KR100847739B1 - Catalyzer for cleaning nitrous oxide, production method thereof, and cleaning method of nitrous oxide using it - Google Patents
Catalyzer for cleaning nitrous oxide, production method thereof, and cleaning method of nitrous oxide using it Download PDFInfo
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Abstract
본 발명은 아산화질소 제거용 촉매와 그 제조방법 및 그 촉매를 이용한 아산화질소 제거방법을 개시한다. 본 발명의 아산화질소 제거용 촉매의 제조방법은 모더나이트형 제올라이트를 준비하여 세척하는 단계와, 모더나이트형 제올라이트를 건조하는 단계와, 이온교환을 통해 0.01~10.0중량%의 철을 모더나이트형 제올라이트에 담지하는 단계와, 모더나이트형 제올라이트를 건조하는 단계와, 함침법을 통해 0.01~5.0중량%의 귀금속 파라듐을 모더나이트형 제올라이트에 담지하는 단계 및 모더나이트형 제올라이트를 건조하고 소성하는 단계를 포함하므로, 350℃정도의 온도에서 아산화질소를 제거율을 증대할 수 있는 이점이 있다.The present invention discloses a catalyst for removing nitrous oxide, a method for producing the same, and a method for removing nitrous oxide using the catalyst. The method for preparing a nitrous oxide removal catalyst of the present invention comprises the steps of preparing and washing a mordenite zeolite, drying the mordenite zeolite, and converting 0.01 to 10.0% by weight of iron to mordenite zeolite through ion exchange. Supporting, drying the mordenite zeolite, impregnating 0.01 to 5.0% by weight of the precious metal palladium into the mordenite zeolite through the impregnation method, and drying and firing the mordenite zeolite. Including, there is an advantage that can increase the removal rate of nitrous oxide at a temperature of about 350 ℃.
아산화질소, 제올라이트, 담지체, 촉매, 활성물질, 귀금속, 반응온도 Nitrous oxide, zeolite, carrier, catalyst, active substance, precious metal, reaction temperature
Description
도 1은 본 발명에 따른 촉매의 제조과정을 도시한 제1실시예,1 is a first embodiment illustrating a process of preparing a catalyst according to the present invention;
도 2는 본 발명에 따른 촉매의 제조과정을 도시한 제2실시예,Figure 2 is a second embodiment showing the manufacturing process of the catalyst according to the present invention,
도 3은 본 발명에 따른 촉매의 제조과정을 도시한 제3실시예,3 is a third embodiment illustrating a process of preparing a catalyst according to the present invention;
도 4는 본 발명에 따른 촉매를 이용하여 아산화질소를 제거하는 절차를 도시한 순서도,4 is a flowchart showing a procedure for removing nitrous oxide using a catalyst according to the present invention;
도 5는 본 발명에 따른 촉매를 이용하여 아산화질소를 제거할 때 온도에 따른 아산화질소의 제거율을 도시한 도면,5 is a diagram illustrating the removal rate of nitrous oxide according to temperature when removing nitrous oxide using the catalyst according to the present invention;
도 6은 본 발명의 촉매를 이용하여 아산화질소를 제거할 때와 종래의 촉매를 이용하여 아산화질소를 제거할 때의 아산화질소의 제거할 때의 반응온도를 비교하여 도시한 도면이다.6 is a view showing a comparison of the reaction temperature when removing nitrous oxide when removing nitrous oxide using the catalyst of the present invention and removing nitrous oxide using a conventional catalyst.
본 발명은 촉매를 이용하여 지구온난화가스인 아산화질소(N₂O)를 제거하는 것으로서, 보다 상세하게는 모더나이트형 제올라이트를 담지체로 하여 전이금속과 귀금속을 담지하여 제조한 촉매와 이의 제조방법 및 이를 이용한 아산화질소 제거 방법에 관한 것이다.The present invention is to remove nitrous oxide (N₂O), a global warming gas by using a catalyst, and more specifically, a catalyst prepared by supporting a transition metal and a noble metal using a mordenite zeolite as a support, and a method for preparing the same A method for removing nitrous oxide.
일반적으로, 촉매를 이용하여 아산화질소(N₂O)를 제거하는 기술은 직접분해와 선택적 촉매환원의 두 가지 기술이 주로 연구되고 있다. In general, two techniques of direct decomposition and selective catalytic reduction are mainly studied for removing nitrous oxide (N₂O) using a catalyst.
직접분해의 경우 850℃ 이상 고온의 조건이 필요하지만, 선택적 촉매환원 방법을 이용하면 주입되는 환원제를 통해 500℃ 전후에서 N₂O를 효과적으로 제거할 수 있다는 장점이 있다. 제올라이트(Zeolite)를 촉매 담지체로 이용하는 경우, 400~450℃ 의 온도범위에서 N₂O가 발생하는 사업장에 선택적 촉매환원을 위한 촉매를 도입할 경우 그보다 낮은 온도에서 최대 활성을 나타내야할 필요성이 있다. 따라서 이를 위한 촉매물성의 개발이 필요하다.In case of direct decomposition, a condition of high temperature of 850 ° C. or higher is required, but the selective catalytic reduction method has an advantage of effectively removing N 2 O around 500 ° C. through a reducing agent injected. In the case of using a zeolite as a catalyst support, when a catalyst for selective catalytic reduction is introduced at a place where N 2 O is generated in a temperature range of 400 to 450 ° C., it is necessary to exhibit maximum activity at a lower temperature. Therefore, it is necessary to develop the catalytic properties for this.
보통 촉매의 담지체로 사용되는 제올라이트는 합성제올라이트(MFI, MOR, FER, BETA 등)이며, 여기에 주로 철(Fe), 구리(Cu), 코발트(Co), 망간(Mn) 등을 활성물질로 담지시켜 제조해왔다. 특히 제올라이트 촉매는 직접분해보다 선택적 촉매환원 방법을 통해 N₂O를 제거하는데 많이 연구되었으며, 질소계 및 탄화수소계 환원제 주입으로 450℃ 내외의 온도범위에서 N₂O가 효과적으로 분해된다. Zeolites, which are usually used as carriers for catalysts, are synthetic zeolites (MFI, MOR, FER, BETA, etc.), and mainly include iron (Fe), copper (Cu), cobalt (Co), and manganese (Mn) as active materials. It has been prepared by loading. In particular, zeolite catalysts have been studied to remove N₂O through selective catalytic reduction method rather than direct decomposition, and N₂O is effectively decomposed in the temperature range of around 450 ℃ by injection of nitrogen-based and hydrocarbon-based reducing agents.
그러나, 실제 N₂O 발생 사업장에 적용할 경우 제올라이트 촉매는 400℃ 이하의 온도에서 높은 활성을 나타내야 한다. 따라서, 400℃ 이하의 온도에서 최대 활성을 나타내는 촉매의 개발이 시급하다.However, the zeolite catalyst should show high activity at temperatures below 400 ℃ when applied to N2O generating plants. Therefore, it is urgent to develop a catalyst that exhibits maximum activity at a temperature of 400 ° C or lower.
본 발명은 상술한 바와 같은 문제점을 해소하기 위해 안출된 것으로서, 본 발명의 목적은 400℃ 이하의 온도에서 N ₂O를 제거할 수 있는 촉매를 제공하는 것이다. The present invention has been made to solve the problems described above, an object of the present invention is to provide a catalyst that can remove N ₂O at a temperature of 400 ℃ or less.
본 발명은 클리놉틸로라이트형 천연제올라이트 촉매와 달리 모더나이트형 합성제올라이트를 담지체로 하여 촉매를 제조하였을 때, 저온에서도 아산화질소의 제거가 우수함을 발견하여 완성하였다.The present invention was completed by finding that the catalyst was prepared using mordenite-type synthetic zeolite as a carrier, unlike the clinoptilolite-type natural zeolite catalyst.
상술한 목적을 달성하기 위한 본 발명은 모더나이트형 제올라이트 담지체에 전이금속 또는 귀금속 중 어느 하나 이상을 담지하여 제조된 아산화질소 제거용 촉매를 제공한다.The present invention for achieving the above object provides a catalyst for removing nitrous oxide prepared by supporting any one or more of transition metals and precious metals in the mordenite zeolite support.
상기 모더나이트형 제올라이트 담지체는 SiO₂/Al₂O₃비가 13 내지 90인 것이 바람직하다.The mordenite zeolite carrier preferably has a SiO 2 / Al 2 O 3 ratio of 13 to 90.
상기 전이금속은 철(Fe)을 이온교환하여 담지하되, 상기 철은 0.01~10중량%를 포함하는 것이 바람직하다.The transition metal is supported by ion exchange of iron (Fe), the iron preferably comprises 0.01 to 10% by weight.
상기 귀금속은 파라듐(Pd)을 함침법으로 담지하되, 상기 파라듐은 0.01~5.0중량%를 포함하는 것이 바람직하다.The noble metal is supported by the impregnation method of palladium (Pd), the palladium preferably contains 0.01 to 5.0% by weight.
본 발명에 따른 아산화질소 제거용 촉매의 제조방법은 모더나이트형 제올라이트를 준비하여 세척하는 단계와, 상기 모더나이트형 제올라이트를 건조하는 단계와, 전이금속 및 귀금속 중 어느 하나 이상을 상기 모더나이트형 제올라이트에 담지하는 단계 및 상기 모더나이트형 제올라이트를 건조하고 소성하는 단계를 포함하 는 아산화질소 제거용 촉매 제조방법을 제공한다. The method for preparing a nitrous oxide removing catalyst according to the present invention includes preparing and washing a mordenite zeolite, drying the mordenite zeolite, and converting any one or more of the transition metal and the precious metal into the mordenite zeolite. It provides a method for producing a catalyst for removing nitrous oxide comprising the step of supporting and drying and calcining the mordenite zeolite.
한편, 본 발명에 따른 아산화질소 제거방법은 상기와 같은 과정을 통해 제조된 아산화질소 제거용 촉매를 준비하는 단계와, 질소계 및 탄화수소계 환원제를 주입하는 단계 및 상기 모더나이트형 제올라이트 담지체 촉매와 상기 환원제를 사용하여 아산화 질소를 제거하는 단계를 포함하는 아산화질소 제거방법을 제공한다.On the other hand, the nitrous oxide removal method according to the present invention comprises the steps of preparing a catalyst for removing nitrous oxide prepared through the above process, injecting a nitrogen-based and hydrocarbon-based reducing agent and the mordenite-type zeolite carrier catalyst and It provides a nitrous oxide removal method comprising the step of removing nitrous oxide using the reducing agent.
또한, 상기 환원제가 주입되는 온도는 400℃ 이내인 것이 바람직하다.In addition, the temperature at which the reducing agent is injected is preferably within 400 ℃.
그리고, 상기 환원제는 메탄인 것이 바람직하다.And, the reducing agent is preferably methane.
이하에서는 도면을 참조하여 본 발명의 아산화질소 제거용 촉매와, 촉매의 제조방법 및 아산화질소 제거방법을 상세하게 설명한다.Hereinafter, with reference to the drawings will be described in detail the catalyst for removing nitrous oxide, the method for preparing the catalyst and the method for removing nitrous oxide of the present invention.
도 1은 본 발명에 따른 촉매의 제조과정을 도시한 제1실시예이고, 도 2는 본 발명에 따른 촉매의 제조과정을 도시한 제2실시예이며, 도 3은 본 발명에 따른 촉매의 제조과정을 도시한 제3실시예이다.1 is a first embodiment showing a process for producing a catalyst according to the present invention, FIG. 2 is a second embodiment showing a process for preparing a catalyst according to the present invention, and FIG. 3 is a preparation of a catalyst according to the present invention. The third embodiment shows the process.
도 4는 본 발명에 따른 촉매를 이용하여 아산화질소를 제거하는 절차를 도시한 순서도이고, 도 5는 본 발명에 따른 촉매를 이용하여 아산화질소를 제거할 때 온도에 따른 아산화질소의 제거율을 도시한 도면이며, 도 6은 본 발명의 촉매를 이용하여 아산화질소를 제거할 때와 종래의 촉매를 이용하여 아산화질소를 제거할 때의 아산화질소의 제거할 때의 반응온도를 비교하여 도시한 도면이다.Figure 4 is a flow chart illustrating a procedure for removing nitrous oxide using a catalyst according to the present invention, Figure 5 shows the removal rate of nitrous oxide with temperature when removing nitrous oxide using a catalyst according to the present invention. FIG. 6 is a view showing a comparison of reaction temperatures when removing nitrous oxide when removing nitrous oxide using a catalyst of the present invention and removing nitrous oxide when removing nitrous oxide using a conventional catalyst.
이들 도면을 참조하면, 본 발명은 모더나이트형 제올라이트 담지체에 철을 이온교환시킨 후, 파라듐(Pd)이나, 백금(Pt) 또는 루테늄(Ru)을 함침법으로 담지시켜 촉매를 제조하고, 2종의 활성물질이 담지된 촉매와 선택적 촉매환원 방법을 이용하여 아산화질소(N₂O)를 효과적으로 제거하는 것이다. 촉매로는 모더나이트형 제올라이트를 담지체로 하고, 철(Fe)과 같은 전이금속과 파라듐(Pd), 백금(Pt), 루테늄(Ru) 등과 같은 귀금속 2종을 함께 활성물질로 담지하여 촉매로 제조하여 N₂O의 제거활성을 증대시킨 것이다. 이때, 모더나이트형 제올라이트는 SiO₂/Al₂O₃비가 약 13 내지 90 정도이며, 제올라이트의 비표면적은 400~500m²/g 인 것을 사용할 수 있다. 또한, 철은 0.01~10중량%를 포함하며, 파라듐은 0.01~5.0중량%를 포함한다. 그리고, 활성전구체로 사용한 철 및 파라듐은 NO₃- , Cl-, CO3 - 및 SO4 - 로 이루어진 음이온을 포함한다. Referring to these drawings, in the present invention, iron is ion-exchanged on a mordenite-type zeolite carrier, and then a catalyst is prepared by impregnating palladium (Pd), platinum (Pt), or ruthenium (Ru) by impregnation. It is effective to remove nitrous oxide (N₂O) by using a catalyst with two active substances and selective catalytic reduction method. As a catalyst, mordenite-type zeolite is supported, and a transition metal such as iron (Fe) and two precious metals such as palladium (Pd), platinum (Pt), ruthenium (Ru), etc. are supported as an active material. It is to increase the removal activity of N₂O. In this case, the mordenite zeolite may have a SiO 2 / Al 2 O 3 ratio of about 13 to about 90, and a specific surface area of the zeolite may be 400 to 500 m 2 / g. In addition, iron contains 0.01 to 10% by weight, and palladium includes 0.01 to 5.0% by weight. And, iron and palladium used as an active precursor NO₃ - comprises an anion consisting of -, Cl -, CO 3 - and SO 4.
[제1실시예][First Embodiment]
본 발명에 따른 아산화질소 제거용 촉매제조방법의 제1실시예는 도 1에 도시된 바와 같이, 산업적으로 입수 가능한 모더나이트형 제올라이트를 준비하여 3회이상 세척하고 건조하는 단계(S100,S110,S120)와, 모더나이트형 제올라이트에 철을 담지하기 위한 이온교환단계(S130)와, 건조/소성 단계(S140,S150)로 이루어진다.A first embodiment of the method for preparing a nitrous oxide removal catalyst according to the present invention, as shown in Figure 1, preparing an industrially available mordenite zeolite three times or more washing and drying step (S100, S110, S120) And an ion exchange step (S130) for supporting iron in the mordenite zeolite, and a drying / firing step (S140 and S150).
도 1을 참조하면, 먼저 모더나이트형 제올라이트는 1차로 증류한 증류수를 이온교환필터나 중공사막필터 등을 통과한 3차 증류수로 적어도 3회이상 세척 후 건조하여 준비한다. (S100,S110,S120)Referring to FIG. 1, first, mordenite zeolite is first prepared by washing distilled water distilled first with tertiary distilled water passed through an ion exchange filter or a hollow fiber membrane filter, and drying at least three times. (S100, S110, S120)
그리고, 전이금속인 철의 이온교환을 위해 0.01~10 중량%정도의 철을 70~80℃의 온도에서 적어도 4시간 동안 모더나이트형 제올나이트에 담지시킨다.(S130)And, in order to ion exchange iron, which is a transition metal, about 0.01 to 10% by weight of iron is supported on mordenite zeolite for at least 4 hours at a temperature of 70 to 80 ° C. (S130)
그 후, 모더나이트형 제올나이트는 105~115℃ 정도의 온도에서 12시간 이상 건조하고, 500℃ 이상에서 4시간 이상 소성하여 Fe-MOR 촉매를 제조한다.(S140,S150)Thereafter, mordenite zeolite is dried at a temperature of about 105 to 115 ° C for at least 12 hours, and calcined at 500 ° C or more for 4 hours to produce a Fe-MOR catalyst. (S140, S150)
이때, 전이 금속 활성물질의 전구체로서 철은 NO₃- , Cl-, CO3 - 및 SO4 - 로 이루어진 음이온을 포함한다. At this time, as a precursor of a transition metal active material it is iron NO₃ - comprises an anion consisting of -, Cl -, CO 3 - and SO 4.
[제2실시예]Second Embodiment
본 발명에 따른 아산화질소 제거용 촉매제조방법의 제2실시예는 도 2에 도시된 바와 같이, 모더나이트형 제올라이트를 준비하여 3회이상 세척하고 건조하는 단계(S200,S210,S220)와, 모더나이트형 제올라이트에 철을 함침하는 단계(S230)와, 건조/소성 단계(S240,S250)로 이루어진다.A second embodiment of the method for preparing a catalyst for removing nitrous oxide according to the present invention includes preparing a mordenite zeolite, washing and drying three or more times (S200, S210, and S220) as shown in FIG. Impregnating iron into the zeolite (S230), and drying / baking step (S240, S250) consists of.
도 2를 참조하면, 먼저 모더나이트형 제올라이트는 3차 증류수로 3회이상 세척 후 건조하여 준비한다. (S200,S210,S220)Referring to Figure 2, first mordenite zeolite is prepared by washing after three or more times with tertiary distilled water and dried. (S200, S210, S220)
다음, 회전증발기(Rotary evaporator)를 이용하여 모더나이트형 제올라이트에 귀금속 전구체인 파라듐이 0.01~5.0중량%를 포함되도록 함침법으로 담지한 후, 물을 증발시켜 건조하고 소성하여 Pd-MOR 촉매를 제조한다.(S230,S240,S250)Next, by impregnating the mordenite zeolite using a rotary evaporator so that the noble metal precursor, palladium, is 0.01 to 5.0% by weight, is dried, calcined, and evaporated to form a Pd-MOR catalyst. (S230, S240, S250)
이때, 활성물질의 전구체로서 파라듐은 NO₃- , Cl-, CO3 - 및 SO4 - 로 이루어진 음이온을 포함한다. At this time, as a precursor of the active material it is palladium NO₃ - comprises an anion consisting of -, Cl -, CO 3 - and SO 4.
제2실시예에서는 제1실시예와 동일한 조건에서 이온교환과정 대신 귀금속의 함침을 진행함으로써 제조과정을 변화시킨 것이다.In the second embodiment, the manufacturing process is changed by impregnating the noble metal instead of the ion exchange process under the same conditions as in the first embodiment.
[제3실시예]Third Embodiment
본 발명에 따른 아산화질소 제거용 촉매제조방법의 제3실시예는 도 3에 도시된 바와 같이, 모더나이트형 제올라이트를 준비하는 단계(S310,S320,S330)와, 모더나이트형 제올라이트에 철을 담지하기 위한 이온교환단계(S330)와, 건조 후, 철이 담지된 모더나이트형 제올라이트에 귀금속을 담지하기 위한 함침단계(S340,S350) 및 건조/소성단계(S360,S370)로 이루어진다.According to a third embodiment of the method for preparing a nitrous oxide removal catalyst according to the present invention, as shown in FIG. 3, a step of preparing mordenite zeolite (S310, S320, S330) and supporting iron on mordenite zeolite After the ion exchange step (S330), and after drying, the impregnation step (S340, S350) and the drying / baking step (S360, S370) for supporting the precious metal in the mordenite-type zeolite loaded with iron.
도 3을 참조하면, 먼저 모더나이트형 제올라이트는 3차 증류수에 적어도 3회 세척한 후 건조하여 준비한다.(S300,S310,S320)Referring to Figure 3, first mordenite zeolite is prepared by washing at least three times in tertiary distilled water and then dried. (S300, S310, S320)
전이금속인 철의 이온교환을 위해 0.01~10 중량%정도의 철을 70~80℃의 온도에서 적어도 4시간 동안 모더나이트형 제올나이트에 담지시킨다.(S330)For ion exchange of iron, a transition metal, about 0.01 to 10% by weight of iron is supported on mordenite zeolite for at least 4 hours at a temperature of 70 to 80 ° C. (S330)
그 후, 모더나이트형 제올나이트는 105~115℃ 정도의 온도에서 12시간 이상 건조한다.(S340)After that, the mordenite zeolite is dried for 12 hours or more at a temperature of about 105 to 115 ° C. (S340)
다음, 앞서 철이 담지된 모더나이트형 제올라이트에 회전증발기(Rotary evaporator)를 이용하여 파라듐을 함침법으로 담지한 후, 105~115℃ 정도의 온도에서 12시간 이상 건조하고, 500℃ 이상에서 4시간 이상 소성하여 Pd-Fe-MOR 촉매를 제조한다.(S350,S360,S370)Next, the iron-supported mordenite zeolite was impregnated with palladium using a rotary evaporator, and then dried at a temperature of about 105 to 115 ° C. for at least 12 hours, and at 500 ° C. or higher for 4 hours. The above baking was performed to prepare Pd-Fe-MOR catalyst. (S350, S360, S370)
이때, 활성물질의 전구체로서 철과 파라듐은 NO₃- , Cl-, CO3 - 및 SO4 - 로 이루어진 음이온을 포함한다. At this time, iron and palladium as a precursor of the active material NO₃ - comprises an anion consisting of -, Cl -, CO 3 - and SO 4.
이와 같이 제3실시예에서는 제1실시예 및 제2실시예와 동일한 조건에서 이온교환과정과 귀금속의 함침을 모두 실시하도록 제조과정을 변화시킨 것이다.As described above, in the third embodiment, the manufacturing process is changed to perform both the ion exchange process and the impregnation of the noble metal under the same conditions as the first and second embodiments.
[아산화질소 제거방법][How to remove nitrous oxide]
위와 같이 본 발명에 따라 제조된 모더나이트형 제올라이트 담지체 촉매를 이용하여 선택적 촉매 환원방법으로 아산화질소(N2O)를제거하는 절차는 도 4에 도시된 바와 같이, 3차증류수에 적어도 3회이상 세척하고, 건조하여 모더나이트형 제올라이트를 준비하여, 전이금속인 철을 담지하고 건조/소성하여 모더나이트형 제올라이트 담지체 촉매를 준비하는 단계(S400) 그리고, 준비된 모더나이트형 제올라이트 담지체 촉매와 환원제를 사용하여 아산화질소를 제거하는 단계(S410)를 포함하여 이루어진다. 이때, 선택적 촉매환원 반응을 위해 주입하는 환원제로는 질소계 및 탄화수소계(CH4, NH3, C3H8 등) 환원제를 사용할 수 있다.As described above, the procedure for removing nitrous oxide (N 2 O) by a selective catalytic reduction method using a mordenite-type zeolite carrier catalyst prepared according to the present invention as shown in FIG. 4 is performed at least three times in tertiary distilled water. Preparing a mordenite zeolite by washing and drying to prepare a mordenite zeolite, and preparing a mordenite zeolite carrier catalyst by supporting iron, which is a transition metal, and drying / firing (S400); and a prepared mordenite zeolite carrier catalyst and a reducing agent It comprises a step (S410) to remove the nitrous oxide using. At this time, the reducing agent to be injected for the selective catalytic reduction reaction is nitrogen-based and hydrocarbon-based (CH 4 , NH 3 , C 3 H 8 Etc.) a reducing agent can be used.
[ 비교예 ]Comparative Example
모더나이트형 제올라이트에 각각 철과 파라듐을 각각 담지하거나 함침한 Fe-MOR 촉매와, Pd-MOR 촉매 그리고, 철과 파라듐 2종의 금속을 담지한 Pd-Fe-MOR 촉매에 대해 아산화질소의 제거율을 실험하였다.Nitrogen oxides were added to the Fe-MOR catalyst supporting or impregnating iron and palladium, respectively, to the mordenite zeolite, the Pd-MOR catalyst, and the Pd-Fe-MOR catalyst supporting iron and palladium two kinds of metals. The removal rate was tested.
모더나이트형 제올라이트, 철, 파라듐 등의 시약과 촉매 제조장치(이온교환, 함침) 및 활성실험 반응장치(가스주입장치, 반응기, 가스분석장치)를 준비한다.Reagents such as mordenite zeolite, iron, and palladium, a catalyst manufacturing device (ion exchange and impregnation), and an active experimental reaction device (gas injection device, reactor, gas analyzer) are prepared.
실험은 공간속도를 5,000~20,000/hr, O2의 농도를 0.5~2%로 맞추어 실험하였으며, 반응가스를 기체유량계를 통해 일정농도로 맞춰 주입하였다. 또한, 선택적 촉매환원 반응을 위해 주입하는 환원제로는 질소계 및 탄화수소계(CH4, NH3, C3H8 등)를 사용하였다. 특히 본 발명에서는 메탄이 환원제로 사용되며 환원제의 농도는 반응가스인 아산화질소와 몰비(Mole ratio)를 1:1로 맞추어 주입하였다.The experiment was conducted by adjusting the space velocity to 5,000 ~ 20,000 / hr and the concentration of O 2 to 0.5 ~ 2%. The reaction gas was injected at a constant concentration through a gas flow meter. In addition, the reducing agent injected for the selective catalytic reduction reaction is nitrogen-based and hydrocarbon-based (CH 4 , NH 3 , C 3 H 8 Etc.) were used. In particular, in the present invention, methane is used as a reducing agent, and the concentration of the reducing agent is injected in a ratio of 1: 1 with nitrous oxide, which is a reaction gas, and a mole ratio.
도 5는 모더나이트형 제올라이트 담지체에 철을 담지한 Fe-MOR 촉매와, 모더나이트형 제올라이트 담지체에 파라듐을 함침한 Pd-MOR 촉매 그리고, 모더나이트형 제올라이트 담지체에 철을 담지하고, 파라듐을 함침한 Pd-Fe-MOR 촉매의 아산화질소 제거 활성을 비교한 결과로, 반응온도가 350℃인 조건에서 아산화질소의 제거율은 각각 35,40,85%로 조사되었다. 5 is a Fe-MOR catalyst in which iron is supported on a mordenite zeolite support, a Pd-MOR catalyst in which palladium is impregnated in a mordenite zeolite support, and iron is supported on a mordenite zeolite support, As a result of comparing the nitrous oxide removal activity of the Pd-Fe-MOR catalyst impregnated with palladium, the removal rate of nitrous oxide was found to be 35, 40 and 85%, respectively, at a reaction temperature of 350 ° C.
따라서, 반응온도가 350℃인 조건에서 아산화질소의 제거가 가능하며, 특히 Pd-Fe-MOR 촉매의 활성이 월등히 증대되는 것을 알 수 있다.Therefore, it can be seen that nitrous oxide can be removed under the reaction temperature of 350 ° C., and in particular, the activity of the Pd-Fe-MOR catalyst is greatly increased.
일반적으로 촉매는 활성물질을 여러개 주입하거나, 양을 많이 넣어 제조한다고 해서 활성이 증대되는 것은 아니다. 그러나, 본 발명자의 실험 결과에 따르면, 전이 금속과 귀금속을 동시에 담지한 촉매의 경우, 이들 1개씩 담지한 촉매보다 350℃의 저온에서 촉매 활성이 월등함을 발견하였다.Generally, catalysts are prepared by injecting a large number of active materials or by adding a large amount of the active substance. However, according to the experimental results of the present inventors, it was found that in the case of a catalyst supporting both a transition metal and a noble metal at the same time, the catalytic activity was superior at a low temperature of 350 ° C. over the catalysts carrying one by one.
도 6은 온도에 따라 천연 제올라이트 담지체에 철과 파라듐을 담지한 촉매에 의한 아산화질소 제거량과, 도 5에 도시된 바와 같이 모더나이트형 제올라이트 담지체에 철과 파라듐을 담지한 촉매에 의한 아산화질소 제거량을 비교하여 도시한 도면으로서, 천연 제올라이트 담지체에 철과 파라듐을 담지한 촉매는 높은 온도 즉, 350~500℃에서 모더나이트형 제올라이트 촉매와 유사한 아산화질소 제거율을 기대할 수 있음을 알 수 있다.6 is a nitrous oxide removal amount by a catalyst supporting iron and palladium on a natural zeolite support according to the temperature, and as shown in FIG. 5 by a catalyst supporting iron and palladium on a mordenite zeolite support As a drawing showing the comparison of nitrous oxide removal amount, it can be seen that a catalyst carrying iron and palladium on a natural zeolite support can expect nitrous oxide removal rate similar to that of a mordenite zeolite catalyst at high temperature, that is, 350 to 500 ° C. Can be.
상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술분야의 숙련된 당업자는 하기의 특허청구범위에 기재된 본 발명이 사상 및 영역으로부터 벗어나지 않은 범위내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.While the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art will be able to variously modify and change the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated.
이상에서 설명한 바와 같이, 본 발명의 모더나이트형 제올라이트 담지체 촉매는 350℃정도의 온도에서 아산화질소를 제거율을 증대할 수 있는 이점이 있다.As described above, the mordenite zeolite carrier catalyst of the present invention has an advantage of increasing the removal rate of nitrous oxide at a temperature of about 350 ° C.
또한, 아산화질소를 제거할 수 있는 반응온도를 낮출 수 있으므로 각종 연소 산업설비의 에너지가 절감될 수 있는 이점이 있다.In addition, since the reaction temperature to remove the nitrous oxide can be lowered, there is an advantage that the energy of various combustion industrial equipment can be reduced.
Claims (14)
Priority Applications (1)
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06154611A (en) * | 1992-07-03 | 1994-06-03 | Sakai Chem Ind Co Ltd | Catalyst for decomposition of nitrous oxide |
KR960000013B1 (en) * | 1992-08-13 | 1996-01-03 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Catalytic reduction of nox and carbon monoxide using methane in the presence of oxyen |
JPH09884A (en) * | 1995-06-16 | 1997-01-07 | Babcock Hitachi Kk | Method and device for removing nitrous oxide or the like in exhaust gas and catalyst |
KR20050081767A (en) * | 2004-02-16 | 2005-08-19 | 한국과학기술원 | Dual functional catalyst system performing reaction of adsorbent and catalyst of voc |
KR20070088335A (en) * | 2006-02-24 | 2007-08-29 | 프라임 뷰 인터내셔널 코오포레이션 리미티드 | Thin film transistor array substrate and electronic ink display device |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06154611A (en) * | 1992-07-03 | 1994-06-03 | Sakai Chem Ind Co Ltd | Catalyst for decomposition of nitrous oxide |
KR960000013B1 (en) * | 1992-08-13 | 1996-01-03 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Catalytic reduction of nox and carbon monoxide using methane in the presence of oxyen |
JPH09884A (en) * | 1995-06-16 | 1997-01-07 | Babcock Hitachi Kk | Method and device for removing nitrous oxide or the like in exhaust gas and catalyst |
KR20050081767A (en) * | 2004-02-16 | 2005-08-19 | 한국과학기술원 | Dual functional catalyst system performing reaction of adsorbent and catalyst of voc |
KR20070088335A (en) * | 2006-02-24 | 2007-08-29 | 프라임 뷰 인터내셔널 코오포레이션 리미티드 | Thin film transistor array substrate and electronic ink display device |
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