KR20030024085A - A catalyst for reduction of emitted gases from automobile with lean-burn engine and the manufacturing method thereof - Google Patents

A catalyst for reduction of emitted gases from automobile with lean-burn engine and the manufacturing method thereof Download PDF

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KR20030024085A
KR20030024085A KR1020010057064A KR20010057064A KR20030024085A KR 20030024085 A KR20030024085 A KR 20030024085A KR 1020010057064 A KR1020010057064 A KR 1020010057064A KR 20010057064 A KR20010057064 A KR 20010057064A KR 20030024085 A KR20030024085 A KR 20030024085A
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oxide
catalyst
exhaust gas
burn engine
lean
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KR1020010057064A
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Korean (ko)
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길정기
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현대자동차주식회사
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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
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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

Abstract

PURPOSE: A catalyst for purifying exhaust gas of automobile with lean-burn engine is provided to efficiently purify nitrogen oxides that are not easily purified by existing catalysts for gasoline engine automobile under the rarefied combustion atmosphere as in the lean-burn engine automobile, and a manufacturing method thereof is provided. CONSTITUTION: The catalyst for purifying exhaust gas of automobile with lean-burn engine is characterized in that activated alumina, rare earth oxides and barium oxide (BaO) cocatalyst and precious metal catalyst activating material are respectively supported onto a ceramic or metallic porous support, wherein 30 to 50 wt.% of activated alumina is supported onto the support for 100 wt.% of the porous support, 1 to 5 wt.% of lanthanum (La) oxide, 10 to 30 wt.% of cerium (Ce) oxide and 10 to 20 wt.% of zirconium (Zr) oxide as the rare earth oxides are supported onto the support, and 5 to 20 wt.% of barium oxide (BaO) is supported onto the support for 100 wt.% of the porous support, and wherein the precious metal catalyst activating material is selected from platinum (Pt), palladium (Pd), rhodium (Rh), or a mixture thereof. The manufacturing method of the catalyst for purifying exhaust gas of automobile with lean-burn engine comprises a step (a) of mixing the materials after impregnating precious metal catalysts into activated alumina; a step (b) of preparing a slurry by adding rare earth oxides and barium oxide to the mixture and milling the materials; and a step (c) of drying and calcining the slurry coated porous support after coating the slurry prepared in the step (b) on a honeycomb monolith ceramic or metallic porous support.

Description

린번엔진 자동차의 배기가스 정화용 촉매 및 그 제조방법{A catalyst for reduction of emitted gases from automobile with lean-burn engine and the manufacturing method thereof}A catalyst for reduction of emitted gases from automobile with lean-burn engine and the manufacturing method

본 발명은 린번엔진 자동차 배기가스 정화용 촉매 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 다공성 담지체(세라믹 또는 금속)에 활성알루미나(γ-Al2O3), 희토류산화물, 및 촉매활성물질로서 귀금속을 각각 담지시키되, 여기에 조촉매로 알칼리금속산화물인 바륨산화물을 첨가함으로써 종래의 가솔린 엔진 자동차용 배기가스 정화용 촉매로는 정화하기 어려운 희박연소 분위기에서도 질소산화물을 효과적으로 정화할 수 있는 린번엔진 자동차 배기가스 정화용 촉매 및 그 제조방법에 관한 것이다.The present invention relates to a catalyst for purifying exhaust gas of a lean burn engine and a method of manufacturing the same. More particularly, the present invention relates to an active alumina (γ-Al 2 O 3 ), a rare earth oxide, and a catalytically active material in a porous support (ceramic or metal). The lean-burn engine automobile which can carry noble metals separately, but adds barium oxide, an alkali metal oxide, as a cocatalyst, to effectively purify nitrogen oxides even in a lean combustion atmosphere that is difficult to purify by the exhaust gas purification catalyst for a conventional gasoline engine vehicle. An exhaust gas purifying catalyst and a method of manufacturing the same.

종래의 가솔린 엔진 자동차의 배기가스 정화용 촉매는 이론공연비 부근에서 탄화수소, 이산화탄소 및 질소산화물을 정화하도록 만들어지고 있다.The catalyst for purifying exhaust gas of a conventional gasoline engine vehicle is made to purify hydrocarbons, carbon dioxide and nitrogen oxides in the vicinity of theoretical fuel consumption.

그러나, 종래의 가솔린 엔진 자동차의 배기가스 정화용 촉매는 효율적으로 질소산화물 등을 완전하게 정화하지는 못하고 있다.However, conventional catalysts for exhaust gas purification of gasoline engine automobiles do not efficiently purify nitrogen oxides and the like.

특히, 상기 촉매의 경우 희박공연비, 즉 산소가 많이 존재하는 운전조건하에서는 산화분위기 때문에 질소산화물을 환원하여 정화하기가 어려웠다.In particular, in the case of the catalyst, it is difficult to purify the nitrogen oxides by reducing the oxidizing atmosphere under the lean fuel ratio, that is, the operating conditions in which oxygen is large.

이에, 본 발명은 종래 상기와 같은 문제점을 해결하기 위하여, 린번엔진 자동차에서와 같은 희박연소분위기에서 기존의 가솔린 엔진 자동차용 배기가스 정화용 촉매로는 정화하기 어려운 질소산화물을 효율적으로 정화할 수 있는 린번엔진 자동차용 배기가스 정화용 촉매 및 그의 제조방법을 제공하는데 그 목적이 있다.Therefore, in order to solve the problems as described above, the lean burn which can efficiently purify nitrogen oxide which is difficult to purify with the exhaust gas purification catalyst for a conventional gasoline engine car in a lean burn atmosphere such as in a lean burn engine car is conventional. It is an object of the present invention to provide a catalyst for exhaust gas purification for an engine vehicle and a method of manufacturing the same.

도 1은 본 발명의 실시예 1 ∼ 2 및 비교예의 온도변화에 따른 질소정화율을 나타낸 것이다.1 shows the nitrogen purification rate according to the temperature change of Examples 1 to 2 and Comparative Examples of the present invention.

본 발명은 세라믹 또는 금속인 다공성 담지체에 활성알루미나와, 희토류산화물 및 바륨산화물(BaO) 조촉매, 및 귀금속 촉매활성물질이 각각 담지되어 있는 것을 특징으로 하는 린번엔진 자동차 배기가스 정화용 촉매를 그 특징으로 한다.The present invention provides a catalyst for purifying exhaust gas for a lean burn engine, characterized in that an active alumina, a rare earth oxide and a barium oxide (BaO) promoter, and a noble metal catalytically active material are respectively supported on a porous support that is ceramic or metal. It is done.

또한, 본 발명은 린번엔진 자동차 배기가스 정화용 촉매의 제조방법에 있어서, a) 귀금속 촉매물질을 각각 활성알루미나에 함침시킨뒤 혼합하는 단계; b) 희토류산화물 및 바륨산화물을 첨가하고 밀링하여 슬러리를 제조하는 단계; 및 c) 상기 b)에서 제조된 슬러리를 벌집구조의 세라믹 또는 금속인 다공성 담지체에 코팅하여 건조시킨 다음 소성하는 단계로 이루어진 것을 특징으로 하는 린번엔진 자동차 배기가스 정화용 촉매의 제조방법을 포함한다.In addition, the present invention provides a method for preparing a catalyst for purifying exhaust gas of a lean burn engine, comprising the steps of: a) impregnating a noble metal catalyst material into activated alumina and then mixing them; b) adding a rare earth oxide and a barium oxide and milling to prepare a slurry; And c) a method of preparing a catalyst for purifying exhaust gas for a lean burn engine, characterized in that the slurry prepared in b) is coated on a porous carrier of a honeycomb ceramic or metal, dried, and then fired.

이하, 본 발명을 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

본 발명은 다공성 담지체(세라믹 또는 금속)에 활성알루미나, 희토류산화물, 알칼리금속산화물 및 촉매활성물질로서 귀금속이 각각 담지되어 있는 것으로, 특히 희박연소 분위기에서도 질소산화물을 효과적으로 정화할 수 있도록 바륨산화물을 사용하는 린번엔진 자동차 배기가스 정화용 촉매 및 그 제조방법에 관한 것이다.In the present invention, active alumina, rare earth oxide, alkali metal oxide and precious metal are supported on the porous support (ceramic or metal), respectively. Particularly, barium oxide is effectively purified so that nitrogen oxide can be effectively purified even in a lean combustion atmosphere. The present invention relates to a catalyst for lean burn engine exhaust gas purification to be used, and a method of manufacturing the same.

본 발명에서 사용하는 귀금속 촉매활성물질은 백금(Pt), 팔라듐(Pd), 및 로듐(Rh) 중에서 선택되는 1 종 또는 2 종 이상의 조합으로 이루어진 것을 말한다.The precious metal catalytically active material used in the present invention refers to one or a combination of two or more selected from platinum (Pt), palladium (Pd), and rhodium (Rh).

본 발명에 따른 촉매는 바람직하게는 백금-로듐 촉매이며, 팔라듐-로듐 담지 촉매의 경우도 상기 백금-로듐 촉매의 제조과정과 동일한 과정을 거쳐 제조할 수 있다.The catalyst according to the present invention is preferably a platinum-rhodium catalyst, and a palladium-rhodium-supported catalyst can also be prepared through the same process as that of the platinum-rhodium catalyst.

본 발명에서 사용하는 담지체에 대한 담지를 위한 귀금속의 소오스(source)로는 귀금속 염화물, 질산염 및 초산염 등이 있다. 또한 촉매에서 담지층으로 사용되는 활성 알루미나, 및 조촉매로 사용되는 희토류산화물과 바륨산화물(BaO)의 소오스로는 산화물, 질산염, 염화물, 초산염 및 황산염 등이 있다.Sources of precious metals for supporting the carriers used in the present invention include noble metal chlorides, nitrates and acetates. In addition, the active alumina used as a supporting layer in the catalyst, and the rare earth oxide and barium oxide (BaO) used as cocatalysts include oxides, nitrates, chlorides, acetates and sulfates.

상기 희토류 산화물은 바람직하게는 란타늄산화물(La2O3), 세륨산화물(CeO2), 및 지르코늄산화물(ZrO2)의 혼합물이다.The rare earth oxide is preferably a mixture of lanthanum oxide (La 2 O 3 ), cerium oxide (CeO 2 ), and zirconium oxide (ZrO 2 ).

본 발명에서 사용하는 알루미나는 다공성 담지체 100 중량%에 대하여 30 ∼ 50 중량%로 사용하는 것이 바람직하다. 또한, 란타늄산화물은 다공성 담지체 100 중량%에 대하여 1 ∼ 5 중량%, 세륨산화물은 10 ∼ 30 중량%, 지르코늄산화물은 10 ∼ 20 중량%의 범위로 사용하는 것이 바람직하다.The alumina used in the present invention is preferably used in 30 to 50% by weight based on 100% by weight of the porous support. The lanthanum oxide is preferably used in an amount of 1 to 5% by weight, 10 to 30% by weight of cerium oxide, and 10 to 20% by weight of zirconium oxide, based on 100% by weight of the porous support.

특히, 본 발명의 핵심인 바륨산화물은 5 ∼ 20 중량%의 범위로 사용하는 것이 바람직하며, 바륨 산화물의 사용량이 5 중량% 미만이면 질소산화물의 정화성능이 현저히 떨어지는 문제가 있고, 20 중량%를 초과하면 바륨산화물이 지지체인 알루미나와 화합물을 형성하므로 첨가 효과가 적다는 문제가 있다.In particular, barium oxide, which is the core of the present invention, is preferably used in the range of 5 to 20% by weight, and when the amount of the barium oxide is less than 5% by weight, there is a problem in that the purification performance of nitrogen oxide is significantly reduced, and 20% by weight If it exceeds, the barium oxide forms a compound with alumina as a support, so there is a problem in that the addition effect is small.

또한, 본 발명에서 백금-로듐촉매를 제조하는 경우 백금:로듐의 함량비는 1∼10 : 1∼2 중량비로 하여 귀금속 농도를 조절하는 것이 바람직하다.In the present invention, when the platinum-rhodium catalyst is prepared, the content ratio of platinum: rhodium is preferably 1 to 10: 1 to 2 to adjust the noble metal concentration.

한편, 본 발명의 린번엔진 자동차 배기가스 정화용 촉매의 제조방법은 백금과, 팔라듐 또는 로듐 등의 귀금속류를 농도를 조절하여 각각 지지체에 함침시킨뒤, 밀링하여 슬러리를 제조하여 벌집구조의 세라믹 또는 금속등의 담체에 코팅하여 건조시킨 다음 소성하는 과정으로 구성된다. 이중에서 백금-로듐 촉매에 대하여 일례를 들어 보다 구체적으로 설명하면 다음과 같다.Meanwhile, in the method for preparing a catalyst for purifying exhaust gas of a lean burn engine of the present invention, after impregnating precious metals such as platinum and palladium or rhodium on a support, the slurry is milled to prepare a slurry and then a ceramic or metal having a honeycomb structure It consists of a process of coating and drying and then firing the carrier. Among them, the platinum-rhodium catalyst will be described in more detail by way of example.

먼저 백금용액, 로듐용액을 지지체인 활성알루미나에 각각 함침시킨다. 다음으로, 귀금속이 함침된 각각의 지지체를 습식밀링하여 슬러리를 제조한다.이때 란타늄산화물, 세륨산화물, 지르코늄산화물 및 바륨산화물을 첨가하여 슬러리를 완성한다.First, a platinum solution and a rhodium solution are impregnated into activated alumina as a support. Next, each of the supports impregnated with the noble metal is wet milled to prepare a slurry. At this time, lanthanum oxide, cerium oxide, zirconium oxide and barium oxide are added to complete the slurry.

상기 과정을 통하여 제조된 슬러리들을 벌집구조의 담체에 코팅한다. 이때 먼저 백금이 함침된 슬러리를 코팅하고, 다음에 로듐이 함침된 슬러리를 코팅하여 이중 코팅한다.The slurry prepared through the above process is coated on the carrier of the honeycomb structure. In this case, first, the platinum-impregnated slurry is coated, and then the rhodium-impregnated slurry is coated and double coated.

상기 과정을 통하여 제조된 워시코트 슬러리를 벌집구조의 촉매 담지체에 코팅한다. 이때 백금 또는 팔라듐이 담지된 와시코트 슬러리를 먼저 코팅하고 로듐이 담지된 슬러리를 나중에 코팅하는 것이 바람직하다. 또한 와시코트 슬러리를 촉매 담체에 단일 코팅하는 것이 더욱 바람직하다.The washcoat slurry prepared through the above process is coated on the catalyst carrier of the honeycomb structure. At this time, it is preferable to coat the washcoat slurry on which platinum or palladium is supported first and the slurry on which rhodium is supported later. It is also more preferred to single coat the washcoat slurry onto the catalyst carrier.

이후, 상기 코팅된 담체는 건조시키고 소결하여 촉매제를 제조한다. 이때 백금 및 로듐 등의 귀금속이 함유된 슬러리가 코팅된 담체를 100 ∼ 150 ℃에서 건조시킨 다음, 400 ∼ 600 ℃에서 소결하는 것이 바람직하다.Thereafter, the coated carrier is dried and sintered to prepare a catalyst. At this time, it is preferable that the carrier coated with the slurry containing noble metals such as platinum and rhodium is dried at 100 to 150 ° C, and then sintered at 400 to 600 ° C.

이하, 본 발명을 다음의 실시예에 의거하여 더욱 상세히 설명하겠는바, 본 발명이 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

실시예 1 :Example 1: 백금(Pt)-로듐(Rh) 담지 촉매의 제조Preparation of platinum (Pt) -rhodium (Rh) supported catalyst

백금:로듐의 함량비는 2:1이며, 백금과 로듐의 농도는 다공성 담지체 100 중량%에 대하여 2.5 중량%이고, 바륨산화물은 5 중량%인 백금-로듐 촉매를 제조하여 촉매가 열화(aged)된 상태에서 배기가스중 질소산화물의 정화성능시험을 실시하였다. 이때, 활성알루미나는 다공성 담지체 100 중량%에 대하여 45 중량%로 담지되어 있고, 란타늄산화물은 5 중량%, 세륨산화물은 15 중량%, 및 지르코늄산화물은 5 중량%가 담지되도록 하였다.The platinum to rhodium content ratio is 2: 1, the concentration of platinum and rhodium is 2.5% by weight based on 100% by weight of the porous support, and the barium oxide is 5% by weight. ), The purification performance of nitrogen oxides in the exhaust gas was tested. At this time, the activated alumina was supported at 45% by weight based on 100% by weight of the porous support, 5% by weight of lanthanum oxide, 15% by weight of cerium oxide, and 5% by weight of zirconium oxide.

이때의 모델가스 조성은 다음 표 1과 같으며, 상온에서 450 ℃까지 10 ℃/min의 승온속도로 질소산화물의 정화 효율을 측정하였다. 이때의 공간속도는 40,000/hr이었고, 그 결과는 도 1에서 -●-로 나타내었다.At this time, the model gas composition is shown in Table 1 below, and the purification efficiency of nitrogen oxide was measured at a temperature rising rate of 10 ° C./min from room temperature to 450 ° C. The space velocity at this time was 40,000 / hr, and the result is represented by-●-in FIG.

실시예 2 :Example 2: 백금(Pt)-로듐(Rh) 담지 촉매의 제조Preparation of platinum (Pt) -rhodium (Rh) supported catalyst

상기 실시예 1과 동일한 방법으로 제조하되, 바륨산화물의 첨가량을 10 중량%로 하는 백금-로듐 촉매를 제조한 후, 이에 대한 질소산화물 정화 효율을 측정하였고, 그 결과는 도 1에서 -◆-로 나타내었다.Prepared in the same manner as in Example 1, but after preparing a platinum-rhodium catalyst having an addition amount of barium oxide of 10% by weight, the nitrogen oxide purification efficiency was measured for this, the result is-◆- Indicated.

비교예Comparative example

현재 일반 가솔린엔진 배기가스 정화용 촉매로 사용되고 있는 백극-로듐 촉매의 경우로 백금:로듐의 함량비는 5:1이며, 백금과 로듐의 농도는 담지체 100 중량%에 대하여 2.5 중량%, 바륨산화물은 첨가되지 않았으며, 촉매가 열화된 상태에서 배기가스중 질소산화물의 정화성능시험을 실시하였다. 그 결과는 도 1에서-○-로 나타내었다.In the case of the anode-rhodium catalyst which is currently used as a catalyst for exhaust gas purification of a general gasoline engine, the content ratio of platinum to rhodium is 5: 1, and the concentration of platinum and rhodium is 2.5% by weight based on 100% by weight of the carrier, and barium oxide It was not added, and the purification performance test of the nitrogen oxide in the exhaust gas was carried out with the catalyst deteriorated. The result is shown as-(circle) in FIG.

도 1에서 보면, 본 발명의 실시예 1 ∼ 2의 경우 질소산화물의 정화율이 비교예에 비해 매우 우수함을 알 수 있다.1, it can be seen that in the case of Examples 1 to 2 of the present invention, the purification rate of nitrogen oxide is very excellent compared to the comparative example.

이상에서 설명한 바와 같이, 본 발명은 다공성 담지체(세라믹 또는 금속)에 활성알루미나, 희토류산화물, 및 촉매활성물질로서 귀금속을 각각 담지시켜 제조되는 귀금속 담지촉매에 조촉매로 알칼리금속산화물인 바륨산화물을 첨가함으로써 종래 가솔린 엔진 자동차용 배기가스 정화용 촉매로는 정화하기 어려운 희박연소 분위기에서도 질소산화물을 효과적으로 정화하여 질소산화물의 정화성능을 향상시켜 린번엔진 자동차 배기가스의 정화용 촉매로 사용하기에 적합하다.As described above, the present invention provides an alkali metal oxide barium oxide as a cocatalyst to a supported catalyst prepared by supporting an alumina, a rare earth oxide, and a precious metal as a catalytically active material on a porous support (ceramic or metal). By adding the catalyst, it is effective to purify nitrogen oxide even in a lean burn atmosphere that is difficult to purify with a gasoline engine exhaust gas purification catalyst for a conventional gasoline engine automobile, and is suitable for use as a catalyst for purification of lean burn engine vehicle exhaust gas.

Claims (4)

세라믹 또는 금속인 다공성 담지체에 활성알루미나와, 희토류산화물 및 바륨산화물(BaO) 조촉매, 및 귀금속 촉매활성물질이 각각 담지되어 있는 것을 특징으로 하는 린번엔진 자동차 배기가스 정화용 촉매.An activated alumina, a rare earth oxide and a barium oxide (BaO) cocatalyst, and a noble metal catalytically active material are supported on a porous support that is ceramic or metal, respectively. 제 1 항에 있어서,The method of claim 1, 상기 활성알루미나는 다공성 담지체 100 중량%에 대하여 30 ∼ 50 중량%로 담지되어 있고,The activated alumina is supported by 30 to 50% by weight relative to 100% by weight of the porous support, 상기 희토류 산화물은 란타늄(La)산화물이 1 ∼ 5 중량% 담지되어 있고, 세륨(Ce)산화물이 10 ∼ 30 중량%로 담지되어 있고, 지르코늄(Zr)산화물이 10 ∼ 20 중량%로 담지되어 있고,The rare earth oxide is supported by 1 to 5% by weight of lanthanum (La) oxide, 10 to 30% by weight of cerium (Ce) oxide, and 10 to 20% by weight of zirconium (Zr) oxide. , 상기 바륨(Ba)산화물이 다공성 담지체 100 중량%에 대하여 5 ∼ 20 중량%로 담지되어 있는 것을 특징으로 하는 린번엔진 자동차 배기가스 정화용 촉매.A catalyst for purifying exhaust gas for a lean burn engine, characterized in that the barium (Ba) oxide is supported at 5 to 20 wt% with respect to 100 wt% of the porous support. 제 1 항에 있어서, 상기 귀금속 촉매활성물질은 백금(Pt), 팔라듐(Pd) 및 로듐(Rh)이 중에서 선택되는 1 종 또는 2 종 이상이 조합되어 있는 것을 특징으로 하는 린번엔진 자동차 배기가스 정화용 촉매.The lean burn engine exhaust gas purification method according to claim 1, wherein the noble metal catalytically active material is one or more selected from platinum (Pt), palladium (Pd) and rhodium (Rh). catalyst. 린번엔진 자동차 배기가스 정화용 촉매의 제조방법에 있어서,In the lean burn engine manufacturing method of the catalyst for exhaust gas purification, a) 귀금속 촉매물질을 각각 활성알루미나에 함침시킨뒤 혼합하는 단계;a) impregnating each of the noble metal catalyst materials into activated alumina and then mixing them; b) 희토류산화물 및 바륨산화물을 첨가하고 밀링하여 슬러리를 제조하는 단계; 및b) adding a rare earth oxide and a barium oxide and milling to prepare a slurry; And c) 상기 b)에서 제조된 슬러리를 벌집구조의 세라믹 또는 금속인 다공성 담지체에 코팅하여 건조시킨 다음 소성하는 단계로 이루어진 것을 특징으로 하는 린번엔진 자동차 배기가스 정화용 촉매의 제조방법.c) a method of preparing a catalyst for purifying exhaust gas for a lean burn engine, characterized in that the slurry prepared in b) is coated on a porous carrier of a honeycomb ceramic or metal, followed by drying.
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CN116212944A (en) * 2023-03-23 2023-06-06 北方稀土华凯高科技河北有限公司 Lean-burn methanol fuel automobile exhaust purification catalyst and preparation method thereof
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