KR100408880B1 - De-NOx CATALYSTS AND METHOD BY DIRECT CATALYTIC REDUCTION - Google Patents

De-NOx CATALYSTS AND METHOD BY DIRECT CATALYTIC REDUCTION Download PDF

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KR100408880B1
KR100408880B1 KR10-2001-0005303A KR20010005303A KR100408880B1 KR 100408880 B1 KR100408880 B1 KR 100408880B1 KR 20010005303 A KR20010005303 A KR 20010005303A KR 100408880 B1 KR100408880 B1 KR 100408880B1
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catalyst
honeycomb
refractory material
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metal
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김문찬
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
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    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8973—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
    • B01J37/08—Heat treatment

Abstract

내화성 물질로 고체 분말상의 Al2O3, Bi2Ti2O7, Cr3C2등의 혼합물을 담체로 사용하여 여기에 금속을 담지시켜 저온에서, 환원제를 별도로 사용하지 않고 질소산화물을 환원시키는 직접촉매환원 방식의 질소산화물 제거 촉매 및 제조방법As a refractory material, a mixture of Al 2 O 3 , Bi 2 Ti 2 O 7 , Cr 3 C 2, etc., as a solid powder is used as a carrier to support a metal to reduce nitrogen oxides at low temperature without using a reducing agent. Nitrogen oxide removal catalyst and production method by direct catalyst reduction method

Description

직접촉매환원방식의 질소산화물 제거 촉매 및 제조방법{De-NOx CATALYSTS AND METHOD BY DIRECT CATALYTIC REDUCTION}Nitrogen oxide removal catalyst and production method by direct catalyst reduction method {De-NOx CATALYSTS AND METHOD BY DIRECT CATALYTIC REDUCTION}

본 발명은 배출가스중 질소산화물을 환원제를 별도로 사용하지 않고, 질소로 환원시키는 직접촉매환원 기술에 관한 것이다. 종래의 선택적 촉매환원법은 암모니아나 요소를 환원제로 사용하여 질소산화물을 질소로 환원시키는 기술이다. 이 기술에 사용되는 촉매는 TiO2나 SiO2등의 담체에 V2O5, MoO3, Fe2O3, SnO2, Mn2O3, CuSO4, WO3, VOSO4등을 담지하여 촉매로 널리 사용하여 왔으며, 여기에 관련된 기술로는 미국특허 US3216953, US3407215, US4010238, US4048112, US4085193, US4113660, US4113660, US4176089, US4188365, US4221768, US4225462, US4280926, US4489172, US4520124, US4705770, US4725572, US4742037, US4774219, US4833113, US4929586 등이 있다.The present invention relates to a direct catalyst reduction technology for reducing nitrogen oxides in exhaust gas to nitrogen without using a reducing agent. Conventional selective catalytic reduction is a technique for reducing nitrogen oxides to nitrogen using ammonia or urea as a reducing agent. The catalyst used in this technique is supported by supporting V 2 O 5 , MoO 3 , Fe 2 O 3 , SnO 2 , Mn 2 O 3 , CuSO 4 , WO 3 , VOSO 4 , and the like on a carrier such as TiO 2 or SiO 2 . And US Patent US3216953, US3407215, US4010238, US4048112, US4085193, US4113660, US4113660, US4176089, US4188365, US4221768, US4225462, US4280926, US4489172, US4520124, US4705770, US4725572, US4742037 US4833113, US4929586.

그러나 이들 촉매는 질소산화물을 질소로 환원시켜 처리하는 속도가 공간속도 3,000h-1~5,000h-1정도이어서 많은량의 촉매가 필요하다. 또한 환원제로 사용하는 암모니아나 요소가 부식성이 강하고, 암모니아는 폭발 위험성까지 내포하고 있다. 그리고 반응후 여분의 암모니아가 배출되면서 다시 질소산화물을 생성하거나 그대로 배출되어 대기오염물질로 작용하고 있다.However, these catalysts, it is necessary that the speed of processing by reducing the nitrogen oxides to nitrogen space velocity 3,000h -1 ~ 5,000h -1 degree and then a large amount of catalyst. In addition, ammonia and urea used as reducing agents are highly corrosive, and ammonia also poses an explosion hazard. After the reaction, the excess ammonia is discharged to form nitrogen oxide or discharged as it acts as an air pollutant.

한편 종래의 비선택적 촉매환원법은 수소, 메탄, 일산화탄소, 탄화수소등을 환원제로 사용하여 질소산화물을 질소로 환원시키는 기술이다. 이 기술에 사용되는 촉매로는 제올라이트에 구리나 코발트를 담지시켜서 사용하거나 귀금속 또는 구리나 코발트를 이온교환시킨 촉매를 사용하고 있다. 그러나 이들 촉매는 전환율이 낮고 수분함량에 취약한 단점을 가지고 있으며, 여분의 환원제를 다시 산화시키는 촉매를 사용하여야 하는 단점을 가지고 있다.Meanwhile, the conventional non-selective catalytic reduction method is a technique of reducing nitrogen oxides to nitrogen using hydrogen, methane, carbon monoxide, hydrocarbons, etc. as a reducing agent. As the catalyst used in this technique, zeolite is supported by supporting copper or cobalt, or a catalyst obtained by ion exchange of precious metals or copper or cobalt. However, these catalysts have the disadvantage of low conversion rate and poor water content, and have the disadvantage of using a catalyst which oxidizes the excess reducing agent again.

본 발명에서는 종래의 기술에서 질소산화물을 환원시키기 위해서 환원제를 사용함으로써 나타나는 단점들을 해결하기 위하여 환원제를 사용하지 않고 질소산화물의 전환율을 높이며, 특히 저온에서 질소산화물의 환원을 촉진시켜 질소로 환원시키는 성능을 극대화 시키는 직접촉매환원에 의한 촉매를 제공하는데 있다.In the present invention, in order to solve the disadvantages of using a reducing agent to reduce the nitrogen oxide in the prior art, to improve the conversion rate of the nitrogen oxide without using a reducing agent, in particular to promote the reduction of nitrogen oxide at low temperatures to reduce the performance to nitrogen It is to provide a catalyst by direct catalyst reduction to maximize the.

본 발명에 사용되는 담체는 내화성 물질로 고체 분말상의 Al2O3, Bi2Ti2O7, Cr3C2등의 혼합물을 사용하게 되는데, 이들 혼합물의 구성은 2개 이상의 물질이 선택된다. 그 사용량은 2개가 선택되었을 때 무게비가 99:1에서 1:99인 상태로 미세하게 분할된 유지물로 포함하는 것을 특징으로 하며, 3가지 내화성 물질이 선택되면 먼저 선택된 2개의 물질에 대하여 3번째 것은 1∼10 중량%로 첨가하는 것을 특징으로 한다. 질소산화물을 환원시키기 위해 본 발명에 사용된 금속 원소들로는 (A)군 금속으로는 Sc, Mn, Fe, Co, Ni, Zn 중에서 선택된 원소를 하나 이상 포함하며, (B)군 금속으로는 Ge, Se, Au, Ag, Cs, Ce중에서 선택된 원소를 하나 이상 함유하는 방법이며, (C)군 금속으로는 Be, Mg, Sr, Ca중에서 선택된 원소를 하나이상 포함하여 사용하는 방법이다. 이들 금속 원소들은 금속 또는 금속산화물 상태로 존재한다. 그리고 이들 금속군들의 사용은 증량비가 (A)/[(B)+(C)] = 0.1∼10 되도록 사용하고, (B) : (C) = 99 : 1 ∼ 1 : 99의 중량%로 사용하는 것을 특징으로 한다. 이들 금속 원소들은 담체로 사용되는 내화성 물질에 대하여 (A) + (B) + (C) 군 금속의 합이 0.5∼25 중량%를 사용함으로써 충분한 발명효과가 발휘된다. 0.5중량% 보다 적은양을 사용하면 충분한 발명효과를 얻기 힘들고, 25중량% 보다 많은 양을 사용하면 금속들이 응집되어 발명의 효과가 떨어진다.The carrier used in the present invention is a refractory material using a mixture of Al 2 O 3 , Bi 2 Ti 2 O 7 , Cr 3 C 2 and the like as a solid powder, the composition of these mixtures are selected from two or more materials. Its usage is characterized in that it comprises as a finely divided holding material in the weight ratio of 99: 1 to 1:99 when two selected, and if the three refractory materials are selected, the third for the two selected materials first It is characterized by the addition of 1 to 10% by weight. Metal elements used in the present invention to reduce nitrogen oxides include (A) group metals including one or more elements selected from Sc, Mn, Fe, Co, Ni, and Zn, and (B) group metals include Ge, It is a method containing one or more elements selected from Se, Au, Ag, Cs, and Ce, and the (C) group metal is a method including one or more elements selected from Be, Mg, Sr, and Ca. These metal elements exist in the metal or metal oxide state. And the use of these metal groups is used so that the increase ratio (A) / [(B) + (C)] = 0.1 to 10, and (B): (C) = 99: 1 to 1: 99 by weight% Characterized in that. These metal elements exhibit sufficient invention effects by using a sum of (A) + (B) + (C) group metals in an amount of 0.5 to 25% by weight based on the refractory material used as a carrier. If the amount is less than 0.5% by weight, it is difficult to obtain sufficient invention effect. If the amount is more than 25% by weight, the metals are aggregated and the effect of the invention is reduced.

내화성 물질로 사용되는 Al2O3, Bi2Ti2O7, Cr3C2등의 혼합물을 볼밀 등을 사용하여 수성 슬러리로 만들고 일체 구조를 갖는 허니콤에 워시코팅하고, 그후 120℃에서 6시간 이상 건조한후 (A), (B), (C)군에서 선택된 원소를 각각 하나 이상 함유하는 혼합수용액을 내화성 무기 산화물이 워시코팅된 허니콤에 담지시켜 120℃ 이상에서 6시간 이상 건조시킨후 400∼650℃에서 1∼4 시간 동안 소성시킨다. 허니콤에 워시코팅되는 내화성 물질은 허니콤 용적에 대하여 30 ∼ 250g/L(허니콤 용적)의 농도로 존재하는 것을 특징으로 한다.A mixture of Al 2 O 3 , Bi 2 Ti 2 O 7 , Cr 3 C 2, and the like, which is used as a refractory material, is made into an aqueous slurry using a ball mill or the like and wash-coated in a honeycomb having an integral structure. After drying for more than hours, the mixed aqueous solution containing at least one element selected from the groups (A), (B) and (C) is dipped in a honeycomb coated with a refractory inorganic oxide and dried at 120 ° C. for at least 6 hours. It is calcined at 400 to 650 ° C. for 1 to 4 hours. The refractory material wash-coated to the honeycomb is characterized by being present at a concentration of 30 to 250 g / L (honeycomb volume) relative to the honeycomb volume.

이러한 본 발명의 촉매는 암모니아나 요소, 탄화수소등의 별도의 환원제를사용하지 않고도, 촉매만을 사용하여 질소산화물을 질소로 환원시키는 특징을 가지고 있다. 다음의 실시예와 비교예에 의하여 본 발명을 더 상세히 설명하는데 본 발명은 이들 실시예에만 한정되는 것은 아니다.Such a catalyst of the present invention has a feature of reducing nitrogen oxides to nitrogen using only a catalyst without using a separate reducing agent such as ammonia, urea, and hydrocarbons. The present invention is explained in more detail by the following examples and comparative examples, but the present invention is not limited to these examples.

실시예1 에서 실시예6 까지는 반응물질은 NO(일산화질소) 2,000ppm, CO(일산화탄소) 2,000ppm이며 산소농도는 4% 로 하였으며, H2O 성분이 10%, 나머지는 질소로 구성되어 있다. 반응온도는 200℃ ∼ 400℃ 이다. 촉매는 고정층 연속 흐름 반응기내에 충전되어 있으며, 공간속도는 50,000/hr 가 되도록 촉매량과 반응물 유속을 결정하였다. 비교예1은 환원제로 NH32,000ppm을 사용하여 선택적 촉매환원법에 사용되는 일반적인 촉매들을 비교하였고, 비교예2는 C2H5OH 2,000ppm을 환원제로 사용하여 비선택적 촉매환원법에 사용되는 일반적인 촉매들을 비교하였다. 실험자료들은 200시간동안 연속으로 실험하여 얻은 값을 나타낸 것이다.From Example 1 to Example 6, the reactants were 2,000 ppm of NO (nitrogen monoxide), 2,000 ppm of CO (carbon monoxide), and the oxygen concentration was 4%, the H 2 O component was 10%, and the rest was composed of nitrogen. Reaction temperature is 200 degreeC-400 degreeC. The catalyst was charged in a fixed bed continuous flow reactor, and the amount of catalyst and reactant flow rate were determined so that the space velocity was 50,000 / hr. Comparative Example 1 compared the general catalysts used in the selective catalytic reduction method using NH 3 2,000 ppm as the reducing agent, and Comparative Example 2 used the general catalysts used in the non-selective catalytic reduction method using 2,000 ppm C 2 H 5 OH as the reducing agent. Were compared. The experimental data shows the values obtained by continuous experiments for 200 hours.

표1은 촉매처리된 허니콤의 구성성분을 나타내었고, 표2에 질소산화물의 환원 전환율을 나타내었다.Table 1 shows the constituents of the catalyzed honeycomb, and Table 2 shows the reduction conversion of nitrogen oxides.

실시예 1)Example 1

Bi2Ti2O7,100g과 Al2O3100g을 혼합하여 볼밀로 20시간동안 습식분쇄하여 수성슬러리를 조제하여, 단면적 1평방인치당 200개의 가스유통셀을 갖는 15cm×15cm×10cm 크기의 하니콤을 상기 슬러리에 침지하고 취출하여 셀내의 과잉 슬러리를 압축공기로 불어내고, 그후 120℃에서 12시간 건조하고, 이것을 (A)군 금속으로 Sc를 2g 함유하는 스칸듐클로라이드와 (B)군 금속으로는 Ge을 2g 함유하는디클로로메탄용액과 (C)군 금속으로 Be를 2g 함유하는 염산용액의 혼합수용액에 침지하여 함침시키고, 120℃에서 12시간동안 건조후 600℃에서 2시간동안 소성시켜 촉매처리된 허니콤을 제조하는데 사용된, 환원제가 필요없는 직접촉매환원 방식의 질소산화물제거 촉매 및 제조방법Mixing 100 g of Bi 2 Ti 2 O 7 and 100 g of Al 2 O 3 , wet milling with a ball mill for 20 hours to prepare an aqueous slurry, and a honeycomb of 15 cm × 15 cm × 10 cm having 200 gas flow cells per square inch of cross section. The comb was immersed in the slurry and taken out, and the excess slurry in the cell was blown with compressed air, and then dried at 120 ° C. for 12 hours, and then, this was made of scandium chloride containing 2 g of Sc and (B) metal. Was impregnated by dipping into a mixed aqueous solution of dichloromethane solution containing 2 g of Ge and hydrochloric acid solution containing 2 g of Be with Group (C) metal, dried at 120 ° C. for 12 hours, and calcined at 600 ° C. for 2 hours. Nitrogen oxide removal catalyst and process for the reduction of the direct catalyst reduction method without the use of reducing agent

실시예 2)Example 2)

표1의 (A) 성분이 Mn 2g, (B) 성분이 Se 2g, (C)성분이 Mg 2g인 것을 제외하고는 실시예 1과 동일한 직접촉매환원 방식의 질소산화물제거 촉매 및 제조방법Nitrogen oxides removal catalyst and production method of the same direct catalyst reduction method as in Example 1 except that (A) component Mn 2g, (B) component Se 2g, (C) component Mg 2g

실시예 3)Example 3

표1의 (A) 성분이 Fe 2g, (B) 성분이 Au 2g, (C) 성분이 Sr 2g인 것을 제외하고는 실시예 1과 동일한 직접촉매환원 방식의 질소산화물제거 촉매 및 제조방법Nitrogen oxide removal catalyst and preparation method of the same catalytic reduction method as in Example 1, except that (A) component of Table 1 is Fe 2g, (B) component Au 2g, (C) component Sr 2g

실시예 4)Example 4

표1의 (A) 성분이 Co 2g, (B) 성분이 Ag 2g, (C)성분이 Ca 2g인 것을 제외하고는 실시예 1과 동일한 직접촉매환원 방식의 질소산화물제거 촉매 및 제조방법Nitrogen oxide removal catalyst and preparation method of the same catalytic reduction method as in Example 1 except that (A) component of Table 1, Ag 2g of component (B), and Ca 2g of component (C)

실시예 5)Example 5

표1의 (D) 성분이 Cr3C250g (E) 성분이 Al2O3150g, (A)성분이 Ni 2g, (B) 성분이 Cs 2g, (C) 성분이 Mg 2g인 것을 제외하고는 실시예 1과 동일한 직접촉매환원 방식의 질소산화물제거 촉매 및 제조방법(D) Table 1 Cr 3 C 2 50g (E) Component Al 2 O 3 150g, (A) Component Ni 2g, (B) Component Cs 2g, (C) Component Mg 2g Nitrogen oxide removal catalyst and production method of the direct catalyst reduction method as in Example 1

실시예 6)Example 6

표1의 (A) 성분이 Zn 2g, (B) 성분이 Ce 2g, (C) 성분이 Ca 2g인 것을 제외하고는 실시예 5와 동일한 직접촉매환원 방식의 질소산화물제거 촉매 및 제조방법Nitrogen oxide removal catalyst and preparation method of the same catalytic reduction method as in Example 5 except that (A) component Zn 2g, (B) component Ce 2g, (C) component Ca 2g

비교예 1)Comparative Example 1)

표1의 (D) 성분이 TiO2200g, (A) 성분이 V 10g, (B),(C),(E) 성분으로는 아무것도 들어가지 않는 일반적인 선택적 촉매환원기술에 사용되는 촉매Catalysts used in general selective catalytic reduction techniques in which (D) in Table 1 contains 200 g of TiO 2 , (A) contains 10 g of V, (B), (C) and (E).

비교예 2)Comparative example 2)

표1의 (D) 성분이 페리오라이트 200g, (A) 성분이 Co 10g으로 (D) 성분을 이온교환 시킨것, (B),(C),(E) 성분으로는 아무것도 들어가지 않는 일반적인 비선택적 촉매환원기술에 사용되는 촉매(1) Ion exchanged component (D) with 200g perilite and (A) component 10g Co in Table 1, and general ratios containing nothing as components (B), (C) and (E) Catalysts for Selective Catalytic Reduction Technology

이상에서 상세히 설명한 바와 같이, 본 발명 환원제가 필요없는 직접환원 방식에 의한 질소산화물제거 촉매 및 제조방법에 있어서, 저온과 빠른 공간속도에서 질소산화물의 환원 성능이 높아 배연탈질 공정에 효과적으로 사용될수 있는 효과를 제공한다.As described in detail above, in the nitrogen oxide removal catalyst and the production method by the direct reduction method that does not require the present reducing agent, the effect that can be effectively used in the flue gas denitrification process with high reduction performance of nitrogen oxide at low temperature and fast space velocity To provide.

Claims (6)

내화성물질로 고체분말상의 Al2O3, Bi2Ti2O7, Cr3C2중 2개 이상의 화합물을 선택하는 것을 특징으로 하는 촉매A catalyst characterized by selecting at least two compounds of Al 2 O 3 , Bi 2 Ti 2 O 7 , Cr 3 C 2 on a solid powder as a refractory material 제 1항에 있어서 Al2O3, Bi2Ti2O7, Cr3C2의 사용량은 2개가 선택되었을 때 무게비가 99:1에서 1:99인 상태로 미세하게 분할된 유지물로 포함하는 것을 특징으로 하며, 3가지 물질이 선택되면 먼저 선택된 2개의 물질에 대하여 3번째 것은 1∼10 중량%로 첨가하는 것을 특징으로 하는 촉매According to claim 1, Al 2 O 3 , Bi 2 Ti 2 O 7 , Cr 3 C 2 The amount of use is to be included as a finely divided oil and fat in a weight ratio of 99: 1 to 1:99 when two selected When three materials are selected, the first one is added in an amount of 1 to 10% by weight based on the two selected materials. 내화성 물질에 담지되는 금속들로는 (A)군 금속으로는 Sc, Mn, Fe, Co, Ni, Zn중에서 선택된 원소를 하나 이상 포함하며, (B)군 금속으로는 Ge, Se, Au, Ag, Cs, Ce중에서 선택된 원소를 하나 이상 함유하는 방법이며, (C)군 금속으로는 Be, Mg, Sr, Ca중에서 선택된 원소를 하나이상 포함하여 사용하는 것을 특징으로 하는 촉매Metals supported on the refractory material include (A) group metals including one or more elements selected from Sc, Mn, Fe, Co, Ni, and Zn, and (B) group metals include Ge, Se, Au, Ag, Cs , Is a method containing at least one element selected from Ce, (C) group as a metal catalyst characterized in that it comprises at least one element selected from Be, Mg, Sr, Ca 제 3항에 있어서 이들 금속군들의 사용은 중량비가 (A)/[B)+(C)] = 0.1∼10 되도록 사용하고, (B) : (C) = 99 : 1 ∼ 1 : 99의 중량%로 사용하는 것을 특징으로 하는 촉매The use of these metal groups according to claim 3 is used so that the weight ratio is (A) / [B) + (C)] = 0.1 to 10, and (B): (C) = 99: 1 to 1: 99 Catalyst, characterized in that used in% 제 3항에 있어서 이들 금속 원소들은 담체로 사용되는 내화성 물질에 대하여 (A) + (B) + (C) 군 금속의 합이 0.5∼25 중량%를 사용하는 것을 특징으로 하는 촉매The catalyst according to claim 3, wherein the metal elements use 0.5 to 25% by weight of the sum of the metals of the groups (A) + (B) + (C) with respect to the refractory material used as the carrier. 제 1항에 있어서 내화성 물질 혼합물은 수성 슬러리로 만들고 일체 구조를 갖는 허니콤에 워시코팅하고, 그후 120℃에서 6시간 이상 건조한후 (A), (B), (C)군에서 선택된 각각 하나 이상의 금속 혼합수용액을 내화성 물질이 워시코팅된 허니콤에 담지시켜 120℃ 이상에서 6시간 이상 건조시킨후 400∼650℃에서 1∼4 시간 동안 소성시키며, 허니콤에 워시코팅되는 내화성 무기산화물은 허니콤 용적에 대하여 30 ∼ 250g/L(허니콤 용적)의 농도로 존재하는 것을 특징으로 하는 촉매 제조방법The refractory material mixture according to claim 1 is made of an aqueous slurry and washcoated in a honeycomb having an integral structure, and then dried at 120 ° C. for at least 6 hours, and then at least one selected from (A), (B) and (C) The mixed metal solution is supported on a honeycomb wash-resistant refractory material, dried at 120 ° C. or higher for 6 hours or more, and then calcined at 400 to 650 ° C. for 1 to 4 hours. The refractory inorganic oxide wash-coated on the honeycomb is honeycomb. Catalyst production method characterized by the presence of a concentration of 30 to 250g / L (honeycomb volume) with respect to the volume
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