KR100343550B1 - Selective Removal of Methane in Flue Gas by Metal Loaded Zeolite - Google Patents
Selective Removal of Methane in Flue Gas by Metal Loaded Zeolite Download PDFInfo
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Abstract
본 발명은 희박농도의 메탄 산화촉매의 제조방법에 관한 것으로서, 높은 실리카 함량의 제올라이트에 팔라듐(Pd), 백금(Pt), 로듐(Rh), 금(Au)을 포함하는 활성 귀금속 성분을 담지하는데 있어서 제올라이트 세공을 보호할 수 있는 특정의 유기물을 미리 제올라이트 세공 내에 채워 넣은 상태에서 활성 귀금속 촉매성분을 담지하여 메탄산화에 필수적인 귀금속 성분을 제올라이트 세공의 원하는 위치에 정확히 담지되도록 하며, 이렇게 제조된 촉매는 제올라이트 세공을 보호하지 않은 상태에서 활성 귀금속 성분을 담지하여 제조한 촉매에 비하여 저온에서 높은 메탄 산화활성을 나타내고, 특히 희박농도의 메탄이 포함되어 있는 배출가스로부터의 메탄을 효과적으로 산화 제거하는데 유용한 메탄 산화촉매의 제조방법에 관한 것이다.The present invention relates to a method of preparing a lean methane oxidation catalyst, wherein an active precious metal component including palladium (Pd), platinum (Pt), rhodium (Rh) and gold (Au) is supported on a high silica content zeolite. In this case, the active noble metal catalyst component is supported in a state in which a specific organic substance that can protect the zeolite pores is pre-filled in the zeolite pore so that the precious metal component essential for methanation is accurately loaded at a desired position of the zeolite pore. Methane oxidation, which shows high methane oxidation activity at low temperatures and is particularly effective for effectively oxidizing and removing methane from exhaust gas containing lean concentration of methane compared to catalysts prepared by supporting active precious metal components without protecting zeolite pores. It relates to a method for producing a catalyst.
Description
본 발명은 희박농도의 메탄 산화촉매의 제조방법에 관한 것으로서, 높은 실리카 함량의 제올라이트에 팔라듐(Pd), 백금(Pt), 로듐(Rh), 금(Au)을 포함하는 활성 귀금속 성분을 담지하는데 있어서 제올라이트 세공을 보호할 수 있는 특정의 유기물을 미리 제올라이트 세공 내에 채워 넣은 상태에서 활성 귀금속 촉매성분을 담지하여 메탄산화에 필수적인 귀금속 성분을 제올라이트 세공의 원하는 위치에 정확히 담지되도록 하며, 이렇게 제조된 촉매는 제올라이트 세공을 보호하지 않은 상태에서 활성 귀금속 성분을 담지하여 제조한 촉매에 비하여 저온에서 높은 메탄 산화활성을 나타내고, 특히 희박농도의 메탄이 포함되어 있는 배출가스로부터의 메탄을 효과적으로 산화 제거하는데 유용한 메탄 산화촉매의 제조방법에 관한 것이다.The present invention relates to a method of preparing a lean methane oxidation catalyst, wherein an active precious metal component including palladium (Pd), platinum (Pt), rhodium (Rh) and gold (Au) is supported on a high silica content zeolite. In this case, the active noble metal catalyst component is supported in a state in which a specific organic substance that can protect the zeolite pores is pre-filled in the zeolite pore so that the precious metal component essential for methanation is accurately loaded at a desired position of the zeolite pore. Methane oxidation, which shows high methane oxidation activity at low temperatures and is particularly effective for effectively oxidizing and removing methane from exhaust gas containing lean concentration of methane compared to catalysts prepared by supporting active precious metal components without protecting zeolite pores. It relates to a method for producing a catalyst.
천연가스는 85% 이상이 매우 안정한 메탄으로 구성되어 있으며, 천연가스의 주성분인 메탄을 선택적으로 산화시키기 위해서는 450℃ 이상의 높은 반응온도가 요구된다. 따라서, 백금, 팔라듐, 코발트, 로듐, 페르브스카이트(perovskite)등과 같이 극히 제한된 금속촉매들만이 메탄 산화반응에 활성을 나타내는 것으로 알려져 있다. Hicks 등이 팔라듐이 담지된 Pd-Al2O3촉매를 가지고 메탄을 효과적으로 산화할 수 있음을 보고한 이후[Robert F. Hicks and Raymond G. Lee,J. of Catal. 122(1990) 280], 메탄 산화의 반응온도가 활성촉매성분의 분산, 촉매성분이 담지된 담체 그리고 반응중의 생성물인 물과 이산화탄소 등에 크게 영향받음을 알게 되었다. 특히, 희박농도조건의 메탄을 산화제거하기 위하여는 백금, 팔라듐 등이 담지된 귀금속 촉매가 매우 효과적이며, 그 활용 연구가 활발히 진행되고 있다[R. Burch and P.K. Loader,Appl. Catal., B 5 149 (1994); R.J. Frrauto, J.K. Lampert,Appl. Catal., B 6 263 (1995); F.H. Ribeiro, and R.A. Dalla Betta,J. Catal.,146 (1994) 537]. 이들 활성 귀금속을 알루미나, 실리카, 지르코니아, 티타늄, 제올라이트 등과 같은 여러 가지 담체에 담지시켜 사용하고 있으나, 담체에 따라 반응온도 및 활성에 큰 차이를 나타내고 있다. 즉, 알루미나, 실리카, 지르코니아, 티타늄 등과 같이 미세세공을 갖지 않는 담체에 담지된 촉매들의 경우 500℃ 이상의 높은 반응 온도가 요구됨과 동시에 담지된 활성 귀금속 촉매의 소결(sintering)이 일어나 반응활성 저하가 일어난다. 반면, 일정한 크기의 미세세공을 갖는 제올라이트에 담지할 경우는 저온에서도 높은 메탄 산화활성을 갖는 우수한 산화특성을 나타낸다. 위에 언급한 귀금속 촉매 이외에도 열적으로 안정한 페르브스카이트의 금속산화물 촉매가 사용되기도 하나, 메탄의 완전산화를 위하여는 550℃ 이상의 온도가 요구되고 있다. 따라서, 가스터빈이나보일러 등과 같이 과량의 산소가 포함되어 있고, 메탄의 농도가 희박한 조건하에서 메탄을 선택적으로 산화시키기 위하여는 귀금속 담지 제올라이트 촉매가 효과적이기 때문에 그 중요성이 크다고 하겠다.Natural gas is composed of more than 85% of the very stable methane, a high reaction temperature of more than 450 ℃ is required to selectively oxidize methane, the main component of natural gas. Therefore, only extremely limited metal catalysts such as platinum, palladium, cobalt, rhodium, perovskite and the like are known to be active in methane oxidation. After Hicks et al. Reported that they could effectively oxidize methane with Pd-Al 2 O 3 catalysts loaded with palladium [Robert F. Hicks and Raymond G. Lee, J. of Catal. 122 (1990) 280], it was found that the reaction temperature of methane oxidation was greatly influenced by the dispersion of the active catalyst component, the carrier supported by the catalyst component, and water and carbon dioxide, which are the products in the reaction. In particular, in order to oxidize and remove methane under lean concentration conditions, a noble metal catalyst loaded with platinum, palladium, etc. is very effective, and its research is being actively conducted [R. Burch and PK Loader, Appl. Catal. , B 5 149 (1994); RJ Frrauto, JK Lampert, Appl. Catal. , B 6 263 (1995); FH Ribeiro, and RA Dalla Betta, J. Catal., 146 (1994) 537. Although these active noble metals are supported on various carriers such as alumina, silica, zirconia, titanium, zeolite and the like, they show a great difference in reaction temperature and activity depending on the carrier. That is, in the case of catalysts supported on a carrier having no micropores such as alumina, silica, zirconia, titanium, etc., a high reaction temperature of 500 ° C. or higher is required, and at the same time, sintering of the supported active noble metal catalyst occurs, resulting in a decrease in reaction activity. . On the other hand, when supported on zeolite having a constant size of micropores, it shows excellent oxidation characteristics with high methane oxidation activity even at low temperatures. In addition to the noble metal catalysts mentioned above, thermally stable metal oxide catalysts of perovskite are used, but temperatures of 550 ° C. or higher are required for the complete oxidation of methane. Therefore, it is important that the precious metal-supported zeolite catalyst is effective to selectively oxidize methane under conditions in which excess oxygen is contained, such as gas turbines or boilers, and the concentration of methane is scarce.
과량 산소 분위기 하에서 희박 농도의 메탄을 산화 제거할 수 있는 귀금속 담지 제올라이트계 촉매 제조시에 담지되는 활성 귀금속 성분으로는 백금, 팔라듐, 로듐 등을 들 수 있다. Kennelly 등은 귀금속 담지 촉매제조시에 제 2의 금속을 첨가시킨 이성분계 촉매를 제조하여 925℃ ∼ 1650℃의 고온에서도 사용이 가능함을 발표한 바 있다[미국특허 제5,378,142호 (1991)]. 즉, 팔라듐에 세륨, 란타륨, 니오비늄, 사마리륨 등이 첨가된 이성분계 촉매를 알루미나, 실리카, 지르코니아 또는 타이타니아에 담지시킨 메탄 산화촉매를 단일담체(monolith)에 코팅하여 사용하였다. 이들 외에도, Fornasari 등은 피로코릭 구조[Pyrochoric structure; XaYbZcSn2O7이때, X는 3가 금속(란탄늄(La), 인디늄(In), 탈리륨(Tl)), Y는 4가 금속(주석(Sn), 납(Pb), 세륨(Ce)), Z는 2가 금속산화물이며, 0≤a≤2, 0≤b≤1, 0≤c≤1, a+b+c=2]를 가지는 금속혼합산화물 촉매를 600℃ ∼ 1400℃에서 가스터빈이나 보일러 등에서 배출되는 메탄 산화에 적용하여 좋은 결과를 얻었다고 보고한 바 있다. 최근의 Kennelly 등의 결과에 의하면, 팔라듐에 알카리 금속 또는 알카리 토금속(세륨(Ce), 란탄니아(La), 나이오비움(Nd) 그리고 사마리움(Sm)) 등이 첨가된 이성분계 금속산화물 촉매의 경우 메탄 산화반응에 매우 높은 활성을 나타냄을 보고하였다[미국특허 제5,863,851호 (1999)].Platinum, palladium, rhodium, etc. are mentioned as an active precious metal component supported at the time of preparation of a precious metal carrying zeolite catalyst which can oxidize and remove lean methane in an excess oxygen atmosphere. Kennelly et al. Have published a two-component catalyst in which a second metal is added to prepare a supported catalyst for noble metal, and has announced that it can be used even at a high temperature of 925 ° C to 1650 ° C (US Patent No. 5,378,142 (1991)). That is, a methane oxidation catalyst in which cerium, lanthanum, niobium, samarium, and the like was added to palladium and supported on alumina, silica, zirconia, or titania was used as a monolithic coating. In addition to these, Fornasari et al. Describe the pyrochoric structure; X a Y b Z c Sn 2 O 7 where X is a trivalent metal (lanthanum (La), indium (In), thalilium (Tl)), Y is a tetravalent metal (tin (Sn), lead ( Pb), cerium (Ce)), and Z are divalent metal oxides, and 0? A? 2, 0? B? 1, 0? C? 1, and a + b + c = 2]. It has been reported that good results were obtained by applying to methane oxidation emitted from gas turbines or boilers at 600 ° C to 1400 ° C. According to the recent results of Kennelly et al., A bicomponent metal oxide catalyst in which an alkali metal or an alkaline earth metal (cerium (Ce), lanthanum (La), niobium (Nd) and samarium (Sm)) is added to palladium In this case, it was reported that the methane oxidation reaction was very high (US Patent No. 5,863,851 (1999)).
이상에서 살펴본 바와 같이 귀금속 담지 메탄 산화촉매들은 고온·고압의 메탄 산화에는 효과적이나, 저온·저압 및 과량의 산소 분위기 하에 존재하는 메탄 산화반응에의 적용에는 한계가 있으며, 그 예 또한 많지 않다.As described above, the precious metal-supported methane oxidation catalysts are effective for methane oxidation at high temperature and high pressure, but there are limitations on the application to methane oxidation reaction under low temperature, low pressure and excessive oxygen atmosphere, and there are not many examples.
이에, 본 발명은 저온·저압 및 과량의 산소 분위기 하에 존재하는 메탄 산화반응에 효과적인 귀금속 담지 제올라이트 촉매를 개발하기에 이르렀으며, 그 결과 귀금속 성분들을 제올라이트 담체에 담지시키기는 방법에 있어서 종래의 단순한 함침법 또는 이온교환법 대신 새로운 개념의 담지 방법을 고안함으로써 본 발명을 완성하게 되었다. 즉, 본 발명에서는 귀금속 성분들을 담지하는데 있어서 이들 귀금속 성분들을 제올라이트 촉매 주위에 효율적으로 고분산 시키기 위하여 분자량 70 ∼ 250 정도의 특정 유기화합물로 제올라이트 세공을 미리 막아놓은 상태에서 귀금속 성분을 담지시켰다. 본 발명에 따른 제조방법에 의해 활성 귀금속 성분을 제올라이트에 담지시킬 경우 종래 방법에 비하여 값비싼 귀금속 성분들을 제올라이트 세공 주위에 정확히 고분산할 수 있다는 장점이 있으며, 이렇게 활성 귀금속 성분의 담지 위치가 조절된 상태에서 담지된 촉매들은 희박농도의 메탄 산화에 있어서 매우 뛰어난 산화능력을 나타내었다.Accordingly, the present invention has led to the development of a noble metal-supported zeolite catalyst effective for methane oxidation under low temperature, low pressure and excessive oxygen atmosphere, and as a result, the conventional simple method for supporting noble metal components on a zeolite carrier. The present invention has been completed by devising a new concept supporting method instead of the acupuncture or ion exchange method. That is, in the present invention, in order to carry out high precious metal components around the zeolite catalyst in supporting the precious metal components, the precious metal components were supported in a state in which the zeolite pores were previously blocked with a specific organic compound having a molecular weight of about 70 to 250. When the active noble metal component is supported on the zeolite by the manufacturing method according to the present invention, there is an advantage that the expensive precious metal components can be accurately dispersed around the zeolite pores accurately compared to the conventional method, and thus the supporting position of the active noble metal component is controlled. The supported catalysts in the state showed an excellent oxidation capacity in the lean methane oxidation.
본 발명에서의 '메탄 산화촉매'라 함은 구체적으로 희박 농도의 메탄을 과잉 산소존재 하에서 선택적으로 산화 제거할 수 있는 촉매를 뜻한다. 본 발명은 박상언 등이 발표한 활성 귀금속 담지 방법에 근거를 두고 있다. 즉, 효율적산화 촉매를 제조하기 위하여 탄화수소를 산화시켜주는 활성 귀금속 촉매성분을 비표면적이 넓은 다공성의 제올라이트 담체에 잘 분산시킬 경우 산화온도를 낮추고, 산화활성을 증가시킬 수 있다는 원리에 근본을 두고 있다[S.-E. Park, React. Kinet. Catal. Lett., 57(1996) 339; 대한민국특허 출원 제98-064109호]. 메탄 산화촉매 제조에 있어서 산화활성을 높이기 위한 방안으로 활성 귀금속 성분을 알루미나, 지르코니아 등과 같이 표면적이 크고 열적으로 안정한 담체에 담지시키는 방법들이 적용되기는 하였으나, 제올라이트와 같이 미세세공과 함께 높은 비표면적을 갖는 담체에 담지된 예는 없다. 또한, 활성 금속성분의 담지방법에 있어서도 그 동안 단순한 이온교환법이나 함침법을 사용하여 왔으나[대한민국특허 출원 제96-0956호;M. Misono, Cattech, Jun(1998) 58], 메탄산화에 효과적인 금속상태로 귀금속 성분을 분산시키는데는 효율적이지 못하였다. 반면, 본 발명에서 개발한 담지방법은 메탄산화능력이 뛰어난 활성 귀금속 성분을 제올라이트 주위에 고분산 담지하는데 매우 효과적이다. 즉, 제올라이트 세공을 유기물로 미리 채워넣은(포접시켜) 상태에서 활성 귀금속 성분을 담지 함으로써 활성 금속 성분을 원하는 곳에만 분산시킬 수 있으며, 세공 보호를 통한 물질전달의 향상을 가져올 수 있다. 그 결과, 산화하기 가장 힘든 탄화수소인 메탄을 400℃ 이하의 낮은 온도에서도 기존의 산화촉매 보다도 높은 활성으로 산화하는 것이 가능해졌다.In the present invention, the term "methane oxidation catalyst" specifically means a catalyst capable of selectively oxidizing and removing lean methane in the presence of excess oxygen. The present invention is based on an active noble metal supporting method published by Park Sang-un et al. That is, it is based on the principle that the oxidation temperature can be lowered and the oxidation activity can be increased when the active noble metal catalyst component for oxidizing hydrocarbon is well dispersed in a zeolite carrier having a large specific surface area in order to prepare an efficient oxidation catalyst. S.-E. Park, React. Kinet. Catal. Lett., 57 (1996) 339; Republic of Korea Patent Application No. 98-064109]. In order to increase oxidation activity in methane oxidation catalysts, active noble metals such as alumina and zirconia are supported on a large surface area and thermally stable carriers. However, they have high specific surface area with fine pores like zeolite. There is no example supported on the carrier. In addition, in the method of supporting the active metal component, a simple ion exchange method or an impregnation method has been used in the past [Korean Patent Application No. 96-0956; M. Misono, Cattech, Jun (1998) 58], have not been effective in dispersing precious metal components in metal states that are effective for methanation. On the other hand, the supporting method developed in the present invention is very effective for carrying out high dispersion of active noble metal component having excellent methane oxidation ability around zeolite. That is, by supporting the active noble metal component in a state in which the zeolite pores are pre-filled (enclosed) with an organic material, the active metal component can be dispersed only where desired, and the material transfer can be improved through pore protection. As a result, it is possible to oxidize methane, which is the most difficult hydrocarbon to oxidize, with higher activity than existing oxidation catalysts even at a low temperature below 400 ° C.
본 발명은 제올라이트에 백금, 팔라듐, 로듐 및 금으로부터 선택된 귀금속을담지시켜 메탄 산화촉매를 제조하는 방법에 있어서, 상기 제올라이트 담체에 귀금속을 담지시키기에 앞서 분자량 70 ∼ 250 범위의 유기화합물으로 제올라이트 세공을 채운 후 귀금속을 담지시키는 메탄 산화촉매 제조방법을 그 특징으로 한다.The present invention is a method for preparing a methane oxidation catalyst by supporting a precious metal selected from platinum, palladium, rhodium and gold in the zeolite, prior to supporting the precious metal on the zeolite carrier, the zeolite pores with an organic compound having a molecular weight in the range of 70 to 250 It is characterized by a method for producing a methane oxidation catalyst supporting the precious metal after filling.
또한, 본 발명은 상기 제조방법에 의해 제조된 메탄 산화촉매를 사용하여 희박농도(30 ∼ 5000 ppm)의 메탄이 포함되어 있는 배기 배출가스로부터 메탄을 210℃ ∼ 400℃ 온도범위에서 제거하는 방법을 포함한다.In addition, the present invention provides a method for removing methane from 210 ℃ to 400 ℃ temperature range from the exhaust gas containing the lean (30 ~ 5000 ppm) of methane using a methane oxidation catalyst prepared by the above production method Include.
또한, 본 발명은 상기 제조방법으로 제조한 촉매를 400℃ ∼ 600℃ 범위에서 소성처리하여 활성화시키고, 여기에 30 ∼ 5000 ppm의 천연가스를 천연가스/산소=1/10 ∼ 1/100의 부피비, 그리고 10,000 ∼ 50,000 h-1의 공간유속으로 도입한 상태에서 메탄을 선택적으로 산화시키는 메탄 산화방법을 포함한다.In addition, the present invention is activated by firing the catalyst prepared by the above production method in the range of 400 ℃ to 600 ℃, where the natural gas of 30 to 5000 ppm natural gas / oxygen = 1/10 to 1/100 volume ratio And a methane oxidation method for selectively oxidizing methane in a state introduced at a space flow rate of 10,000 to 50,000 h −1 .
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 과량의 산소존재 하에서 희박농도의 메탄을 선택적으로 산화시키는 산화촉매 제조에 있어서, 종래의 일반적 촉매제조방법을 이용하는 대신 귀금속 담지시 촉매 각각의 기능을 충분히 유지한 상태에서 분자수준의 담지가 가능하도록 한 함침법 또는 이온교환법을 사용하였다.The present invention provides an oxidation catalyst for selectively oxidizing lean concentration of methane in the presence of excess oxygen. An impregnation method or ion exchange method was used which made it possible.
본 발명에 따른 메탄 산화촉매의 제조과정을 구체적으로 설명하면 다음과 같다.Referring to the manufacturing process of the methane oxidation catalyst according to the present invention in detail.
담체로서는 암모늄이온 또는 수소이온이 교환된 MFI, BEA, USY 구조를 갖는 H-형 또는 Na-형 제올라이트를 사용하며, 바람직하기로는 Si/Al 몰비가 10 ∼ 100으로서 실리카의 함량이 높은 제올라이트를 사용한다.As the carrier, an H-type or Na-type zeolite having an MFI, BEA, or USY structure in which ammonium ion or hydrogen ion is exchanged is used. Preferably, a zeolite having a high silica content with a Si / Al molar ratio of 10 to 100 is used. do.
그리고, 제올라이트 담체에 활성 귀금속 성분을 담지하기 전에 제올라이트 세공을 채우기 위하여 분자량 70 ∼ 250 범위의 유기화합물을 사용한다. 유기화합물의 분자량이 70 미만으로 작으면 제올라이트 세공을 통과하게 되므로 유기화합물의 처리효과를 얻을 수 없게 되고, 250을 초과하여 분자량이 큰 유기화합물을 사용하게 되면 제올라이트 세공에 채울 수 없게 되는 바, 사용되는 제올라이트 세공크기를 감안하여 볼 때 유기화합물의 분자량 범위는 70 ∼ 250 범위가 바람직한 것입니다. 본 발명이 사용하게 되는 유기 화합물을 구체적으로 예시하면 t-부틸알코올 등의 알킬알코올 화합물; 트리프로필아민 등의 알킬아민 화합물; 테트라프로필암모늄 하이드록사이드(TPAOH), 테트라부틸암모늄 하이드록사이드(TBAOH) 등의 알킬암모늄 하이드록사이드; 테트라프로필암모늄 브로마이드(TPABr), 테트라부틸암모늄 브로마이드(TBABr) 등의 알킬암모늄 할라이드 화합물들이다. 상기한 유기 화합물은 제올라이트의 세공을 채우기에 적절한 양을 사용하고, 채우고 난후 세공 외에 존재하는 잉여 유기 화합물은 용매로 완전히 세척한다. 제올라이트 세공을 채우기에 적절한 유기 화합물의 양은 0.5N 용액을 기준으로할 때 대략 0.3 ∼ 10 ㎖/g-담체 정도이다.An organic compound having a molecular weight in the range of 70 to 250 is used to fill the zeolite pores before the active noble metal component is supported on the zeolite carrier. When the molecular weight of the organic compound is less than 70, the zeolite pores are passed through, so that the effect of treating the organic compound cannot be obtained, and when the organic compound having a molecular weight greater than 250 is used, the zeolite pores cannot be filled. Considering the zeolite pore size, the molecular weight range of the organic compound is preferably 70 to 250. Specific examples of the organic compound to be used by the present invention include alkyl alcohol compounds such as t-butyl alcohol; Alkylamine compounds such as tripropylamine; Alkyl ammonium hydroxides such as tetrapropylammonium hydroxide (TPAOH) and tetrabutylammonium hydroxide (TBAOH); Alkyl ammonium halide compounds such as tetrapropylammonium bromide (TPABr) and tetrabutylammonium bromide (TBABr). The above organic compound is used in an appropriate amount to fill the pores of the zeolite, and after filling the excess organic compound present outside the pores is thoroughly washed with a solvent. Suitable amounts of organic compounds to fill the zeolite pores are on the order of approximately 0.3 to 10 ml / g-carrier based on a 0.5N solution.
유기물에 의해 세공이 채워진 제올라이트 담체에 백금, 팔라듐, 로듐, 금 등의 활성 귀금속 성분들은 제올라이트 담체를 기준으로 0.1 ∼ 5 중량%의 범위에서 진공증발에 의한 함침법 또는 이온교환법으로 담지시킨다. 함침법에 의한 담지방법에서는 원하는 양의 귀금속염이 함유된 수용액을 제올라이트 1 g당 5 ∼ 10 ㎖비로 만들어 제올라이트를 투입하며, 투입한 상태에서 2 ∼ 3시간 방치한 후 회전식 진공건조기로 상온에서 용매가 날아갈때가지 건조시킨다. 또한, 이온교환법에 의한 담지방법에서는 원하는 양의 귀금속염이 함유된 수용액을 제올라이트 1 g당 수용액이 100 ∼ 1000배가 되게 제조한 후 저어준 상태에서 제올라이트를 투입하며, 투입한 상태에서 12 ∼ 24시간동안 방치하여 충분한 이온교환이 이루어지도록 하고, 이온 교환이 이루어진 촉매는 필터플라스크에서 증류수로 충분히 세척하여 외부에 묻어있는 귀금속 염을 완전히 제거한다.The active noble metal components such as platinum, palladium, rhodium and gold are supported on the zeolite carrier filled with pores by the organic material by impregnation or ion exchange by vacuum evaporation in the range of 0.1 to 5% by weight based on the zeolite carrier. In the supporting method by impregnation method, the aqueous solution containing the desired amount of noble metal salt is made into a ratio of 5 to 10 ml per 1 g of zeolite, and the zeolite is added thereto, and the solvent is kept at room temperature with a rotary vacuum dryer after being left for 2 to 3 hours. Dry until it flies away. In addition, in the supporting method by ion exchange method, an aqueous solution containing a desired amount of a noble metal salt is prepared so that the aqueous solution is 100 to 1000 times per 1 g of zeolite, and then the zeolite is added in a stirred state for 12 to 24 hours. It is left for a while to allow sufficient ion exchange, and the catalyst which has been ion exchanged is thoroughly washed with distilled water in a filter flask to completely remove noble metal salts from outside.
만약, 두 종류 이상의 활성금속이 함유된 촉매를 제조하려는 경우, 두 종류 이상의 활성금속을 함유하고 있는 용액을 만들어 상기에서 언급한 바와 같은 담지법으로 제올라이트에 담지시킨다. 특히, 백금-로듐, 팔라듐-로듐, 금-로듐 등으로 예시되는 바와 같이, 로듐(B성분)과 백금, 팔라듐 및 금 중에서 선택된 또다른 활성금속(A성분)을 혼합사용하는 것이 단일 성분만으로 담지한 촉매보다 높은 활성을 나타내었다. 두 활성금속 A와 B를 담지시키는 경우 A/B 성분의 몰비는 0.1 ∼ 9 범위를 유지토록 한다.If a catalyst containing two or more active metals is to be prepared, a solution containing two or more active metals is prepared and supported on the zeolite by the supporting method as mentioned above. In particular, as exemplified by platinum-rhodium, palladium-rhodium, gold-rhodium, and the like, a mixture of rhodium (component B) and another active metal (component A) selected from platinum, palladium and gold is supported by only a single component. It showed higher activity than one catalyst. When supporting two active metals A and B, the molar ratio of the A / B component is maintained in the range of 0.1-9.
특히, 촉매의 메탄산화 활성을 더욱 향상시키기 위하여 상기한 귀금속 성분 이외에도 세륨, 타이타니아 및 코발트 중에서 선택된 조촉매를 제올라이트 담체를 기준으로 0.5 ∼ 5 중량% 범위내에서 귀금속과 함께 담지시킬 수도 있다.In particular, in order to further improve the methanation activity of the catalyst, in addition to the above noble metal components, a promoter selected from cerium, titania and cobalt may be supported together with the noble metal within the range of 0.5 to 5 wt% based on the zeolite carrier.
상기 담지방법에 의해 담지된 촉매는 100 ∼ 150℃의 범위에서 3 ∼ 5시간동안 건조한 후 500 ∼ 600℃의 범위의 공기분위기 하에서 3 ∼ 6시간동안 소성한다. 만일 소성온도가 400℃ 미만이거나 소성시간이 짧으면 금속성분들이 제올라이트 주위에 제대로 분산되지 않아 메탄 산화 활성이 떨어지게 된다. 또한, 소성온도가 너무 높아 700℃를 초과하면 촉매의 구조가 파괴되어 메탄 산화 효율이 낮아지게 된다.The catalyst supported by the supporting method is dried for 3 to 5 hours in the range of 100 to 150 ° C. and then calcined for 3 to 6 hours under an air atmosphere in the range of 500 to 600 ° C. If the firing temperature is less than 400 ℃ or the firing time is short, the metal components are not dispersed properly around the zeolite, methane oxidation activity is reduced. In addition, when the calcination temperature is too high and exceeds 700 ° C., the structure of the catalyst is destroyed and methane oxidation efficiency is low.
이상의 제조방법으로 제조된 분말상 촉매들은 공기분위기, 100 ∼ 200℃ 범위에서 3시간 활성화한 후 그 산화활성을 측정하였다. 반응은 유량조절기를 통하여 도입되는데, 이때 혼합가스는 천연가스, 산소, 헬륨으로 구성되어 있으며, 10,000 ∼ 50,000 h-1의 공간유속으로 주입되었을 때 280℃ 온도에서 50% 이상의 메탄 산화효율을 나타내었다. 촉매들은 210℃부터 산화활성을 나타나며, 400℃ 이상에서는 100%의 메탄 산화활성이 나타낸다. 따라서, 본 발명의 메탄 산화촉매는 210℃ ∼ 400℃ 온도범위에서 30 ∼ 5000 ppm의 희박농도로 메탄이 포함되어 있는 배기 배출가스로부터 메탄을 효과적으로 제거할 수 있다.Powdered catalysts prepared by the above production method were activated in an air atmosphere, 100-200 ° C. for 3 hours, and their oxidation activity was measured. The reaction is introduced through a flow controller, where the mixed gas consists of natural gas, oxygen, and helium, and when injected at a space flow rate of 10,000 to 50,000 h -1 , it exhibited more than 50% methane oxidation efficiency at 280 ° C. . The catalysts exhibit oxidative activity from 210 ° C and 100% methane oxidation activity above 400 ° C. Therefore, the methane oxidation catalyst of the present invention can effectively remove methane from exhaust gas containing methane at a lean concentration of 30 to 5000 ppm in the temperature range of 210 ° C to 400 ° C.
본 발명에서 사용된 메탄 산화촉매들에 있어서 반응물 중의 메탄/산소의 적정 부피비는 1/10 ∼ 1/100이며, 2 이하가 되면 활성이 떨어지게 된다.In the methane oxidation catalysts used in the present invention, the proper volume ratio of methane / oxygen in the reactants is 1/10 to 1/100, and when it is 2 or less, the activity is deteriorated.
이상에서 설명한 본 발명의 내용은 다음의 실시예에 의거하여 더욱 상세히 설명되나, 본 발명이 실시예 및 비교예에 한정되는 것은 아니다.The content of the present invention described above will be described in more detail based on the following examples, but the present invention is not limited to the examples and the comparative examples.
실시예 1 : t-BuOH에 의해 세공이 보호된 팔라듐 함침 β-제올라이트 촉매의 제조Example 1 Preparation of Palladium Impregnated β-zeolite Catalysts Protected by Pore by t-BuOH
0.5N t-부틸알코올(t-BuOH) 50 ㎖에 β-제올라이트(SiO2/Al2O3=25) 10 g을 넣고 5시간동안 교반한 후, 증류수로 충분히 세척하여 잉여 t-부틸알코올을 제거하였다. 그리고 70 ∼ 200℃ 조건에서 건조하여 t-BuOH에 의해 세공이 보호된 제올라이트 담체를 제조하였다.10 g of β-zeolite (SiO 2 / Al 2 O 3 = 25) was added to 50 mL of 0.5N t-butyl alcohol (t-BuOH), stirred for 5 hours, and then washed with distilled water sufficiently to remove excess t-butyl alcohol. Removed. And it dried on the conditions of 70-200 degreeC, and manufactured the zeolite support which the pore was protected by t-BuOH.
28 중량% 암모니아수 40 ㎖와 PdCl20.165 g이 혼합 용해되어 있는 수용액 200 ㎖에, 상기에서 제조한 담체를 넣고 상온에서 3시간 동안 교반하였다. 충분히 교반한 후, 70℃에서 3시간 진공건조기에서 교반하면서 건조시켜 1 중량%의 팔라듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '1.0PdB/BEA'라 칭함). 제조된 촉매는 120℃에서 12시간 건조한 후 550℃에서 5시간 산소분위기 하에서 소성하였다.The carrier prepared above was added to 200 ml of an aqueous solution in which 40 ml of 28% by weight aqueous ammonia and 0.165 g of PdCl 2 were dissolved, followed by stirring at room temperature for 3 hours. After sufficient stirring, the resultant was dried with stirring in a vacuum dryer at 70 ° C. for 3 hours to prepare a β-zeolite catalyst carrying 1 wt% of palladium (hereinafter, referred to as '1.0 PdB / BEA'). The prepared catalyst was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an oxygen atmosphere.
비교예 1 : 팔라듐 함침 β-제올라이트 촉매의 제조Comparative Example 1: Preparation of Palladium Impregnated β-zeolite Catalyst
상기 실시예 1과 동일한 방법으로 제조하되, β-제올라이트(SiO2/Al2O3=25) 세공을 t-부틸알코올로 보호하지 않은 상태에서 팔라듐을 함침하였다.Prepared in the same manner as in Example 1, but impregnated with palladium in a state in which the β-zeolite (SiO 2 / Al 2 O 3 = 25) pores were not protected with t-butyl alcohol.
즉, 28 중량% 암모니아수 40 ㎖와 PdCl20.165 g이 혼합 용해되어 있는 수용액 200 ㎖에, β-제올라이트 담체(10 g)를 넣고 상온에서 3시간 동안 교반하였다. 충분히 교반한 후, 70℃에서 3시간 진공건조기에서 교반하면서 건조시켜 1 중량%의 팔라듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '1.0PdC/BEA'라 칭함). 제조된 촉매는 120℃에서 12시간 건조한 후 550℃에서 5시간 산소분위기 하에서 소성하였다.That is, β-zeolite carrier (10 g) was added to 200 mL of an aqueous solution in which 40 mL of 28% by weight aqueous ammonia and 0.165 g of PdCl 2 were mixed and stirred, followed by stirring at room temperature for 3 hours. After sufficient stirring, the resultant was dried with stirring in a vacuum dryer at 70 ° C. for 3 hours to prepare a β-zeolite catalyst carrying 1% by weight of palladium (hereinafter, referred to as '1.0PdC / BEA'). The prepared catalyst was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an oxygen atmosphere.
실시예 2 : TPAOH에 의해 세공이 보호된 팔라듐 함침 β-제올라이트 촉매의 제조Example 2 Preparation of Palladium-impregnated β-zeolite Catalysts Protected by Pores by TPAOH
상기 실시예 1과 동일한 방법으로 제조하되, β-제올라이트(SiO2/Al2O3=25) 세공을 보호하기 위하여 t-BuOH를 대신하여 t-프로필암모늄 하이드록사이드(TPAOH)를 사용하였다. 즉, 0.5N TPAOH 수용액 50 ㎖에 β-제올라이트(SiO2/Al2O3=25)10 g을 넣고 5시간동안 교반한 후, 증류수로 충분히 세척하여 잉여 TPAOH를 제거하였다. 이후 제조과정은 상기 실시예 1과 동일한 방법으로 수행하였으며, 그 결과 1 중량%의 팔라듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '1.0PdT/BEA'라 칭함).Prepared in the same manner as in Example 1, in order to protect the β-zeolite (SiO 2 / Al 2 O 3 = 25) pores t-propylammonium hydroxide (TPAOH) was used in place of t-BuOH. That is, 10 g of β-zeolite (SiO 2 / Al 2 O 3 = 25) was added to 50 mL of 0.5N TPAOH aqueous solution, and stirred for 5 hours, followed by washing with distilled water to remove excess TPAOH. Thereafter, the manufacturing process was carried out in the same manner as in Example 1, and as a result, a β-zeolite catalyst carrying 1 wt% of palladium was prepared (hereinafter, referred to as '1.0 PdT / BEA').
비교예 2 : 적심법에 의해 제조된 촉매와의 비교Comparative Example 2: Comparison with Catalyst Prepared by Wetting
대한민국특허 출원 제96-0956호의 실시예 1에 나타난 방법(일명, '적심법')을 이용하여 팔라듐을 담지하였다. 즉, 28 중량% 암모니아수 18 ㎖에 PdCl20.165 g을 넣고 교반하여 적심용액을 제조하였다. 한편, 세공이 보호되지 않은 β-제올라이트 담체(10 g)를 넣고 120℃에서 2시간 건조시킨 후, 건조제가 내장된 데시케이터에 보관하여 실온으로 냉각시킴으로써 무수 담체를 준비하였다. 무수 담체에 상기 적심용액을 한방울씩 가하여 담체가 간신히 젖을 때까지 가하였다. 제조된 촉매는 120℃에서 12시간 건조하여 1 중량%의 팔라듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '1.0PdCW/BEA'라 칭함).Palladium was supported by using the method shown in Example 1 of Korean Patent Application No. 96-0956 (aka, 'wetting method'). In other words, 0.165 g of PdCl 2 was added to 18 ml of 28% by weight aqueous ammonia to prepare a wet solution. On the other hand, after the β-zeolite carrier (10 g) unprotected pores were put and dried at 120 ℃ for 2 hours, the anhydrous carrier was prepared by storing in a desiccator with a drying agent and cooling to room temperature. The dropping solution was added dropwise to the dry carrier until the carrier barely got wet. The prepared catalyst was dried at 120 ° C. for 12 hours to prepare a β-zeolite catalyst loaded with 1% by weight of palladium (hereinafter, referred to as '1.0 PdCW / BEA').
실시예 3 : t-BuOH에 의해 세공이 보호된 백금 함침 β-제올라이트 촉매의 제조Example 3 Preparation of Platinum Impregnated β-zeolite Catalysts Protected by Pore by t-BuOH
상기 실시예 1과 동일한 방법으로 제조하되, 팔라듐 활성금속을 대신하여 백금 활성금속을 함침하였다. 즉, H2PtCl6(0.21 g)가 용해된 수용액 200 ㎖에, t-BuOH에 의해 세공이 보호된 β-제올라이트(SiO2/Al2O3=25) 담체 10 g을 넣고 진공건조시켜 1 중량%의 백금이 담지된 β-제올라이트 촉매를 제조하였다(이하, '1.0PtB/BEA'라 칭함). 제조된 촉매는 120℃에서 12시간 건조한 후 550℃에서 5시간 산소분위기 하에서 소성하였다.Prepared in the same manner as in Example 1, but impregnated with a platinum active metal in place of the palladium active metal. That is, in 200 ml of an aqueous solution in which H 2 PtCl 6 (0.21 g) was dissolved, 10 g of β-zeolite (SiO 2 / Al 2 O 3 = 25) carrier protected by pore by t-BuOH was added and dried in vacuo. A β-zeolite catalyst carrying a weight% platinum was prepared (hereinafter, referred to as '1.0 PtB / BEA'). The prepared catalyst was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an oxygen atmosphere.
실시예 4 : t-BuOH에 의해 세공이 보호된 팔라듐-로듐 함침 β-제올라이트 촉매의 제조Example 4 Preparation of Palladium-Rhodium Impregnated β-zeolite Catalysts Protected Pore by t-BuOH
상기 실시예 1과 동일한 방법으로 제조하되, 활성금속으로 팔라듐과 로듐을 함께 함침하였다. 즉, 28 중량% 암모니아수 40 ㎖와 PdCl20.132 g과 RhCl3·xH2O(Rh 함량 40 중량%) 0.05 g이 혼합 용해되어 있는 수용액 200 ㎖에, t-BuOH에 의해 세공이 보호된 β-제올라이트(SiO2/Al2O3=25) 담체 10 g을 넣고 상온에서 3시간 동안 교반하였다. 충분히 교반한 후, 70℃에서 3시간 진공건조기에서 교반하면서 건조시켜 1 중량%의 팔라듐-로듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '0.8Pd-0.2RhB/BEA'라 칭함). 제조된 촉매는 120℃에서 12시간 건조한 후 550℃에서 5시간 산소분위기 하에서 소성하였다.Prepared in the same manner as in Example 1, but impregnated with palladium and rhodium as the active metal. That is, β- protected by t-BuOH in 200 ml of an aqueous solution in which 40 ml of 28% by weight aqueous ammonia, 0.132 g of PdCl 2 and 0.05 g of RhCl 3 .xH 2 O (40% by weight of Rh) are mixed and dissolved. 10 g of zeolite (SiO 2 / Al 2 O 3 = 25) was added thereto, followed by stirring at room temperature for 3 hours. After sufficient stirring, the resultant was dried with stirring in a vacuum dryer at 70 ° C. for 3 hours to prepare a β-zeolite catalyst carrying 1 wt% of palladium-rhodium (hereinafter referred to as '0.8 Pd-0.2RhB / BEA'). The prepared catalyst was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an oxygen atmosphere.
실시예 5 : t-BuOH에 의해 세공이 보호된 백금-로듐 함침 β-제올라이트 촉매의 제조Example 5 Preparation of Platinum-Rhodium Impregnated β-zeolite Catalysts Protected by Pore by t-BuOH
상기 실시예 1과 동일한 방법으로 제조하되, 활성금속으로 백금과 로듐을 함께 함침하였다. 즉, H2PtCl60.168 g과 RhCl3·xH2O(Rh함량 40 중량%) 0.05 g이혼합 용해되어 있는 수용액 200 ㎖에, t-BuOH에 의해 세공이 보호된 β-제올라이트(SiO2/Al2O3=25) 담체 10 g을 넣고 상온에서 3시간 동안 교반하였다. 충분히 교반한 후, 70℃에서 3시간 진공건조기에서 교반하면서 건조시켜 1 중량%의 백금-로듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '0.8Pt-0.2RhB/BEA'라 칭함). 제조된 촉매는 120℃에서 12시간 건조한 후 550℃에서 5시간 산소분위기 하에서 소성하였다.Prepared in the same manner as in Example 1, but impregnated with platinum and rhodium with an active metal. That is, β-zeolite (SiO 2 /) in which pores were protected by t-BuOH in 200 ml of an aqueous solution of 0.168 g of H 2 PtCl 6 and 0.05 g of RhCl 3 .xH 2 O (Rh content 40% by weight) was mixed. 10 g of Al 2 O 3 = 25) was added thereto, followed by stirring at room temperature for 3 hours. After sufficient stirring, the resultant was dried with stirring in a vacuum dryer at 70 ° C. for 3 hours to prepare a β-zeolite catalyst loaded with 1% by weight of platinum-rhodium (hereinafter, referred to as 0.8Pt-0.2RhB / BEA). The prepared catalyst was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an oxygen atmosphere.
실시예 6 : t-BuOH에 의해 세공이 보호된 금-로듐 함침 β-제올라이트 촉매의 제조Example 6 Preparation of Gold-Rhodium Impregnated β-zeolite Catalysts Protected by Pore by t-BuOH
상기 실시예 1과 동일한 방법으로 제조하되, 활성금속으로 금과 로듐을 함께 함침하였다. 즉, HAuCl4·xH2O 0.138 g과 RhCl3·xH2O(Rh함량 40 중량%) 0.05 g이 혼합 용해되어 있는 수용액 200 ㎖에, t-BuOH에 의해 세공이 보호된 β-제올라이트(SiO2/Al2O3=25) 담체 10 g을 넣고 상온에서 3시간 동안 교반하였다. 충분히 교반한 후, 70℃에서 3시간 진공건조기에서 교반하면서 건조시켜 1 중량%의 백금-로듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '0.8Au-0.2RhB/BEA'라 칭함). 제조된 촉매는 120℃에서 12시간 건조한 후 550℃에서 5시간 산소분위기 하에서 소성하였다.Prepared in the same manner as in Example 1, but impregnated with gold and rhodium with an active metal. That is, β-zeolite (SiO) in which pores were protected by t-BuOH in 200 ml of an aqueous solution in which 0.138 g of HAuCl 4 xH 2 O and 0.05 g of RhCl 3 xH 2 O (40 wt% Rh) were mixed and dissolved. 2 / Al 2 O 3 = 25) 10 g of the carrier was added and stirred at room temperature for 3 hours. After sufficient stirring, the resultant was dried with stirring in a vacuum dryer at 70 ° C. for 3 hours to prepare a β-zeolite catalyst loaded with 1% by weight of platinum-rhodium (hereinafter, referred to as 0.8Au-0.2RhB / BEA). The prepared catalyst was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an oxygen atmosphere.
실시예 7 : 세슘이 첨가된 팔라듐 담지 β-제올라이트 촉매의 제조Example 7 Preparation of Palladium Supported β-zeolite Catalyst Added with Cesium
상기 실시예 1과 동일한 방법으로 제조하되, 촉매의 산화력 증가를 위하여 세슘을 함께 담지하였다. 즉, Ce(NO3)2·6H2O 0.310 g이 혼합 용해되어 있는 수용액 200 ㎖에 상기 실시예 1에서 제조한 팔라듐 담지 제올라이트 촉매(1.0PdB/BEA)를 넣고 상온에서 3시간 동안 교반하였다. 충분히 교반한 후, 70℃에서 3시간 진공건조기에서 교반하면서 건조시켜 1 중량%의 팔라듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '1.0Ce-1.0PdB/BEA'라 칭함). 제조된 촉매는 120℃에서 12시간 건조한 후 550℃에서 5시간 산소분위기 하에서 소성하였다.Prepared in the same manner as in Example 1, but supported with cesium to increase the oxidation power of the catalyst. That is, palladium-supported zeolite catalyst (1.0PdB / BEA) prepared in Example 1 was added to 200 ml of an aqueous solution in which 0.310 g of Ce (NO 3 ) 2 .6H 2 O was mixed and dissolved, followed by stirring at room temperature for 3 hours. After sufficient stirring, the resultant was dried with stirring in a vacuum dryer at 70 ° C. for 3 hours to prepare a β-zeolite catalyst carrying 1 wt% of palladium (hereinafter, referred to as '1.0Ce-1.0PdB / BEA'). The prepared catalyst was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an oxygen atmosphere.
실시예 8 : 티타늄이 첨가된 팔라듐 담지 β-제올라이트 촉매의 제조Example 8 Preparation of Palladium Supported β-zeolite Catalyst Added with Titanium
상기 실시예 1과 동일한 방법으로 제조하되, 활성금속 팔라듐의 분산도를 높이기 위하여 티타늄을 함께 담지하였다. 즉, Ti[OCH(CH3)2]41.18 g이 용해되어 있는 이소프로필알코올 용액 200 ㎖에 상기 실시예 1에서 제조한 팔라듐 담지 제올라이트 촉매(1.0PdB/BEA)를 넣고 상온에서 3시간 동안 교반하였다. 충분히 교반한 후, 70℃에서 3시간 진공건조기에서 교반하면서 건조시켜 1 중량%의 팔라듐이 담지된 β-제올라이트 촉매를 제조하였다(이하, '2.0Ti-1.0PdB/BEA'라 칭함). 제조된 촉매는 120℃에서 12시간 건조한 후 550℃에서 5시간 산소분위기 하에서 소성하였다.Prepared in the same manner as in Example 1, but also loaded with titanium to increase the dispersion of the active metal palladium. That is, to 200 ml of isopropyl alcohol solution in which 1.18 g of Ti [OCH (CH 3 ) 2 ] 4 is dissolved, the palladium-supported zeolite catalyst (1.0 PdB / BEA) prepared in Example 1 was added and stirred at room temperature for 3 hours. It was. After sufficient stirring, the resultant was dried with stirring in a vacuum dryer at 70 ° C. for 3 hours to prepare a β-zeolite catalyst carrying 1% by weight of palladium (hereinafter referred to as '2.0 Ti-1.0 PdB / BEA'). The prepared catalyst was dried at 120 ° C. for 12 hours and then calcined at 550 ° C. for 5 hours in an oxygen atmosphere.
실시예 9 : 팔라듐 이온교환된 H-ZSM-5 촉매의 제조Example 9 Preparation of Palladium Ion Exchanged H-ZSM-5 Catalyst
상기 실시예 1과 동일한 방법으로 제조하되, 함침법을 대신하여 이온교환법을 적용하였다. 즉, 28 중량% 암모니아수 160 ㎖와 PdCl20.330 g이 혼합 용해되어 있는 수용액 1,000 ㎖에, t-BuOH에 의해 세공이 보호된 H-ZSM-5(SiO2/Al2O3=30) 담체 10 g을 넣고 상온에서 12시간동안 교반하면서 2 중량%의 팔라듐이 이온교환된 H-ZSM-5 촉매를 제조하였다(이하, '1.0PdB-I/MFI'라 칭함). 이온교환된 촉매는 증류수로 충분히 세척하였으며, 120℃에서 12시간 건조한 후 500℃에서 5시간 산소분위기 하에서 소성하였다.It was prepared in the same manner as in Example 1, but the ion exchange method was applied in place of the impregnation method. That is, H-ZSM-5 (SiO 2 / Al 2 O 3 = 30) carrier 10 in which pores were protected by t-BuOH in 1,000 ml of an aqueous solution in which 160 ml of 28% by weight aqueous ammonia and 0.330 g of PdCl 2 were mixed and dissolved. 2 g of palladium-ion-exchanged H-ZSM-5 catalyst was prepared by adding g and stirring for 12 hours at room temperature (hereinafter, referred to as '1.0 PdB-I / MFI'). The ion exchanged catalyst was sufficiently washed with distilled water, dried at 120 ° C. for 12 hours, and calcined at 500 ° C. under an oxygen atmosphere for 5 hours.
비교예 3 : 팔라듐 이온교환된 H-ZSM-5 촉매의 제조Comparative Example 3 Preparation of Palladium Ion Exchanged H-ZSM-5 Catalyst
상기 실시예 9과 동일한 방법으로 제조하되, H-ZSM-5(SiO2/Al2O3=30) 세공을 t-부틸알코올로 보호하지 않은 상태에서 팔라듐을 이온교환하였다. 즉, 28 중량% 암모니아수 160 ㎖와 PdCl20.165 g이 혼합 용해되어 있는 수용액 200 ㎖에 β-제올라이트 담체 10 g을 넣고 상온에서 12시간동안 교반하면서 1.0 중량%의 팔라듐이 이온교환된 H-ZSM-5 촉매를 제조하였다(이하, '1.0PdC-I/MFI'라 칭함). 이온교환된 촉매는 증류수로 충분히 세척하였으며, 120℃에서 12시간 건조한 후 500℃에서 5시간 산소분위기 하에서 소성하였다.It was prepared in the same manner as in Example 9, but palladium was ion-exchanged in the state that H-ZSM-5 (SiO 2 / Al 2 O 3 = 30) pores were not protected with t-butyl alcohol. In other words, 10 g of β-zeolite carrier was added to 200 ml of an aqueous solution in which 160 ml of 28% by weight aqueous ammonia and 0.165 g of PdCl 2 were dissolved. H-ZSM- having 1.0% by weight of palladium ion exchanged while stirring at room temperature for 12 hours. Five catalysts were prepared (hereinafter referred to as '1.0 PdC-I / MFI'). The ion exchanged catalyst was sufficiently washed with distilled water, dried at 120 ° C. for 12 hours, and calcined at 500 ° C. under an oxygen atmosphere for 5 hours.
실시예 10 : TPAOH에 의해 세공이 보호된 팔라듐 이온교환된 H-ZSM-5 촉매의 제조Example 10 Preparation of Palladium Ion-Exchanged H-ZSM-5 Catalysts Protected Pore by TPAOH
상기 실시예 9과 동일한 방법으로 제조하되, H-ZSM-5(SiO2/Al2O3=30) 세공을 보호하기 위하여 t-BuOH를 대신하여 t-프로필암모늄 하이드록사이드(TPAOH)를 사용하였다. 즉, 0.5N TPAOH 수용액 50 ㎖에 H-ZSM-5 10 g을 넣고 5시간동안 교반한 후, 증류수로 충분히 세척하여 잉여 TPAOH를 제거하였다. 이후 제조과정은 상기 실시예 9과 동일한 방법으로 수행하였으며, 그 결과 팔라듐이 이온교환된 H-ZSM-5 촉매를 제조하였다(이하, '1.0PdT-I/MFI'라 칭함).Prepared in the same manner as in Example 9, but using t-propylammonium hydroxide (TPAOH) in place of t-BuOH to protect the H-ZSM-5 (SiO 2 / Al 2 O 3 = 30) pores It was. That is, 10 g of H-ZSM-5 was added to 50 mL of 0.5N TPAOH aqueous solution, and stirred for 5 hours, followed by washing with distilled water sufficiently to remove excess TPAOH. Thereafter, the manufacturing process was performed in the same manner as in Example 9, and as a result, a p-dium ion-exchanged H-ZSM-5 catalyst was prepared (hereinafter, referred to as '1.0PdT-I / MFI').
실시예 11 : TPABr에 의해 세공이 보호된 팔라듐 이온교환된 H-ZSM-5 촉매의 제조Example 11 Preparation of Palladium Ion Exchanged H-ZSM-5 Catalysts Protected Pore by TPABr
상기 실시예 9과 동일한 방법으로 제조하되, H-ZSM-5(SiO2/Al2O3=30) 세공을 보호하기 위하여 t-BuOH를 대신하여 t-프로필암모늄 브로마이드(TPABr)를 사용하였다. 즉, 0.5N TPABr 수용액 50 ㎖에 H-ZSM-5 10 g을 넣고 5시간동안 교반한 후, 증류수로 충분히 세척하여 잉여 TPABr를 제거하였다. 이후 제조과정은 상기 실시예 9과 동일한 방법으로 수행하였으며, 그 결과 팔라듐이 이온교환된 H-ZSM-5 촉매를 제조하였다(이하, '1.0PdTB-I/MFI'라 칭함).Prepared in the same manner as in Example 9, in order to protect the H-ZSM-5 (SiO 2 / Al 2 O 3 = 30) pores t-propylammonium bromide (TPABr) was used in place of t-BuOH. That is, 10 g of H-ZSM-5 was added to 50 ml of 0.5N TPABr aqueous solution, stirred for 5 hours, and then washed with distilled water sufficiently to remove excess TPABr. Thereafter, the manufacturing process was performed in the same manner as in Example 9, and as a result, a p-dium ion-exchanged H-ZSM-5 catalyst was prepared (hereinafter, referred to as '1.0 PdTB-I / MFI').
실시예 12 : t-BuOH에 의해 세공이 보호된 백금 이온교환된 H-ZSM-5 촉매의 제조Example 12 Preparation of Platinum Ion Exchanged H-ZSM-5 Catalysts Protected Pore by t-BuOH
상기 실시예 9과 동일한 방법으로 제조하되, 팔라듐 활성금속을 대신하여 백금 활성금속을 이온교환하여 담지하였다. 즉, H2PtCl6(0.21 g)가 용해된 수용액 1,000 ㎖에, t-BuOH에 의해 세공이 보호된 H-ZSM-5(SiO2/Al2O3=30) 담체 10 g을 넣고 상온에서 12시간 동안 교반하면서 1 중량%의 백금이 이온교환된 H-ZSM-5 촉매를 제조하였다(이하, '1.0PtB-I/MFI'라 칭함). 이온교환된 촉매는 증류수로 충분히 세척하였으며, 120℃에서 12시간 건조한 후 500℃에서 5시간 산소분위기 하에서 소성하였다.Prepared in the same manner as in Example 9, in place of the palladium active metal was supported by ion-exchanged platinum active metal. That is, H2PtCl6(0.21 g) in an aqueous solution At 1,000 ml, H-ZSM-5 (SiO) in which pores were protected by t-BuOH2/ Al2O330 g of H-ZSM-5 catalyst with 1 wt% platinum was exchanged with 10 g of the carrier and stirred at room temperature for 12 hours (hereinafter referred to as '1.0 PtB-I / MFI'). The ion exchanged catalyst was sufficiently washed with distilled water, dried at 120 ° C. for 12 hours, and calcined at 500 ° C. under an oxygen atmosphere for 5 hours.
실시예 13 : t-BuOH에 의해 세공이 보호된 금 이온교환된 H-ZSM-5 촉매의 제조Example 13 Preparation of Gold Ion Exchanged H-ZSM-5 Catalysts with Pore Protection by t-BuOH
상기 실시예 9과 동일한 방법으로 제조하되, 팔라듐 활성금속을 대신하여 금 활성금속을 이온교환하여 담지하였다. 즉, HAuCL4·xH2O 0.172 g가 용해된 수용액 1,000 ㎖에, t-BuOH에 의해 세공이 보호된 H-ZSM-5(SiO2/Al2O3=30) 담체 10 g을 넣고 상온에서 12시간 동안 교반하면서 1 중량%의 금이 이온교환된 H-ZSM-5 촉매를 제조하였다(이하, '1.0AuB-I/MFI'라 칭함). 이온교환된 촉매는 증류수로 충분히 세척하였으며, 120℃에서 12시간 건조한 후 500℃에서 5시간 산소분위기 하에서 소성하였다.Prepared in the same manner as in Example 9, but was supported by ion-exchange the gold active metal in place of the palladium active metal. That is, HAuCL 4 · xH 2 O 0.172 g is put into the pores is covered by the dissolved solution to 1,000 ㎖, t-BuOH H- ZSM-5 (SiO 2 / Al 2 O 3 = 30) the carrier 10 g at room temperature, An H-ZSM-5 catalyst was prepared in which 1% by weight of gold was ion-exchanged with stirring for 12 hours (hereinafter referred to as '1.0AuB-I / MFI'). The ion exchanged catalyst was sufficiently washed with distilled water, dried at 120 ° C. for 12 hours, and calcined at 500 ° C. under an oxygen atmosphere for 5 hours.
실험예 : 촉매활성도 평가Experimental Example: Evaluation of Catalytic Activity
상기 실시예 및 비교예에서 제조한 각각의 촉매 0.30 g을 외경 1.2 ㎝, 길이 70 ㎝의 석영관 반응기에 충전하여 온도조절기가 부착된 전기로에서 반응활성을 측정였다. 모든 촉매는 반응 전에 수소로 200℃에서 5시간 전처리한 후에 동일한 온도에서 150 ㏄/min의 유속으로 헬륨을 유입하면서 2시간 유지시킨 후 실온으로 냉각하였다. 촉매활성은 메탄가스 30 ppm과 나머지 산소의 혼합가스를 200 ㏄/min의 유속으로 촉매에 유입하면서 측정하였다. 촉매의 활성도 평가는 150 ∼ 600 ℃ 범위에서 측정하였으며, 다음 수학식 1에 의해 메탄(CH4) 제거율을 계산하였다. 그 결과는 다음 표 1, 표 2 및 표 3에 나타내었다.0.30 g of each catalyst prepared in Examples and Comparative Examples was charged in a quartz tube reactor having an outer diameter of 1.2 cm and a length of 70 cm to measure reaction activity in an electric furnace equipped with a temperature controller. All the catalysts were pretreated with hydrogen at 200 ° C. for 5 hours before the reaction and then held for 2 hours with helium at a flow rate of 150 kW / min at the same temperature and then cooled to room temperature. Catalytic activity was measured while introducing a mixed gas of 30 ppm of methane gas and the remaining oxygen into the catalyst at a flow rate of 200 dl / min. The activity evaluation of the catalyst was measured in the range of 150 ~ 600 ℃, methane (CH 4 ) removal rate was calculated by the following equation (1). The results are shown in the following Table 1, Table 2 and Table 3.
상기 표 1, 표 2 및 표 3의 결과는 본 발명에 의해 담체인 제올라이트 세공을 유기물로 보호한 상태에서 팔라듐, 백금, 금 등의 활성 귀금속 성분을 담지하여 제조한 촉매와, 종래의 일반적인 제조방법에 의해 팔라듐, 백금, 로듐 등의 활성 귀금속이 함침 또는 이온교환하여 제조한 제올라이트 촉매들 각각에 대한 메탄산화활성을 여러 온도에서 측정 및 비교한 것이다. 일반적인 담지방법에 의하여 제조한 촉매의 경우는 메탄의 산화온도가 350 ∼ 400℃에서 시작되어 600 ∼ 700℃에서 최대 활성을 나타내지만, 본 발명에 따른 제조방법에서 제조한 촉매의 경우는 반응시작온도가 210℃ 정도로 낮으며 메탄의 완전산화가 400℃ 이하에서 가능함을 보여준다(표 3).The results of Table 1, Table 2 and Table 3 show a catalyst prepared by supporting active noble metal components such as palladium, platinum and gold in a state in which the zeolite pores serving as carriers are protected with an organic material according to the present invention, and a conventional general manufacturing method. The methanation activity of each zeolite catalyst prepared by impregnation or ion exchange of active noble metals such as palladium, platinum, and rhodium was measured and compared at various temperatures. In the case of the catalyst prepared by the general supporting method, the oxidation temperature of methane starts at 350-400 ° C. and shows the maximum activity at 600-700 ° C., but in the case of the catalyst prepared in the production method according to the present invention, the reaction start temperature Is as low as 210 ° C. and shows that complete oxidation of methane is possible below 400 ° C. (Table 3).
상기 표 1, 표 2 및 표 3의 결과에 의하면, 실시예 1과 실시예 4 ∼ 7의 촉매들이 비교예 1과 비교예 3의 촉매보다 더 우수한 메탄산화능을 보였다. 즉, 세공을 보호한 담체에 팔라듐을 담지한 촉매는 3% 산소, 450℃, GHSV=30,000 h-1에서 적어도 100%의 메탄 제거율을 나타내었다.According to the results of Tables 1, 2 and 3, the catalysts of Examples 1 and 4 to 7 showed better methane oxidation ability than those of Comparative Examples 1 and 3. That is, the catalyst supporting palladium on the pore-protected carrier showed at least 100% methane removal at 3% oxygen, 450 ° C., and GHSV = 30,000 h −1 .
본 발명에서는 천연가스의 메탄 산화활성을 높이기 위하여 담체의 세공을 유기물로서 보호한 상태에서 활성 귀금속을 담지하는 제조방법을 제시하고 있다. 제올라이트 담체의 세공을 유기물로 보호한 상태에서 귀금속을 담지하게 되면 산화활성이 뛰어난 귀금속 성분들이 제올라이트 담체의 표면에 존재함으로써 메탄의 산화반응 온도를 낮추는 것으로 해석된다.In the present invention, in order to increase the methane oxidation activity of natural gas, a production method for supporting an active noble metal while protecting the pores of the carrier as an organic material is proposed. When the precious metal is supported while the pores of the zeolite carrier are protected with an organic substance, it is interpreted that the oxidation reaction temperature of methane is lowered by the presence of noble metal components having excellent oxidation activity on the surface of the zeolite carrier.
이에, 본 발명에서 제조한 산화촉매는 보일러 등과 같은 고정원에서 발생하는 희박농도의 메탄을 과산소 분위기하에서 산화시켜 제거하는데 매우 유용하다.Accordingly, the oxidation catalyst prepared in the present invention is very useful for oxidizing and removing lean concentration of methane generated from a fixed source such as a boiler in a peroxygen atmosphere.
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| KR20210075543A (en) | 2019-12-13 | 2021-06-23 | 연세대학교 산학협력단 | Methane oxidation catalyst, preparation method thereof and partial oxidation of methane using the same |
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| JPH06254352A (en) * | 1993-03-04 | 1994-09-13 | Tokyo Gas Co Ltd | Method for purifying waste combustion gas and catalyst used in this method |
| US5811067A (en) * | 1993-06-30 | 1998-09-22 | Gaz De France | Catalytic method for selectively reducing nitrogen oxides |
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| KR20210075543A (en) | 2019-12-13 | 2021-06-23 | 연세대학교 산학협력단 | Methane oxidation catalyst, preparation method thereof and partial oxidation of methane using the same |
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