 유리셀에 투입함.A) Sample (0.05g) of the catalyst used in the preparation of the catalyst is put into the glass cell.

나)전처리로 550℃의 온도까지 30℃/min 승온하면서 산소가스를 흘려줌.B) Oxygen gas flows while preheating up to 30 ℃ / min to 550 ℃.

다)전처리 후 온도를 40℃ 까지 하강한 후 40 내지 1000℃ 까지 30℃/min 승온 하면서 수소가스를 흘려준다.C) After the pretreatment, the temperature is lowered to 40 ° C and hydrogen gas is flowed while raising the temperature to 40 ° C to 1000 ° C by 30 ° C / min.

라)일정한 온도가 되면 조촉매에 수소가스가 흡착되는 시점에서 Detector가 감지하여 신호로 나타남.D) When the temperature reaches a certain temperature, the detector detects and displays a signal when hydrogen gas is adsorbed to the promoter.

즉, 조촉매의 성능이 좋은 것은 저온구간에서 수소가스를 흡착하는 경우와 흡착량이 상대적으로 많은 경우가 해당된다. 따라서, 그래프의 곡선이 낮은 온도에서 시작되며 peak의 높이가 높을수록 향상된 것이다.)That is, the good performance of the promoter corresponds to the case of adsorbing hydrogen gas in the low temperature section and the case where the amount of adsorption is relatively large. Therefore, the curve in the graph starts at a lower temperature, and the higher the height of the peak, the better.)

아래 도 3에 나타낸 것처럼 TPR 시험결과 본 발명에 의해 제조된 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매에 첨가되는 조촉매혼합물은 비교예 1에 의해 제조된 가솔린 자동차용 촉매에 사용되고 있는 조촉매혼합물에 비해 400 내지 600℃ 부근에서 peak가 높게 나타나기 때문에 수소의 저장량이 많은 것을 알 수 있고, 수소의 저장량 향상으로 인해 정화성능이 향상된 것을 알 수 있다.
As shown in FIG. 3 below, the promoter mixture containing the rare earth metal produced by the present invention and added to the palladium-rhodium-based automobile catalyst having improved heat resistance is used in the gasoline automobile catalyst prepared by Comparative Example 1 as shown in FIG. 3. It can be seen that the storage amount of hydrogen is high because the peak appears around 400 to 600 ° C. higher than that of the cocatalyst mixture, and the purification performance is improved due to the improvement of the storage amount of hydrogen.

전술한 실시예 2 및 비교예 2를 통해 제조된 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매 및 가솔린 자동차용 촉매의 활성능력 및 정화율을 평가하여 아래 표 1 내지 2 및 도 4 내지 6에 나타내었다.The activity and purification rate of the palladium-rhodium-based automobile catalyst and the gasoline automobile catalyst containing the rare earth metals prepared by the above-described Examples 2 and Comparative Example 2 and improved heat resistance were evaluated. To 6 are shown.

{단, 촉매의 황성능력 평가는 모의활성 가스벤치(Synthetic Gas Bench) 평가조건에서 촉매의 성능평가를 진행하였다.{However, the evaluation of the sulfur capacity of the catalyst was carried out to evaluate the performance of the catalyst under the conditions of the simulation of the simulated gas bench.

평가 방법 : 활성능력 Conversion(%), 전화온도(Ligh Off Temperature)Evaluation Method: Active Capacity Conversion (%), Telephone Temperature (Ligh Off Temperature)

Model : HINZECAT-1004(Korea)Model: HINZECAT-1004 (Korea)

Aanlyzer : HC, CO, NOx, O2, CO2 Aanlyzer: HC, CO, NOx, O 2 , CO 2

주파수(Hz) : 1.0Frequency (Hz): 1.0

공간속도(Hr-1) : 100,000Space Speed (Hr-1): 100,000

승온속도(℃/min) : 30Temperature increase rate (℃ / min): 30

시료Size(mm) : (D)25.4 × 56Sample Size (mm): (D) 25.4 × 56

Aging Condition : 1100℃ × 10시간 (Oven Aging)}
Aging Condition: 1100 ℃ × 10 hours (Oven Aging)}

<표 1>TABLE 1

Figure 112010084032495-pat00001
Figure 112010084032495-pat00001

Light-Off Temperature 평가결과 정화율 50% 도달시점의 전화온도가 약 20℃이상으로 빨라져 정화효율이 향상되는 것을 알 수 있다.
As a result of light-off temperature evaluation, the conversion temperature is improved to about 20 ℃ or more when the purification rate reaches 50%.

<표 2><Table 2>

Figure 112010084032495-pat00002
Figure 112010084032495-pat00002

위에 표 2에 나타낸 것처럼 전환율 비교결과 CO의 경우 Lambda값이 0.98인 희박연소 영역(Rich)에서 10%이상의 정화효율이 향상되었으며, NOx의 경우 Lambda값이 1.02인 영역(Lean)에서 10% 이상의 정화효율이 향상된 것을 알 수 있다.
As shown in Table 2 above, as a result of the conversion rate comparison, the purification efficiency of CO was improved by 10% or more in the lean burn zone (Rich) with Lambda value of 0.98, and by 10% or more in the zone (Lean) with Lambda value of 1.02 for NOx. It can be seen that the efficiency is improved.

10 ; 담체
20 ; 제1코팅층
30 ; 제2코팅층10; carrier
20; First coating layer
30; 2nd coating layer

Claims (7)

담체;
상기 담체의 외표면에 형성되며, 알루미늄 55 내지 57 중량부, 산화스트론듐 5 내지 10 중량부, 조촉매혼합물 30 내지 40 중량부 및 팔라듐 1.5 내지 2 중량부로 이루어진 제1코팅층; 및
상기 제1코팅층의 외표면에 형성되며, 알루미늄 54 내지 56 중량부, 조촉매혼합물 43 내지 45 중량부 및 로듐 0.1 내지 0.5 중량부로 이루어진 제2코팅층;을 포함하며,
상기 조촉매 혼합물은 세륨 30 내지 65 중량부, 지르코늄 35 내지 60 중량부, 란타늄 1 내지 2 중량부, 네오듐 1 내지 2 중량부 및 이트륨 1 내지 2 중량부로 이루어지는 것을 특징으로 하는 희토류 금속을 함유하여 내열성이 향상된 팔라듐-로듐계 자동차용 촉매.carrier;
A first coating layer formed on an outer surface of the carrier and composed of 55 to 57 parts by weight of aluminum, 5 to 10 parts by weight of strontium oxide, 30 to 40 parts by weight of the promoter mixture, and 1.5 to 2 parts by weight of palladium; And
And a second coating layer formed on an outer surface of the first coating layer and comprising 54 to 56 parts by weight of aluminum, 43 to 45 parts by weight of the promoter mixture, and 0.1 to 0.5 parts by weight of rhodium.
The promoter mixture contains a rare earth metal, characterized in that consisting of 30 to 65 parts by weight of cerium, 35 to 60 parts by weight of zirconium, 1 to 2 parts by weight of lanthanum, 1 to 2 parts by weight of neodium and 1 to 2 parts by weight of yttrium. Palladium-rhodium-based automotive catalyst with improved heat resistance. 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090045214A (en) * 2006-06-29 2009-05-07 우미코레 아게 운트 코 카게 Three-way catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090045214A (en) * 2006-06-29 2009-05-07 우미코레 아게 운트 코 카게 Three-way catalyst

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