KR100362108B1 - METHOD OF FABRICATING Cu-Pt-ZSM-5 CATALYST FOR LEAN BURN ENGINE FOR VEHICLE - Google Patents

METHOD OF FABRICATING Cu-Pt-ZSM-5 CATALYST FOR LEAN BURN ENGINE FOR VEHICLE Download PDF

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KR100362108B1
KR100362108B1 KR1019970021596A KR19970021596A KR100362108B1 KR 100362108 B1 KR100362108 B1 KR 100362108B1 KR 1019970021596 A KR1019970021596 A KR 1019970021596A KR 19970021596 A KR19970021596 A KR 19970021596A KR 100362108 B1 KR100362108 B1 KR 100362108B1
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zsm
catalyst
lean burn
filtering
vehicle
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KR19980085493A (en
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김창대
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기아자동차주식회사
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening

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  • Organic Chemistry (AREA)
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Abstract

PURPOSE: A method of fabricating Cu-Pt-ZSM-5 catalyst with excellent durability at high temperatures and activity to NOx for use in lean burn engine for vehicle is provided. CONSTITUTION: The method comprises the steps of introducing Na-ZSM-5 catalyst for lean burn engine for vehicle into a mixing means; pouring distilled water including H2PtCl·6H2O to the mixing means, followed by agitation for 24 hrs at 70 to 80 deg.C; adjusting the mixed solution of the first step at pH 7.5, followed by filtration; pouring distilled water including Cu(NO3)2·3H2O into the mixing means, followed by agitation for 24 hrs at 70 to 80 deg.C; adjusting the mixed solution obtained through above steps at pH 7.5, followed by filtration; drying catalyst particles obtained proceeding step; and calcining the obtained catalyst particles.

Description

희박연소용 자동차 촉매 Cu-Pt-ZSM-5 제조방법Manufacturing method of Cu-Pt-ZSM-5 automobile catalyst for lean burning

본 발명은 가솔린엔진의 희박연소용 자동차촉매에 있어서 Pt-ZSM-5의 격자구조를 가지면서도 Cu-ZSM-5의 우수한 NOx 활성을 유지하여, 내열성과 우수한 NOx활성을 갖는 희박연소용 자동차 촉매 Cu-Pt-ZSM-5 제조방법에 관한 것이다.The present invention maintains the excellent NOx activity of Cu-ZSM-5 while having a lattice structure of Pt-ZSM-5 in the lean burn car catalyst of gasoline engine, and has a heat resistance and excellent NOx activity. -Pt-ZSM-5.

일반적으로 차량엔진의 가솔린 연료분사는 엔진에 흡입되는 공기량을 직접 또는 간접적으로 검출하여 필요한 공연비가 되도록 가솔린의 분사량을 계산한다. 인젝터의 니들밸브를 열어 가솔린을 흡기관내 또는 연소실에 공급하는 것으로 컴퓨터에 의해 제어되는 것을 전자제어 연료분사라고 부르고 있다.In general, gasoline fuel injection of a vehicle engine directly or indirectly detects the amount of air sucked into the engine and calculates the injection amount of gasoline to achieve the required air-fuel ratio. The control of the computer by opening the needle valve of the injector and supplying gasoline into the intake pipe or the combustion chamber is called electronically controlled fuel injection.

이러한 전자제어 연료분사에 있어서 희박연소(Lean Burn)란 이론 공연비보다 엷은 혼합기를 연소시키는 것으로서, 안전된 희박연소가 실현되면 배기가스의 정화와 저연비가 동시에 달성되지만 엷은 혼합기는 착화성이 나쁘고 연소속도도 느리므로 연소가스가 불안정하여 실화되기 쉽고 출력도 나오지 않게 된다. 희박혼합기를 단시간에 안정된 상태로 연소시키기 위하여 흡기 계통의 기구나 연소실의 형상을 연구하여 적합한 와류를 발생시켜 연료 분사시기가 가장 적합한 층상 흡기, 강력 점화 등에 따라 확실한 착화를 실시하는 방법이 개발되었다.In such electronically controlled fuel injection, lean burn is to burn a mixer that is thinner than the theoretical air-fuel ratio. When safe lean combustion is realized, purifying exhaust gas and low fuel consumption are achieved at the same time, but a thin mixer is poor in ignition and combustion speed. In addition, since the combustion gas is unstable, it is easy to be misfired, and power is not output. In order to burn the lean mixer in a stable state in a short time, a method of developing the vortex by studying the shape of the intake system or the shape of the combustion chamber to generate a suitable vortex, and to perform the ignition reliably according to the laminar intake, the strong ignition, etc., where the fuel injection timing is most suitable.

해결에 어려운 문제점은 NOx로서 이것은 가장 많은 이론 공연비보다 조금 큰 쪽에 있고, 토크가 필요한 가속시나 고속주행시 NOx가 많게 배출되는 것이다. 이러한 문제점들이 희박연소엔진 개발상에서 애로점이다.The problem that is difficult to solve is NOx, which is slightly larger than the most theoretical air-fuel ratio, and a large amount of NOx is emitted during acceleration or high speed driving requiring torque. These problems are painful in the development of lean burn engines.

이에 따라 차량의 NOx 제거를 위하여 희박연소용 촉매가 사용되는 바, 이러한 촉매로는 흡장형 및 제올라이트(Zeolite)형을 들 수 있는데, 흡장형의 경우, 희박연소 조건하에서 NOx을 흡장하고, 엔진을 조절하여 일시적으로 이론공연비로 운전하여 이때 NOx을 제거하는 시스템을 갖는다.Accordingly, a catalyst for lean burn is used to remove NOx of a vehicle. Examples of the catalyst include occlusion type and zeolite type. In the case of occlusion type, the NOx is occluded under lean combustion conditions, and the engine is It has a system to regulate and temporarily operate at theoretical performance ratio and remove NOx at this time.

그러나 상기 제올라이트형 촉매의 경우에는 이론공연비쪽으로 운전하지 않고 항상 희박연소 조건하에서 NOx을 제거하는 것으로서, 이러한 제올라이트형 촉매의 개발이 엔진 측면에서는 손쉬우나 촉매적 측면에서는 좀 더 어려운 문제가 많다. 특히 제올라이트가 700℃ 이상이 열적 내구성이 취약하다는 것에 문제가 있다.However, in the case of the zeolite catalyst, NOx is always removed under lean combustion conditions without operating toward the theoretical air-fuel ratio. The development of such a zeolite catalyst is easy on the engine side, but more difficult on the catalytic side. In particular, the zeolite has a problem that the thermal durability is more than 700 ℃.

그리고, 이러한 제올라이트형 촉매인, ZSM-5 촉매의 합성에 관하여는 미국 특허 제 3, 702, 886호에 잘 나타나 있으며, 금속이온 교환된 ZSM-5 촉매중에서 Cu-ZSM-5(Iwamoto, M. and Hamada, H. , Catalysis Today, 10권 57p, 1991)가 가장 널리 사용되고 있다.And, the synthesis of such a zeolite-type catalyst, ZSM-5 catalyst is well described in U.S. Patent Nos. 3, 702, 886, and Cu-ZSM-5 (Iwamoto, M. and Hamada, H., Catalysis Today, Vol. 10, 57p, 1991).

즉, 이러한 제올라이트 계통의 촉매인 Cu-ZSM-5가 근래 일본에서 제공되어희박연소 조건하에서 NOx의 정화율이 있다고 알려진 이후 자동차업계 및 촉매제조 회사를 중심으로 ZSM-5의 연구가 활발히 진행되고 있다.That is, since zeolite-based catalyst Cu-ZSM-5 has been provided in Japan recently, and it is known that NOx purification rate is known under lean burning conditions, research on ZSM-5 is being actively conducted mainly in the automobile industry and catalyst manufacturing companies. .

그러나, 도 3에 종래 Pt-ZSM-5 및 Cu-ZSM-5의 NOx제거 활성 예시 그래프를 나타낸 바와 같이 각 촉매들에 대하여 상기 Pt-ZSM-5는 촉매 활성이 40% 근처이며 낮은 온도인 반면에 Cu-ZSM-5는 약 60%의 NOx 활성을 보이는 반면 내수성 및 내열성이 취약하다는 문제점이 있다.However, as shown in the graphs illustrating the NOx removal activity of the conventional Pt-ZSM-5 and Cu-ZSM-5 in FIG. 3, the Pt-ZSM-5 has a catalytic activity of about 40% and a low temperature for each catalyst. Cu-ZSM-5 shows about 60% NOx activity, but has a problem in that water resistance and heat resistance are weak.

따라서 본 발명은 상기한 문제점을 감안하여 안출한 것으로서, 본 발명의 목적은 상기 Pt-ZSM-5의 활성을 개선하고, 낮은 온도 영역에서의 NOx 활성을 이용하여 Cu-ZSM-5의 높은 NOx 활성의 장점을 접목하여 이에 따라 NOx 활성도 우수하고 내열성과 내수성도 개선된 희박연소 촉매인 희박연소용 자동차 촉매 Cu-Pt-ZSM-5 제조방법을 제공하는 데 있다.Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to improve the activity of the Pt-ZSM-5 and to utilize the high NOx activity of Cu-ZSM-5 by using the NOx activity in the low temperature region. The present invention provides a method for preparing a Cu-Pt-ZSM-5 catalyst for lean combustion, which is a lean combustion catalyst having excellent NOx activity and improved heat resistance and water resistance.

도 1 은 본 발명의 제조공정 블록도,1 is a manufacturing process block diagram of the present invention,

도 2 는 본 발명의 Cu-Pt-ZSM의 NO제거 활성 상태 예시 그래프,2 is an exemplary graph of NO removal activity of Cu-Pt-ZSM of the present invention;

도 3 은 종래 Pt-ZSM-5 및 Cu-ZSM-5의 NOx제거 활성 예시 그래프.3 is a graph illustrating NOx removal activity of conventional Pt-ZSM-5 and Cu-ZSM-5.

상기한 목적을 이루기 위하여 본 발명은 가솔린엔진의 희박연소용 촉매 Na-ZSM-5를 교반기에 넣고 H2PtCl·6H2O를 포함한 증류수를 넣어 70∼80℃에서 24시간 동안 교반시키는 단계(a);In order to achieve the above object, the present invention is to put a catalyst for lean burn of gasoline engine Na-ZSM-5 into a stirrer and put distilled water containing H 2 PtCl.6H 2 O and stirred at 70 ~ 80 ℃ for 24 hours (a );

상기 교반공정(a) 상기 혼합체를 PH 7.5로 맞추고 필터링하는 단계(b);The stirring step (a) adjusting the mixture to PH 7.5 and filtering (b);

상기 필터링(b)후 다시 Cu(NO3)2·3H2O를 포함한 증류수를 넣고 70∼80℃에서 24시간 동안 교반시키는 단계(c);(C) adding distilled water containing Cu (NO 3 ) 2 .3H 2 O again after the filtering (b) and stirring at 70 to 80 ° C. for 24 hours;

상기 교반공정(c)후 상기 혼합체를 PH 7.5로 맞추고 재차 필터링하는 단계(d);(D) adjusting the mixture to pH 7.5 after the stirring step (c) and filtering again;

상기 필터링(d)후 세척(e)하고, 재차 필터링(f)을 거쳐 건조시키는 단계(g);Washing (e) after the filtering (d) and drying again through filtering (f);

상기 건조공정(g)후 소성공정(h)을 거쳐 제조하는 것을 특징으로 하는 희박연소용 자동차 촉매 Cu-Pt-ZSM-5 제조방법을 제공한다.It provides a method for producing lean-burning automotive catalyst Cu-Pt-ZSM-5, characterized in that the drying step (g) after the firing step (h).

이하 처부된 예시도면을 참조하여 본 발명의 바람직한 실시예를 보다 상세히 설명하면 다음과 같다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the illustrated exemplary drawings.

이하 첨부된 예시도면을 참조하여 본 발명의 바람직한 실시예를 보다 상세히 설명하면 다음과 같다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

도 1 은 본 발명의 제조공정 블록도로서, Na-ZSM-5로 부터 여러 공정을 거쳐 NOx 활성이 우수하고 내수성 및 내열성을 갖는 Cu-Pt-ZSM-5로의 변화가 유도되는 공정을 나타낸 것이다.1 is a block diagram of the manufacturing process of the present invention, showing a process in which a change from Na-ZSM-5 to Cu-Pt-ZSM-5 which is excellent in NOx activity and has water resistance and heat resistance is induced.

본 발명에 사용되는 Na-ZSM-5을 제조하기 위하여 H-ZSM-5 분말을 나트륨염 수용액 중에 분산시킨 후 상온 이상의 온도(35 ∼ 45℃)에서 12시간 이상, 바람직하게는 24시간동안 교반한다.In order to prepare Na-ZSM-5 used in the present invention, H-ZSM-5 powder is dispersed in an aqueous sodium salt solution and then stirred at a temperature higher than room temperature (35 to 45 ° C) for at least 12 hours, preferably for 24 hours. .

그리고, Na-ZSM-5을 제조하기 위해 사용되는 상기 나트륨염으로는 질산나트륨, 황산나트륨, 염산나트륨, 초산나트륨등이 사용된다.As the sodium salt used to prepare Na-ZSM-5, sodium nitrate, sodium sulfate, sodium hydrochloride, sodium acetate, and the like are used.

또한, 상기한 바와 같은 교반 과정에 의하여 H-ZSM-5에 포함된 수소이온이 Na+으로 교환되고, 교환된 Na+는 후술될 Pt(백금)으로 교환되어 진다.Further, the hydrogen ions contained in the stirring process by the H-ZSM-5 as described above are exchanged by Na +, the Na + exchange shall be exchanged with Pt (platinum), which will be described later.

즉, Na-ZSM-5를 교반기에 넣고, H2PtCl·6H2O를 포함한 증류수를 넣어 70 ∼ 80℃에서 24시간 동안 교반시켜 Na이온을 Pt이온으로 교환하는 것이다.That is, Na-ZSM-5 is put in a stirrer, distilled water including H 2 PtCl.6H 2 O is stirred at 70 to 80 ° C. for 24 hours to exchange Na ions with Pt ions.

이 경우, 상기 H2PtCl·6H2O를 포함한 증류수, 즉 백금수용액은 10 ∼ 100mM 농도이며, 이 백금수용액에 Na-ZSM-5는 1 ∼ 10w/v%로 첨가된다.In this case, the H 2 PtCl · 6H distilled water containing 2 O, i.e., a platinum solution is a concentration of 10 ~ 100mM, in the platinum solution Na-ZSM-5 is added at a 1 ~ 10w / v%.

상기한 바와 같이 교반공정(a) 후 상기 혼합체를 적정(Titration) 등을 통하여 PH를 7.5로 맞춘다.As described above, after the stirring step (a), the mixture is adjusted to pH 7.5 by titration.

그리고, 상기한 바와 같이 PH가 7.5로 유지되면 치환된 Pt이온은 ZSM-5 메트릭스상에 고착하며, 이때 PH를 조정하는 조정체는 암모니아수가 바람직하다.As described above, when the pH is maintained at 7.5, the substituted Pt ions are fixed on the ZSM-5 matrix, and the modulator for adjusting the pH is preferably ammonia water.

상기한 바와 같이 암모니아수로 처리한 후, 필터링(b; Filtering) 하면, 습윤상태의 Pt-ZSM-5케이크를 얻을 수 있다.After treatment with ammonia water as described above, filtering (b; filtering) yields a wet Pt-ZSM-5 cake.

그리고, 이 Pt-ZSM-5케이크는 다시 Cu(NO3)2·3H2O를 포함한 증류수에 넣고, 70∼80℃에서 24시간 동안 교반공정(c)를 수행한 후, 다시 PH를 암모니아수로 7.5로 적정한다.The Pt-ZSM-5 cake was further put in distilled water containing Cu (NO 3 ) 2 .3H 2 O, followed by stirring (c) at 70-80 ° C. for 24 hours. Titrate to 7.5.

또 이경우 상기 Pt-ZSM-5케이크는 10 ∼ 100mM 농도의 Cu(NO3)2·3H2O를 포함한 증류수, 또는 10 ∼ 100mM 농도의 초산구리, 황산구리, 염산구리등의 수용액 중에 1 ∼ 10w/v%농도로 재분산시켜, 70∼80℃에서 12시간 이상 바람직하게는 24시간동안 교반하는 것이다.In this case, the Pt-ZSM-5 cake is used in distilled water containing Cu (NO 3 ) 2 .3H 2 O at a concentration of 10 to 100 mM, or in an aqueous solution of copper acetate, copper sulfate, copper hydrochloride, etc. at a concentration of 10 to 100 mM. redispersion at v% concentration, and stirring at 70-80 degreeC for 12 hours or more, Preferably it is 24 hours.

그 다음, 필터링(d)을 다시 시행하고 세척(e), 재차필터링하면, ZSM-5메트릭스 상의 H이온이 Cu이온과 Pt이온으로 이온교환된 Cu-Pt-ZSM-5 공이온 교환체를 얻을 수 있다.Then, filtering (d) again, washing (e), and filtering again yields a Cu-Pt-ZSM-5 co-ion exchanger in which the H ions on the ZSM-5 matrix are ion-exchanged with Cu and Pt ions. Can be.

그리고, 상기한 습윤상태의 Cu-Pt-ZSM-5는 건조(g) 및 소성(h)을 거쳐 본 발명의 촉매인 분말타입의 Cu-Pt-ZSM-5가 생성되는 것이다.In the wet Cu-Pt-ZSM-5, the powder-type Cu-Pt-ZSM-5 which is the catalyst of the present invention is produced through drying (g) and calcining (h).

상기 건조는 통상적으로 110℃에서 12시간 정도 지속하는 것이 바람직하고, 소성은 550℃이상의 고온에서 3시간정도 진행하는 것이 좋다.Preferably, the drying is continued at 110 ° C. for about 12 hours, and the firing is preferably performed at about 550 ° C. or more for 3 hours.

본 발명의 Cu-Pt-ZSM-5는 Pt-ZSM-5의 격자구조를 가지면서 Cu-ZSM-5의 우수한 NOx 활성을 유지하게 되어 열적으로 안정된 구조이면서도 우수한 NOx 활성을 갖는다.Cu-Pt-ZSM-5 of the present invention has a lattice structure of Pt-ZSM-5 and maintains excellent NOx activity of Cu-ZSM-5, and thus has a thermally stable structure and excellent NOx activity.

또한 도 2에 본 발명의 Cu-Pt-ZSM-5의 NO제거 활성 상태 예시 그래프를 나타낸 바와 같이, 본 발명의 촉매 Cu-Pt-ZSM-5는 최대 전환(Max. Conversion)이 370℃에서 68%로 근 70%에 이르며, 최대 정화율에 이르는 온도 역시 Cu-ZSM-5보다 약 50% 정도 낮은 350∼375℃ 영역에 있다. 이는 모노리스(Monolith)에서의 정화율이므로 상업화된 기존의 촉매 정화율 60%를 상회하는 수치가 된다.In addition, as shown in the graph illustrating an exemplary NO removal activity state of Cu-Pt-ZSM-5 of the present invention, the catalyst Cu-Pt-ZSM-5 of the present invention has a maximum conversion of 68 at 370 ° C. The temperature reaches a maximum of 70%, and the maximum purification rate is also in the region of 350-375 ° C., which is about 50% lower than Cu-ZSM-5. This is a purification rate in Monolith, which is over 60% of the conventional catalyst purification rate.

이상과 같이 본 발명은 Pt-ZSM-5의 격자구조를 가지면서 Cu-ZSM-5의 우수한 NOx 활성을 유지하게 되어 열적으로 안정된 구조이면서도 우수한 NOx 활성을 갖는 촉매를 얻을 수 있게 된다. 즉 내열적인 측면이 강화되면서도 NO 제거기능이 증진되는 효과가 있다.As described above, the present invention maintains excellent NOx activity of Cu-ZSM-5 while having a lattice structure of Pt-ZSM-5, thereby obtaining a catalyst having excellent NOx activity while having a thermally stable structure. In other words, there is an effect of enhancing the NO removal function while enhancing the heat-resistant aspects.

Claims (1)

가솔린엔진의 희박연소용 촉매 Na-ZSM-5를 교반기에 넣고 H2PtCl·6H2O를 포함한 증류수를 넣어 70∼80℃에서 24시간 동안 교반시키는 단계(a);Putting a catalyst for lean burn of gasoline engine Na-ZSM-5 into a stirrer, distilled water containing H 2 PtCl.6H 2 O, and stirring the mixture at 70 to 80 ° C. for 24 hours; 상기 교반공정(a) 상기 혼합체를 PH 7.5로 맞추고 필터링하는 단계(b);The stirring step (a) adjusting the mixture to PH 7.5 and filtering (b); 상기 필터링(b)후 다시 Cu(NO3)2·3H2O를 포함한 증류수를 넣고 70∼80℃에서 24시간 동안 교반시키는 단계(c);(C) adding distilled water containing Cu (NO 3 ) 2 .3H 2 O again after the filtering (b) and stirring at 70 to 80 ° C. for 24 hours; 상기 교반공정(c)후 상기 혼합체를 PH 7.5로 맞추고 재차 필터링하는 단계(d);(D) adjusting the mixture to pH 7.5 after the stirring step (c) and filtering again; 상기 필터링(d)후 세척(e)하고, 재차 필터링(f)을 거쳐 건조시키는 단계(g);Washing (e) after the filtering (d) and drying again through filtering (f); 상기 건조공정(g)후 소성공정(h)을 거쳐 제조하는 것을 특징으로 하는 희박 연소용 자동차 촉매 Cu-Pt-ZSM-5 제조방법.Method for producing lean-burning catalyst Cu-Pt-ZSM-5 for automobiles, characterized in that the drying step (g) and then the firing step (h).
KR1019970021596A 1997-05-29 1997-05-29 METHOD OF FABRICATING Cu-Pt-ZSM-5 CATALYST FOR LEAN BURN ENGINE FOR VEHICLE KR100362108B1 (en)

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CN107029751A (en) * 2017-06-01 2017-08-11 南通百应能源有限公司 The preparation method of high activity platinum copper catalyst

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JPH0549934A (en) * 1991-08-08 1993-03-02 Babcock Hitachi Kk Catalyst for purifying exhaust gas and its preparation
JPH0788379A (en) * 1993-09-24 1995-04-04 Honda Motor Co Ltd Catalyst for purifying exhaust gas
JPH0788335A (en) * 1993-09-22 1995-04-04 Nippon Steel Corp Method for denitrating low-temperature waste gas
JPH08173761A (en) * 1994-12-26 1996-07-09 Tosoh Corp Method for removing nitrogen oxide

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JPH0549934A (en) * 1991-08-08 1993-03-02 Babcock Hitachi Kk Catalyst for purifying exhaust gas and its preparation
JPH0788335A (en) * 1993-09-22 1995-04-04 Nippon Steel Corp Method for denitrating low-temperature waste gas
JPH0788379A (en) * 1993-09-24 1995-04-04 Honda Motor Co Ltd Catalyst for purifying exhaust gas
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107029751A (en) * 2017-06-01 2017-08-11 南通百应能源有限公司 The preparation method of high activity platinum copper catalyst

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