KR20220075530A - A Catalyst for dehydrogenation of liquid organic hydrogen carriers and method for producing the same - Google Patents
A Catalyst for dehydrogenation of liquid organic hydrogen carriers and method for producing the same Download PDFInfo
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- KR20220075530A KR20220075530A KR1020200163686A KR20200163686A KR20220075530A KR 20220075530 A KR20220075530 A KR 20220075530A KR 1020200163686 A KR1020200163686 A KR 1020200163686A KR 20200163686 A KR20200163686 A KR 20200163686A KR 20220075530 A KR20220075530 A KR 20220075530A
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- South Korea
- Prior art keywords
- catalyst
- dehydrogenation
- lohc
- liquid organic
- organic hydrogen
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 239000001257 hydrogen Substances 0.000 title claims abstract description 118
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 118
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- 239000007788 liquid Substances 0.000 title claims abstract description 71
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 60
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- FUUPYXUBNPJSOA-UHFFFAOYSA-N 9-ethyl-1,2,3,4,4a,4b,5,6,7,8,8a,9a-dodecahydrocarbazole Chemical compound C12CCCCC2N(CC)C2C1CCCC2 FUUPYXUBNPJSOA-UHFFFAOYSA-N 0.000 claims description 5
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
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- Catalysts (AREA)
Abstract
본 발명은 액상유기수소운반체 탈수소화용 촉매 및 이의 제조방법에 관한 것으로써, 본 발명에 따라 제조된 액상유기수소운반체(LOHC) 탈수소화용 촉매는 분자량이 상대적으로 큰 액상유기수소운반체(LOHC)에 사용됨에도 불구하고, 상기 촉매에 포함되는 지지체는 내부기공인 메조기공을 복수로 포함하고 있어 지지체의 표면적이 매우 넓어 촉매금속이 상기 지지체 상에 고르게 분포할 수 있으므로, 촉매금속 간에 엉김현상(sintering)이 억제되는 바, 기존 촉매에 비해 적은 양의 활성금속으로도 우수한 촉매 활성이 안정적으로 유지되면서도 수소 전환율이 높아 수소 생산의 효율을 크게 향상시킬 수 있다.The present invention relates to a catalyst for dehydrogenation of a liquid organic hydrogen carrier and a method for preparing the same, and the catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) prepared according to the present invention is used in a liquid organic hydrogen carrier (LOHC) having a relatively large molecular weight In spite of this, since the support included in the catalyst includes a plurality of mesopores, which are internal pores, the surface area of the support is very wide so that the catalyst metal can be evenly distributed on the support, so that sintering between the catalyst metals As a result, the efficiency of hydrogen production can be greatly improved due to the high hydrogen conversion rate while stably maintaining excellent catalytic activity even with a small amount of active metal compared to the conventional catalyst.
Description
본 발명은 액상유기수소운반체 탈수소화용 촉매 및 이의 제조방법에 관한 것이다.The present invention relates to a catalyst for dehydrogenation of a liquid organic hydrogen carrier and a method for preparing the same.
화석 에너지의 고갈 및 환경오염 문제로 인하여 화석 연료를 대체할 수 있는 신재생 대체 에너지에 대한 요구가 크며, 그러한 대체 에너지의 하나로서 수소가 주목받고 있다.Due to the depletion of fossil energy and environmental pollution problems, there is a great demand for new and renewable alternative energy that can replace fossil fuels, and hydrogen is attracting attention as one of such alternative energy.
연료전지와 수소연소장치는 수소를 반응 가스로 사용하고 있는데, 연료전지와 수소연소장치를 예컨대 자동차나 각종 전자 제품 등에 응용하기 위하여 수소의 안정적이고 지속적인 공급 내지 저장 기술이 필요하다. Fuel cells and hydrogen combustion devices use hydrogen as a reactive gas. In order to apply fuel cells and hydrogen combustion devices to automobiles and various electronic products, for example, a stable and continuous supply or storage technology of hydrogen is required.
수소를 이용하는 장치에 수소를 공급하기 위하여 별도로 설치된 수소 공급소로부터 수소가 필요할 때마다 수소를 공급받는 방식을 사용할 수 있다. 이러한 방식에서는 수소 저장을 위하여 압축 수소나 액화 수소를 사용할 수 있다.In order to supply hydrogen to a device using hydrogen, a method in which hydrogen is supplied whenever hydrogen is needed from a separately installed hydrogen supply station may be used. In this way, compressed hydrogen or liquid hydrogen can be used for hydrogen storage.
또는, 수소를 저장하고 발생시키는 물질을 수소 이용 장치에 탑재한 후 해당 물질의 반응을 통하여 수소를 발생시키고 이를 수소 이용 장치에 공급하는 방식을 사용할 수 있다. 이 방식에는 예컨대, 금속수소화물(metal hydride) 이용 방법, 흡착, 탈착/탄소(absorbents/carbon) 이용 방법, 화학적 방법(chemical hydrogen storage) 등이 제안되고 있다.Alternatively, a method may be used in which a material for storing and generating hydrogen is loaded in a hydrogen-using device, then hydrogen is generated through a reaction of the material and supplied to the hydrogen-using device. For this method, for example, a method using metal hydride, a method using adsorption, desorption/carbon, and a chemical hydrogen storage have been proposed.
이러한 수소 발생 물질로서 예컨대 암모니아 보란, 실란화합물, 개미산, 암모니아 등과 같은 다양한 화학수소화물을 이용한 수소저장기술이 연구되고 있고, 최근에는 액상유기수소운반체(Liquid organic hydrogen carrier; LOHC)를 이용하여 액상으로 수소를 저장하는 기술이 연구 되고 있다.As such a hydrogen generating material, hydrogen storage technology using various chemical hydrides such as ammonia borane, silane compound, formic acid, ammonia, etc. are being studied, and recently, liquid organic hydrogen carrier (LOHC) is used to convert it into a liquid phase. A technology for storing hydrogen is being researched.
다만, 현재 위와 같은 수소를 저장할 수 있는 물질, 또는 이의 탈수소화 반응의 촉매로써 담지된 촉매금속은 연구되었지만, 촉매금속이 지지체 중에 잘 분산되지 않고, 촉매활성이 저조하는 등 개선의 여지가 많았다.However, currently, a material capable of storing hydrogen as described above, or a catalyst metal supported as a catalyst for its dehydrogenation reaction has been studied, but there was a lot of room for improvement, such as the catalyst metal is not well dispersed in the support and the catalytic activity is low.
본 발명은 위와 같은 문제점을 해결하기 위한 것으로서, 그 구체적인 목적은 다음과 같다.The present invention is intended to solve the above problems, and the specific objects thereof are as follows.
본 발명은 3차원 골격을 갖고, 상기 골격에 의해 형성된 메조기공을 복수로 포함하는 지지체 상에 담지된 촉매금속을 포함하는 액상유기수소운반체(LOHC) 탈수소화용 촉매 및 이의 제조방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) comprising a catalyst metal supported on a support having a three-dimensional skeleton and including a plurality of mesopores formed by the skeleton, and a method for preparing the same do it with
본 발명의 목적은 이상에서 언급한 목적으로 제한되지 않는다. 본 발명의 목적은 이하의 설명으로 보다 분명해 질 것이며, 특허청구범위에 기재된 수단 및 그 조합으로 실현될 것이다.The object of the present invention is not limited to the object mentioned above. The object of the present invention will become clearer from the following description, and will be realized by means and combinations thereof described in the claims.
본 발명의 일 실시예에 따른 액상유기수소운반체(Liquid organic hydrogen carrier; LOHC) 탈수소화용 촉매는 3차원 골격을 갖고, 상기 골격에 의해 형성된 메조기공을 복수로 포함하는 지지체; 및 상기 지지체 상에 담지된 촉매금속;을 포함한다.A catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) according to an embodiment of the present invention includes a support having a three-dimensional skeleton and including a plurality of mesopores formed by the skeleton; and a catalyst metal supported on the support.
상기 지지체는 TiO2, SiO2, ZrO2, Al203, SnO2, Ta2O5, HfO2, La2O3, V2O5, CeO2, Fe2O3, Cr2O3, MoO3, ZnO, MgO, 및 WO3 로 이루어진 군에서 선택된 1종 이상의 산화물을 포함할 수 있다.The support is TiO 2 , SiO 2 , ZrO 2 , Al 2 O 3 , SnO 2 , Ta 2 O 5 , HfO 2 , La 2 O 3 , V 2 O 5 , CeO 2 , Fe 2 O 3 , Cr 2 O 3 , MoO 3 , ZnO, MgO, and WO 3 It may include at least one oxide selected from the group consisting of.
상기 지지체는 KIT(Korea Advanced Institute of Sience and Technology, KAIST) 계열, MCM(Mobil Composition of Matter) 계열, SBA(Santa Babara Amorphous) 계열, AMS (Anionic-surfactant-templated mesoporous silica)계열, FSM (Folded sheets mechanism) 계열, FDU (Fudan University) 계열, KSW (Kagami memorial lab, Materials Science and Technology, Waseda University) 계열, CMI (Chimie des Materiaux Inorganiques) 계열, IBN (Institute of Bioengineering and Nanotechnology) 계열, MSU (Michigan State University) 계열, TUD (Delft University of Technology) 계열, 및 HMS(Hexagonal Mesoporous Silica) 계열로 이루어진 군으로부터 선택되는 1종 이상의 계열일 수 있다.The support is KIT (Korea Advanced Institute of Sience and Technology, KAIST) series, MCM (Mobil Composition of Matter) series, SBA (Santa Babara Amorphous) series, AMS (Anionic-surfactant-templated mesoporous silica) series, FSM (Folded sheets) mechanism), FDU (Fudan University), KSW (Kagami memorial lab, Materials Science and Technology, Waseda University), CMI (Chimie des Materiaux Inorganiques), IBN (Institute of Bioengineering and Nanotechnology), MSU (Michigan State) University) series, TUD (Delft University of Technology) series, and HMS (Hexagonal Mesoporous Silica) series may be at least one selected from the group consisting of series.
상기 지지체는 KIT-6일 수 있다.The support may be KIT-6.
상기 메조기공의 직경은 4 ~ 11nm 일 수 있다.The diameter of the mesopores may be 4 to 11 nm.
상기 지지체의 표면적은 600~850m2/g일 수 있다.The surface area of the support may be 600 ~ 850 m 2 /g.
상기 지지체에 포함된 복수의 메조기공의 기공부피는 0.5~1.5cm3/g일 수 있다.The pore volume of the plurality of mesopores included in the support may be 0.5 to 1.5 cm 3 /g.
상기 촉매금속은 레늄(Re), 주석(Sn), 망간(Mn), 아연(Zn), 마그네슘(Mg), 바나듐(V), 세륨(Ce), 란다넘(La), 이트륨(Y), 사마륨(Sm), 가돌리늄(Gd), 나트륨(Na), 칼륨(K), 세슘(Cs), 루비늄(Rb), 루테늄(Ru), 니켈(Ni), 로듐(Rh), 이리듐(Ir), 코발트(Co), 철(Fe), 백금(Pt), 크롬(Cr), 팔라듐(Pd) 및 구리(Cu)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The catalyst metal is rhenium (Re), tin (Sn), manganese (Mn), zinc (Zn), magnesium (Mg), vanadium (V), cerium (Ce), randanium (La), yttrium (Y), Samarium (Sm), gadolinium (Gd), sodium (Na), potassium (K), cesium (Cs), rubinium (Rb), ruthenium (Ru), nickel (Ni), rhodium (Rh), iridium (Ir) , cobalt (Co), iron (Fe), platinum (Pt), chromium (Cr), palladium (Pd), and may include at least one selected from the group consisting of copper (Cu).
상기 촉매금속은 탈수소화용 촉매 전체 중량을 기준으로 0.5~10중량%의 함량으로 담지될 수 있다.The catalyst metal may be supported in an amount of 0.5 to 10% by weight based on the total weight of the catalyst for dehydrogenation.
상기 액상유기수소운반체(LOHC)는 메틸사이클로헥산(Methylcylohexane; MCH), 퍼하이드로-벤질톨루엔 (Perhydro-benzyltoluene), 퍼하이드로-디벤질톨루엔(Perhydro-dibenzyltoluene), 바이사이클로헥실-디사이클로헥실 메탄(Bicyclohexyl-Dicyclohexyl methane), 사이클로헥산(Cyclohexane), 데칼린(Decalin), 4-아미노-피퍼리딘(4-amino-piperidine), 2-메틸퍼하이드로린돌(2-methylperhydrolindole), N-메틸퍼하이드로린돌(N-methylperhydrolindole), 및 도데카하이드로-N-에틸카바졸(Dodecahydro-N-ethylcarbazole)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The liquid organic hydrogen carrier (LOHC) is methylcyclohexane (Methylcylohexane; MCH), perhydro-benzyltoluene (Perhydro-benzyltoluene), perhydro-dibenzyltoluene (Perhydro-dibenzyltoluene), bicyclohexyl-dicyclohexyl methane ( Bicyclohexyl-Dicyclohexyl methane), cyclohexane, decalin, 4-amino-piperidine, 2-methylperhydrolindole, N-methylperhydrolindole ( N-methylperhydrolindole), and dodecahydro-N-ethylcarbazole (Dodecahydro-N-ethylcarbazole) may include at least one selected from the group consisting of.
본 발명의 일 실시예에 따른 액상유기수소운반체(Liquid organic hydrogen carrier; LOHC) 탈수소화용 촉매 제조방법은 3차원 골격을 갖고, 상기 골격에 의해 형성된 메조기공을 복수로 포함하는 지지체에 촉매금속 전구체 용액을 함침시키는 단계; 및 함침된 결과물을 건조시켜 상기 지지체 상에 촉매금속이 담지된 촉매를 얻는 단계;를 포함한다.The method for preparing a catalyst for liquid organic hydrogen carrier (LOHC) dehydrogenation according to an embodiment of the present invention is a catalyst metal precursor solution on a support having a three-dimensional skeleton and including a plurality of mesopores formed by the skeleton impregnating the and drying the impregnated product to obtain a catalyst having a catalyst metal supported thereon on the support.
상기 함침된 결과물을 80~120℃의 온도에서 12~24시간 동안 건조시킬 수 있다.The impregnated product may be dried at a temperature of 80 to 120° C. for 12 to 24 hours.
본 발명에 따라 제조된 액상유기수소운반체(LOHC) 탈수소화용 촉매는 분자량이 상대적으로 큰 액상유기수소운반체(LOHC)에 사용됨에도 불구하고, 상기 촉매에 포함되는 지지체는 내부기공인 메조기공을 복수로 포함하고 있어 지지체의 표면적이 매우 넓어 촉매금속이 상기 지지체 상에 고르게 분포할 수 있으므로, 촉매금속 간에 엉김현상(sintering)이 억제되는 바, 기존 촉매에 비해 적은 양의 활성금속으로도 우수한 촉매 활성이 안정적으로 유지되면서도 LOHC 전환율이 높아 수소 생산의 효율을 크게 향상시킬 수 있다.Although the catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) prepared according to the present invention is used for a liquid organic hydrogen carrier (LOHC) having a relatively large molecular weight, the support included in the catalyst has a plurality of mesopores, which are internal pores. Since the surface area of the support is very wide and the catalyst metal can be evenly distributed on the support, sintering between catalyst metals is suppressed. While maintaining stable, the LOHC conversion rate is high, which can greatly improve the efficiency of hydrogen production.
본 발명의 효과는 이상에서 언급한 효과로 한정되지 않는다. 본 발명의 효과는 이하의 설명에서 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 할 것이다.The effects of the present invention are not limited to the above-mentioned effects. It should be understood that the effects of the present invention include all effects that can be inferred from the following description.
도 1은 실시예 1에 따라 제조한 액상유기수소운반체(LOHC) 탈수소화용 촉매의 반응온도에 따른 액상유기수소운반체(LOHC)의 전환율 및 이에 따른 수소생성속도(공간속도를 고정)를 측정한 결과를 나타낸 그래프이다.
도 2a 및 도 2b는 실시예 1에 따라 제조한 액상유기수소운반체(LOHC) 탈수소화용 촉매의 공간속도에 따른 액상유기수소운반체(LOHC)의 전환율 및 이에 따른 수소생성속도(반응온도를 300℃로 고정한 것은 도 2a, 반응온도를 340℃로 고정한 것은 도 2b)를 측정한 결과를 나타낸 그래프이다.
도 3은 실시예 2에 따라 제조한 액상유기수소운반체(LOHC) 탈수소화용 촉매의 반응온도에 따른 액상유기수소운반체(LOHC)의 전환율 및 이에 따른 수소생성속도(공간속도를 고정)를 측정한 결과를 나타낸 그래프이다.
도 4a 및 도 4b는 실시예 2에 따라 제조한 액상유기수소운반체(LOHC) 탈수소화용 촉매의 공간속도에 따른 액상유기수소운반체(LOHC)의 전환율 및 이에 따른 수소생성속도(반응온도를 300℃로 고정한 것은 도 2a, 반응온도를 340℃로 고정한 것은 도 2b)를 측정한 결과를 나타낸 그래프이다.
도 5는 실시예 1에 따라 제조한 액상유기수소운반체(LOHC) 탈수소화용 촉매에서 공간속도와 반응온도를 고정한 채 촉매 사용시간을 늘려 촉매내구성을 평가한 결과를 나타낸 그래프이다.
도 6은 실시예 2에 따라 제조한 액상유기수소운반체(LOHC) 탈수소화용 촉매에서 공간속도와 반응온도를 고정한 채 촉매 사용시간을 늘려 촉매내구성을 평가한 결과를 나타낸 그래프이다.
도 7은 실시예 1, 실시예 2 및 비교예에 따라 제조한 액상유기수소운반체(LOHC) 탈수소화용 촉매의 반응온도에 따른 액상유기수소운반체(LOHC)의 전환율(공간속도를 고정)을 각각 측정한 결과를 비교한 그래프이다.
도 8a 및 도 8b는 실시예 1, 실시예 2 및 비교예에 따라 제조한 액상유기수소운반체(LOHC) 탈수소화용 촉매의 공간속도에 따른 액상유기수소운반체(LOHC)의 전환율(반응온도를 300℃로 고정한 것은 도 8a, 340℃로 고정한 것은 도 8b)을 각각 측정한 결과를 비교한 그래프이다.1 is a result of measuring the conversion rate of a liquid organic hydrogen carrier (LOHC) according to the reaction temperature of a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) prepared according to Example 1 and the hydrogen production rate (space speed is fixed) accordingly is a graph showing
2a and 2b show the conversion rate of the liquid organic hydrogen carrier (LOHC) according to the space velocity of the catalyst for dehydrogenation of the liquid organic hydrogen carrier (LOHC) prepared according to Example 1 and the hydrogen production rate (reaction temperature of 300° C.) The fixed one is a graph showing the measurement result of FIG. 2A, and the fixed one is FIG. 2B) with the reaction temperature fixed at 340°C.
3 is a result of measuring the conversion rate of the liquid organic hydrogen carrier (LOHC) according to the reaction temperature of the catalyst for dehydrogenation of the liquid organic hydrogen carrier (LOHC) prepared according to Example 2 and the hydrogen production rate (space speed is fixed) accordingly is a graph showing
4a and 4b show the conversion rate of the liquid organic hydrogen carrier (LOHC) according to the space velocity of the catalyst for dehydrogenation of the liquid organic hydrogen carrier (LOHC) prepared according to Example 2 and the hydrogen production rate accordingly (reaction temperature was set to 300 ° C.) The fixed one is a graph showing the measurement result of FIG. 2A, and the fixed one is FIG. 2B) with the reaction temperature fixed at 340°C.
5 is a graph showing the results of evaluating catalyst durability by increasing the catalyst usage time while fixing the space velocity and the reaction temperature in the liquid organic hydrogen carrier (LOHC) dehydrogenation catalyst prepared according to Example 1. FIG.
6 is a graph showing the results of evaluating the catalyst durability by increasing the catalyst usage time while fixing the space velocity and the reaction temperature in the liquid organic hydrogen carrier (LOHC) dehydrogenation catalyst prepared according to Example 2.
7 shows the conversion rate (space velocity fixed) of the liquid organic hydrogen carrier (LOHC) according to the reaction temperature of the catalyst for dehydrogenation of the liquid organic hydrogen carrier (LOHC) prepared according to Examples 1, 2 and Comparative Examples, respectively. This is a graph comparing the results.
8A and 8B show the conversion rate (reaction temperature of 300 ° C. It is a graph comparing the measurement results of Fig. 8a, fixed at 340°C, and Fig. 8b) fixed at 340°C.
이상의 본 발명의 목적들, 다른 목적들, 특징들 및 이점들은 첨부된 도면과 관련된 이하의 바람직한 실시예들을 통해서 쉽게 이해될 것이다. 그러나 본 발명은 여기서 설명되는 실시예들에 한정되지 않고 다른 형태로 구체화될 수도 있다. 오히려, 여기서 소개되는 실시예들은 개시된 내용이 철저하고 완전해질 수 있도록 그리고 통상의 기술자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 제공되는 것이다.The above objects, other objects, features and advantages of the present invention will be easily understood through the following preferred embodiments in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed subject matter may be thorough and complete, and that the spirit of the present invention may be sufficiently conveyed to those skilled in the art.
각 도면을 설명하면서 유사한 참조부호를 유사한 구성요소에 대해 사용하였다. 첨부된 도면에 있어서, 구조물들의 치수는 본 발명의 명확성을 위하여 실제보다 확대하여 도시한 것이다. 제1, 제2 등의 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 상기 구성요소들은 상기 용어들에 의해 한정되어서는 안 된다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다. 예를 들어, 본 발명의 권리 범위를 벗어나지 않으면서 제1 구성요소는 제2 구성요소로 명명될 수 있고, 유사하게 제2 구성요소도 제1 구성요소로 명명될 수 있다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다.In describing each figure, like reference numerals have been used for like elements. In the accompanying drawings, the dimensions of the structures are enlarged than actual for clarity of the present invention. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The singular expression includes the plural expression unless the context clearly dictates otherwise.
본 명세서에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. 또한, 층, 막, 영역, 판 등의 부분이 다른 부분 "상에" 있다고 할 경우, 이는 다른 부분 "바로 위에" 있는 경우뿐만 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다. 반대로 층, 막, 영역, 판 등의 부분이 다른 부분 "하부에" 있다고 할 경우, 이는 다른 부분 "바로 아래에" 있는 경우뿐만 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다.In this specification, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, component, part, or a combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Also, when a part of a layer, film, region, plate, etc. is said to be “on” another part, it includes not only the case where the other part is “directly on” but also the case where there is another part in between. Conversely, when a part, such as a layer, film, region, plate, etc., is "under" another part, this includes not only cases where it is "directly under" another part, but also a case where another part is in the middle.
달리 명시되지 않는 한, 본 명세서에서 사용된 성분, 반응 조건, 폴리머 조성물 및 배합물의 양을 표현하는 모든 숫자, 값 및/또는 표현은, 이러한 숫자들이 본질적으로 다른 것들 중에서 이러한 값을 얻는 데 발생하는 측정의 다양한 불확실성이 반영된 근사치들이므로, 모든 경우 "약"이라는 용어에 의해 수식되는 것으로 이해되어야 한다. 또한, 본 기재에서 수치범위가 개시되는 경우, 이러한 범위는 연속적이며, 달리 지적되지 않는 한 이러한 범위의 최소값으로부터 최대값이 포함된 상기 최대값까지의 모든 값을 포함한다. 더 나아가, 이러한 범위가 정수를 지칭하는 경우, 달리 지적되지 않는 한 최소값으로부터 최대값이 포함된 상기 최대값까지를 포함하는 모든 정수가 포함된다.Unless otherwise specified, all numbers, values, and/or expressions expressing quantities of ingredients, reaction conditions, polymer compositions and formulations used herein, contain all numbers, values and/or expressions in which such numbers essentially occur in obtaining such values, among others. Since they are approximations reflecting various uncertainties in the measurement, it should be understood as being modified by the term "about" in all cases. Also, when numerical ranges are disclosed in this description, such ranges are continuous and inclusive of all values from the minimum to the maximum inclusive of the range, unless otherwise indicated. Furthermore, when such ranges refer to integers, all integers inclusive from the minimum to the maximum inclusive are included, unless otherwise indicated.
본 명세서에 있어서, 범위가 변수에 대해 기재되는 경우, 상기 변수는 상기 범위의 기재된 종료점들을 포함하는 기재된 범위 내의 모든 값들을 포함하는 것으로 이해될 것이다. 예를 들면, "5 내지 10"의 범위는 5, 6, 7, 8, 9, 및 10의 값들뿐만 아니라 6 내지 10, 7 내지 10, 6 내지 9, 7 내지 9 등의 임의의 하위 범위를 포함하고, 5.5, 6.5, 7.5, 5.5 내지 8.5 및 6.5 내지 9 등과 같은 기재된 범위의 범주에 타당한 정수들 사이의 임의의 값도 포함하는 것으로 이해될 것이다. 예를 들면, "10% 내지 30%"의 범위는 10%, 11%, 12%, 13% 등의 값들과 30%까지를 포함하는 모든 정수뿐만 아니라 10% 내지 15%, 12% 내지 18%, 20% 내지 30% 등의 임의의 하위 범위를 포함하고, 10.5%, 15.5%, 25.5% 등과 같이 기재된 범위의 범주 내의 타당한 정수 사이의 임의의 값도 포함하는 것으로 이해될 것이다.In this specification, when a range is described for a variable, the variable will be understood to include all values within the stated range including the stated endpoints of the range. For example, a range of “5 to 10” includes the values of 5, 6, 7, 8, 9, and 10, as well as any subranges such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc. It will be understood to include any value between integers that are appropriate for the scope of the recited range, such as 5.5, 6.5, 7.5, 5.5 to 8.5 and 6.5 to 9, and the like. For example, a range of “10% to 30%” includes values such as 10%, 11%, 12%, 13%, and all integers up to and including 30%, as well as 10% to 15%, 12% to 18%. , including any subranges from 20% to 30%, and the like, and will be understood to include any value between reasonable integers within the scope of the recited ranges, such as 10.5%, 15.5%, 25.5%, and the like.
본 발명의 일 실시예에 따른 액상유기수소운반체(Liquid organic hydrogen carrier; LOHC) 탈수소화용 촉매는 3차원 골격을 갖고, 상기 골격에 의해 형성된 메조기공을 복수로 포함하는 지지체, 및 상기 지지체 상에 담지된 촉매금속을 포함한다.The catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) according to an embodiment of the present invention has a three-dimensional backbone, a support including a plurality of mesopores formed by the backbone, and supported on the support containing catalytic metals.
일반적으로, 규칙적 또는 불규칙적으로 배열된 나노기공 구조를 갖는 물질을 나노기공(nanoporous) 물질이라고 표현하는데, IUPAC(International Union of Pure and Applied Chemictry)의 정의에 의하면, 기공의 직경에 따라 3가지로 나누어진다. 기공의 직경이 가장 작은 것을 마이크로기공(microporous), 중간 크기인 것을 메조기공(mesoporous), 마지막으로 가장 큰 직경을 갖는 것을 매크로기공(macroporous)로 분류한다.In general, a material having a regular or irregularly arranged nanopore structure is expressed as a nanoporous material. lose Those with the smallest diameter are classified as microporous, those with the medium size are classified as mesoporous, and finally those with the largest diameter are classified as macroporous.
그 중, 메조기공 물질은 일반적으로 2~50nm 정도의 나노미터 크기의 균일한 기공 및 큰 비표면적을 가진다. 이러한 물성은 유체의 침투성, 필터 효과, 열과 소리의 차단 능력과 같은 유용한 성질을 유도하게 된다. 낮은 밀도와 높은 표면적 특성을 이용하여 거대 분자들의 반응 촉매로써 이용이 가능하고, 전자 및 광학용 기반 재료, 수소저장 및 에너지 재료, 정밀화학용 재료, 의료용 재료 등의 용도로 활발히 응용되고 있으며, 전통적으로 촉매, 흡착제 또는 담체 물질로 응용되어 왔다.Among them, mesoporous materials generally have uniform pores with a nanometer size of about 2 to 50 nm and a large specific surface area. These properties lead to useful properties such as fluid permeability, filter effect, and ability to block heat and sound. It can be used as a reaction catalyst of macromolecules by using its low density and high surface area characteristics, and is actively applied to electronic and optical base materials, hydrogen storage and energy materials, fine chemistry materials, and medical materials. It has been applied as a catalyst, adsorbent or carrier material.
본 발명에서 사용되는 지지체는 3차원 골격을 갖고, 상기 골격에 의해 형성된 메조기공(mesoporous)을 복수로 포함하여 넓은 표면적을 가짐으로써 촉매가 상기 지지체 상에 엉김현상 없이 고르게 분포됨으로써 기존 촉매에 비해 적은 양의 활성금속으로도 우수한 촉매 활성이 안정적으로 유지되면서도 수소 전환율이 높아 수소 생산의 효율을 크게 향상시킬 수 있는 장점이 있다.The support used in the present invention has a three-dimensional skeleton, and has a large surface area including a plurality of mesoporous formed by the skeleton, so that the catalyst is evenly distributed on the support without agglomeration, so less than the existing catalyst Although excellent catalytic activity is stably maintained even with a positive active metal, the hydrogen conversion rate is high, which has the advantage of greatly improving the efficiency of hydrogen production.
종래 액상유기수소운반체(Liquid organic hydrogen carrier; LOHC) 탈수소화용 촉매에 사용되는 지지체는 주로 탄소로 구성되어 있었는데, 탄소로 구성된 지지체는 산업적인 조건하에서 수소첨가에 민감하고, 작동과정에서 메탄으로 서서히 변형되어 지지체의 점차적으로 손실되는 문제가 있었고, 또한, 공기/산소에 의해 고열에서 재생하는 것이 어려운 문제가 있었는 바, 결과적으로 작업의 어려움을 초래하는 문제점이 있었다.The support used in the conventional liquid organic hydrogen carrier (LOHC) dehydrogenation catalyst was mainly composed of carbon. There was a problem in that the support was gradually lost, and there was also a problem in that it was difficult to regenerate at high heat by air/oxygen, and as a result, there was a problem causing difficulties in operation.
이에, 본 발명의 일 실시예에 따른 지지체는 탄소로 구성되어 있지 않아 수소첨가에 민감하지 않으면서도 작동과정에서 지지체의 변형이 일어나지 않는 것이라면 특별히 제한되지 않는다. Therefore, the support according to an embodiment of the present invention is not particularly limited as long as it is not made of carbon and thus is not sensitive to hydrogenation and does not cause deformation of the support during operation.
예를 들어, 상기 지지체는 TiO2, SiO2, ZrO2, Al203, SnO2, Ta2O5, HfO2, La2O3, V2O5, CeO2, Fe2O3, Cr2O3, MoO3, ZnO, MgO, 및 WO3 로 이루어진 군에서 선택된 1종 이상의 산화물을 포함할 수 있고, 특정 성분을 포함하는 것으로 제한하지 아니하나, 바람직하게는 상대적으로 적은 산점으로 인해 산점에 서 발생하는 부반응(Cracking, isomerization, coking 등)의 억제가 가능하고, 고도로 발달한 메조 기공의 상대적으로 넓은 표면적 및 기공에 의한 낮은 활성금속과의 상호작용에도 불구하고 반응 활성점으 의 고분산화 및 반응물의 물질 전달 강화에 이로운 SiO2을 포함할 수 있다.For example, the support may be TiO 2 , SiO 2 , ZrO 2 , Al 2 O 3 , SnO 2 , Ta 2 O 5 , HfO 2 , La 2 O 3 , V 2 O 5 , CeO 2 , Fe 2 O 3 , Cr 2 O 3 , MoO 3 , ZnO, MgO, and may include one or more oxides selected from the group consisting of WO 3 , but is not limited to including a specific component, preferably due to relatively few acid sites It is possible to suppress side reactions (cracking, isomerization, coking, etc.) occurring at acid sites, and highly dispersed reaction sites despite the relatively large surface area of the highly developed mesopores and low interaction with active metals due to pores and SiO 2 beneficial for enhancing mass transfer of reactants.
상기 지지체는 KIT(Korea Advanced Institute of Sience and Technology, KAIST) 계열, MCM(Mobil Composition of Matter) 계열, SBA(Santa Babara Amorphous) 계열, AMS (Anionic-surfactant-templated mesoporous silica)계열, FSM (Folded sheets mechanism) 계열, FDU (Fudan University) 계열, KSW (Kagami memorial lab, Materials Science and Technology, Waseda University) 계열, CMI (Chimie des Materiaux Inorganiques) 계열, IBN (Institute of Bioengineering and Nanotechnology) 계열, MSU (Michigan State University) 계열, TUD (Delft University of Technology) 계열, 및 HMS(Hexagonal Mesoporous Silica) 계열로 이루어진 군으로부터 선택되는 1종 이상의 계열일 수 있고, 특정 계열로 한정되지 않으나, 바람직하게는 3차원의 bi-continuous cubic pore structure로 인해 한쪽의 pore(기공)이 coke deposition에 의해 막힌 경우에도 다른 쪽의 기공을 통해 반응물 및 생성물의 물질 전달이 용이하게 이뤄짐, 및 곡선형태의 cubic interconnected structure, 촉매 단위 질량당 큰 pore volume에 의한 반응물의 기공 내 체류시간이 길어짐에 의해 반응물과 활성점과의 contact time이 늘어나는 효과가 있는 KIT 계열의 KIT-6일 수 있다.The support is KIT (Korea Advanced Institute of Sience and Technology, KAIST) series, MCM (Mobil Composition of Matter) series, SBA (Santa Babara Amorphous) series, AMS (Anionic-surfactant-templated mesoporous silica) series, FSM (Folded sheets) mechanism), FDU (Fudan University), KSW (Kagami memorial lab, Materials Science and Technology, Waseda University), CMI (Chimie des Materiaux Inorganiques), IBN (Institute of Bioengineering and Nanotechnology), MSU (Michigan State) University) series, TUD (Delft University of Technology) series, and HMS (Hexagonal Mesoporous Silica) series may be one or more series selected from the group consisting of, but not limited to a specific series, preferably three-dimensional bi- Due to the continuous cubic pore structure, even when one pore (pore) is blocked by coke deposition, mass transfer of reactants and products through the other pore is facilitated, and curved cubic interconnected structure, large per unit mass of catalyst It may be KIT-6 of the KIT series, which has the effect of increasing the contact time between the reactant and the active point by increasing the residence time in the pores of the reactant by the pore volume.
상기 지지체 내 메조기공의 직경은 4 ~ 11nm 일 수 있다. 상기 범위를 벗어나, 상기 메조기공의 직경이 작으면 촉매금속 전구체 용액이 깊이 침투하기 우려워 촉매금속이 지지체의 기공 내부에 위치하지 못하고 표면으로 나와서 뭉쳐질 가능성이 큰 단점이 있고, 직경이 크면 너무 많은 양의 촉매금속 전구체 용액이 기공으로 들어가거나 덜 발달된 기공구조로 인해 함침된 촉매금속이 조밀한 형태로 위치하여 서로 엉겨서 뭉침(aggregation)이 일어날수 있는 단점이 있다.The diameter of the mesopores in the support may be 4 to 11 nm. Out of the above range, if the diameter of the mesopores is small, the catalyst metal precursor solution is afraid to penetrate deeply. There is a disadvantage that a large amount of the catalyst metal precursor solution enters the pores or the impregnated catalyst metal is located in a dense form due to an underdeveloped pore structure, and aggregation may occur due to agglomeration.
상기 지지체의 표면적은 600~850m2/g일 수 있다. 상기 범위를 벗어나, 상기 지지체의 표면적이 너무 작으면 메조다공성이 덜 발달된 상태이므로 촉매금속이 고르게 표면 및 기공 내부에 분산되기 어려운 단점이 있다.The surface area of the support may be 600 ~ 850 m 2 /g. Out of the above range, if the surface area of the support is too small, the mesoporosity is less developed, so it is difficult to evenly disperse the catalyst metal on the surface and inside the pores.
상기 지지체에 포함된 복수의 메조기공의 기공부피는 0.5~1.5cm3/g일 수 있다. 상기 범위를 벗어나, 상기 메조기공의 기공부피가 너무 낮으면 메조다공성이 덜 발달된 상태이므로 반응물이나 반응 생성물이 위치할 수 있는 공간이 줄어드는 것이므로 반응물과 촉매 활성점 간의 contact time(촉매 기공 부피로 계산한 접촉시간)이 줄어들어서 활성이 줄어들 수 있다는 단점이 있고, 메조기공의 기공부피가 너무 크면 촉매 표면 및 기공에 발달된 활성점의 수가 감소할 수 있으므로 촉매 활성점 기준으로의 contact time은 오히려 감소하는 단점이 있다.The pore volume of the plurality of mesopores included in the support may be 0.5 to 1.5 cm 3 /g. Out of the above range, if the pore volume of the mesopores is too low, the mesoporosity is less developed, so the space where the reactants or reaction products can be located is reduced. One contact time) is reduced, so the activity may decrease, and if the pore volume of the mesopores is too large, the number of active sites developed on the catalyst surface and pores may decrease, so the contact time based on the catalyst active points is rather reduced. There is a downside to
또한, 상기 지지체는 정렬된 메조포러스 실리카(Ordered mesoporous silica) 계열 물질로써, 특유의 독특한 다공성 구조 때문에, 메조 다공성 구조를 가진 전이금속 산화물 계열의 재료 합성을 위한 희생 물질(sacrificial agent)로 활용될 수 있다. 구체적으로, 정렬된 메조포러스 실리카(Ordered mesoporous silica)의 기공 내에 전이금속의 전구체를 침투시킨 후 건조 & 소성 과정을 거쳐 전이금속 산화물을 정렬된 메조포러스 실리카(Ordered mesoporous silica)의 기공 내에 형성시킨 후 단단한 템플릿(hard template) 으로 사용된 정렬된 메조포러스 실리카(Ordered mesoporous silica)를 강염기나 강산으로 녹여내면 정렬된 메조포러스 실리카(Ordered mesoporous silica)의 기공 형태를 골격으로 갖는 메조 다공성 전이금속 산화물을 합성할 수 있다. 특히, 이러한 메조 다공성 전이금속 촉매는 귀금속 계열 보다는 비교적 값이 저렴한 여타 전이금속 촉매를 메조 다공성의 특징을 가진 촉매로 합성하는데 활용될 수 있다.In addition, the support is an ordered mesoporous silica-based material, and because of its unique porous structure, it can be used as a sacrificial agent for synthesizing a transition metal oxide-based material having a mesoporous structure. have. Specifically, after infiltrating the precursor of the transition metal into the pores of the ordered mesoporous silica, drying & firing processes to form a transition metal oxide in the pores of the ordered mesoporous silica When ordered mesoporous silica used as a hard template is dissolved with a strong base or strong acid, a mesoporous transition metal oxide having the pore shape of ordered mesoporous silica as a skeleton is synthesized. can do. In particular, such a mesoporous transition metal catalyst can be used to synthesize other transition metal catalysts, which are relatively inexpensive than noble metals, as catalysts having mesoporous characteristics.
이에 따라, 본 발명의 일 실시예에 따른 지지체는 상기 특징을 만족하는 성분, 및 상기 특징을 만족하는 메조기공을 복수로 포함하고 있어 지지체의 표면적이 매우 넓어 촉매금속이 상기 지지체 상에 고르게 분포할 수 있으므로, 촉매금속 간에 엉김현상(sintering)이 억제되는 바, 기존 촉매에 비해 적은 양의 활성금속으로도 우수한 촉매 활성이 안정적으로 유지되면서도 LOHC 전환율이 높아 수소 생산의 효율을 크게 향상시킬 수 있다.Accordingly, the support according to an embodiment of the present invention includes a component satisfying the above characteristics and a plurality of mesopores satisfying the above characteristics, so that the surface area of the support is very wide so that the catalyst metal is evenly distributed on the support. Therefore, sintering between catalyst metals is suppressed, and excellent catalytic activity is stably maintained even with a small amount of active metal compared to conventional catalysts, and the LOHC conversion rate is high, thereby greatly improving the efficiency of hydrogen production.
본 발명의 일 실시예에 따른 촉매 금속은 상기 지지체 상에 고르게 분포하여 액상유기수소운반체(LOHC) 탈수소화 반응에 사용될 수 있는 것이라면 특별히 제한되지 않는다.The catalyst metal according to an embodiment of the present invention is not particularly limited as long as it is uniformly distributed on the support and can be used in a liquid organic hydrogen carrier (LOHC) dehydrogenation reaction.
예를 들어, 상기 촉매금속은 레늄(Re), 주석(Sn), 망간(Mn), 아연(Zn), 마그네슘(Mg), 바나듐(V), 세륨(Ce), 란다넘(La), 이트륨(Y), 사마륨(Sm), 가돌리늄(Gd), 나트륨(Na), 칼륨(K), 세슘(Cs), 루비늄(Rb), 루테늄(Ru), 니켈(Ni), 로듐(Rh), 이리듐(Ir), 코발트(Co), 철(Fe), 백금(Pt), 크롬(Cr), 팔라듐(Pd) 및 구리(Cu)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있고, 특정 성분을 포함하는 것으로 제한되지 않으나, 바람직하게는, 높은 C-H 결합 활성화(C-H bond activation) 능력, 낮은 C-C cleavage 능력으로 인한 선택적으로 매우 높은 탈수소화 반응 선택도를 갖는 백금(Pt)을 포함할 수 있다.For example, the catalyst metal is rhenium (Re), tin (Sn), manganese (Mn), zinc (Zn), magnesium (Mg), vanadium (V), cerium (Ce), randanium (La), yttrium (Y), samarium (Sm), gadolinium (Gd), sodium (Na), potassium (K), cesium (Cs), rubinium (Rb), ruthenium (Ru), nickel (Ni), rhodium (Rh), It may include at least one selected from the group consisting of iridium (Ir), cobalt (Co), iron (Fe), platinum (Pt), chromium (Cr), palladium (Pd), and copper (Cu), and a specific component Although not limited to including, preferably, platinum (Pt) having a very high dehydrogenation reaction selectivity due to a high C-H bond activation ability, a low C-C cleavage ability may be included.
상기 촉매금속은 넓은 지지체의 표면적 상에 고르게 분포하여 담지할 수 있고, 그 함량은 탈수소화용 촉매 전체 중량을 기준으로 0.5~10중량%으로 지지체 상에 담지될 수 있다. 상기 범위를 벗어나, 상기 촉매금속의 담지량이 너무 적으면 LOHC 탈수소화능 능력을 발휘하기 어려운 단점이 있고, 상기 촉매금속의 담지량이 너무 많으면 촉매금속이 분산되지 못하고 뭉쳐질 가능성이 높고 비용단가가 비싸지는 단점이 있다.The catalyst metal may be uniformly distributed and supported on the surface area of a large support, and the content thereof may be supported on the support in an amount of 0.5 to 10% by weight based on the total weight of the catalyst for dehydrogenation. Outside the above range, if the supported amount of the catalyst metal is too small, it is difficult to exhibit the LOHC dehydrogenation ability. There are disadvantages.
상기 촉매금속은 구형(sphere or truncated cube)에 근접한 나노입자 형태로써, 그 크기는 대부분 1~2 nm 수준으로 비교적 고르게 분포할 수 있다. 구체적으로, 열처리 전에는 금속에 리간드가 붙은 복합체(complex) 형태의 금속 전구체로 용매에 용해되어 지지체의 기공 내부 혹은 표면에 추가되지만, 건조 이후 고온의 공기중 열처리(소성) 단계에서 Pt 산화물 혹은 Pt의 나노입자 형태로 변화하여, 대부분 1-2 nm 정도의 입자 크기를 갖을 수 있다.The catalyst metal is in the form of nanoparticles close to a sphere or truncated cube, and the size of most of them can be relatively evenly distributed at the level of 1 to 2 nm. Specifically, before heat treatment, a metal precursor in the form of a complex with a ligand attached to the metal is dissolved in a solvent and added to the inside or surface of the pores of the support. By changing into nanoparticle form, most may have a particle size of about 1-2 nm.
본 발명의 일 실시예에 따른 액상유기수소운반체(LOHC) 탈수소화용 촉매와 함께 사용할 수 있는 액상유기수소운반체(LOHC)는 수소생산 및 수소 정제/저장 방법들에게서 필요로 하는 정제공정을 배제할 수 있고, 액상으로 수소를 저장할 수 있어 최종 소비자에게 대량으로 안전하게 수소를 공급할 수 있는 특징이 있다.A liquid organic hydrogen carrier (LOHC) that can be used together with a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) according to an embodiment of the present invention can exclude the purification process required for hydrogen production and hydrogen purification / storage methods. In addition, hydrogen can be stored in liquid form, so it can safely supply hydrogen in large quantities to end consumers.
이에 따라, 본 발명의 액상유기수소운반체(LOHC) 탈수소화용 촉매와 함께 사용할 수 있는 액상유기수소운반체(LOHC)는 예를 들어, 상기 액상유기수소운반체(LOHC)는 메틸사이클로헥산(Methylcylohexane; MCH), 퍼하이드로-벤질톨루엔 (Perhydro-benzyltoluene), 퍼하이드로-디벤질톨루엔(Perhydro-dibenzyltoluene), 바이사이클로헥실-디사이클로헥실 메탄(Bicyclohexyl-Dicyclohexyl methane), 사이클로헥산(Cyclohexane), 데칼린(Decalin), 4-아미노-피퍼리딘(4-amino-piperidine), 2-메틸퍼하이드로린돌(2-methylperhydrolindole), N-메틸퍼하이드로린돌(N-methylperhydrolindole), 및 도데카하이드로-N-에틸카바졸(Dodecahydro-N-ethylcarbazole) 로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있고, 특정 성분을 포함하는 것으로 제한되지 아니한다.Accordingly, the liquid organic hydrogen carrier (LOHC) that can be used together with the catalyst for dehydrogenation of the liquid organic hydrogen carrier (LOHC) of the present invention is, for example, the liquid organic hydrogen carrier (LOHC) is methylcyclohexane (Methylcylohexane; MCH) , perhydro-benzyltoluene, perhydro-dibenzyltoluene, bicyclohexyl-dicyclohexyl methane, cyclohexane, decalin, 4-amino-piperidine, 2-methylperhydrolindole, N-methylperhydrolindole, and dodecahydro-N-ethylcarbazole -N-ethylcarbazole) may include one or more selected from the group consisting of, it is not limited to including a specific component.
본 발명의 일 실시예에 따른 액상유기수소운반체(Liquid organic hydrogen carrier; LOHC) 탈수소화용 촉매 제조방법은 3차원 골격을 갖고, 상기 골격에 의해 형성된 메조기공을 복수로 포함하는 지지체에 촉매금속 전구체 용액을 함침시키는 단계; 및 함침된 결과물을 건조시켜 상기 지지체 상에 촉매금속이 담지된 촉매를 얻는 단계;를 포함한다. 상기 촉매의 제조방법은 전술한 촉매에 관한 내용과 실질적으로 중복되는 내용을 포함할 수 있고, 중복된 부분에 대한 설명은 생략한다.The method for preparing a catalyst for liquid organic hydrogen carrier (LOHC) dehydrogenation according to an embodiment of the present invention is a catalyst metal precursor solution on a support having a three-dimensional skeleton and including a plurality of mesopores formed by the skeleton impregnating the and drying the impregnated product to obtain a catalyst having a catalyst metal supported thereon on the support. The method for preparing the catalyst may include content substantially overlapping with the content related to the catalyst described above, and a description of the overlapping portion will be omitted.
먼저, 상기 특징을 만족하는 지지체 상에 촉매금속 전구체 용액을 함침시킨다. 예시적인 구현예서, 상기 촉매금속이 백금인 경우, 상기 촉매금속 전구체는 Tetraammineplatinum(II) nitrate (Pt(NH3)4(NO3)2), Tetraammineplatinum(II) hydroxide hydrate (Pt(NH2)4(OH)2·xH2O), Tetraammineplatinum(II) chloride hydrate (Pt(NH3)4Cl2·xH2O), Tetraammineplatinum(II) chloride monohydrate (Pt(NH3)4Cl2·H2O), Chloroplatinic acid hexahydrate (H2PtCl6·6H2O), Platinum(II) acetylacetonate (Pt(C 5 H 7 O 2 ) 2 ), Platinum(II) chloride (PtCl 2 ), Platinum(IV) chloride (PtCl 4 ), Potassium hexachloroplatinate(IV) (K 2 PtCl 6 ), Potassium tetrachloroplatinate(II) (K 2 PtCl 4 ), Sodium hexachloroplatinate(IV) hexahydrate (Na 2 PtCl 6 ·6H 2 O), Sodium tetrachloroplatinate(II) hydrate (Na 2 PtCl 4 ·xH 2 O), Ammonium hexachloroplatinate(IV) ((NH 4 ) 2 PtCl 6 ), 및 Ammonium tetrachloroplatinate(II) ((NH 4 ) 2 PtCl 4 )로 이루어진 군에서 선택된 1종 이상을 포함할 수 있고, 특정 성분을 포함하는 것으로 제한되지 않는다.First, a catalyst metal precursor solution is impregnated on a support satisfying the above characteristics. In an exemplary embodiment, when the catalyst metal is platinum, the catalyst metal precursor is Tetraammineplatinum(II) nitrate (Pt(NH 3 ) 4 (NO 3 ) 2 ), Tetraammineplatinum(II) hydroxide hydrate (Pt(NH 2 ) 4 (OH) 2 ·xH 2 O), Tetraammineplatinum(II) chloride hydrate (Pt(NH 3 ) 4 Cl 2 ·xH 2 O), Tetraammineplatinum(II) chloride monohydrate (Pt(NH 3 ) 4 Cl 2 ·H 2 O ), Chloroplatinic acid hexahydrate (H 2 PtCl 6 6H 2 O), Platinum(II) acetylacetonate (Pt(C 5 H 7 O 2 ) 2 ), Platinum(II) chloride (PtCl 2 ), Platinum(IV) chloride ( PtCl 4 ), Potassium hexachloroplatinate(IV) (K 2 PtCl 6 ), Potassium tetrachloroplatinate(II) (K 2 PtCl 4 ), Sodium hexachloroplatinate(IV) hexahydrate (Na 2 PtCl 6 6H 2 O), Sodium tetrachloroplatinate(II) At least one selected from the group consisting of hydrate (Na 2 PtCl 4 ·xH 2 O), Ammonium hexachloroplatinate(IV) ((NH 4 ) 2 PtCl 6 ), and Ammonium tetrachloroplatinate(II) ((NH 4 ) 2 PtCl 4 ) It may include, but is not limited to including a specific component.
이어서, 함침된 결과물을 건조할 수 있다. 예시적인 구현 예에서 공기 분위기에서 80~120℃의 온도에서 12~24시간 동안 건조시킬 수 있고, 바람직하게는 80℃의 온도에서 12시간 동안 건조시킬 수 있다. 또한, 상기 함침된 결과물을 진공 건조할 수도 있다. 상기 범위를 벗어나, 건조시간이 짧거나 건조 온도가 낮을 경우 용매가 충분히 증발하지 못해 잔여 용매가 촉매 소성시에 증발하며 촉매의 활성 물질 분포에 영향을 주는 또 하나의 변수로 작용할 수 있는 단점이 있고, 건조시간이 너무 길면 지지체 물성에 영향을 줄 수 있다. Then, the impregnated result may be dried. In an exemplary embodiment, it may be dried in an air atmosphere at a temperature of 80 to 120° C. for 12 to 24 hours, preferably at a temperature of 80° C. for 12 hours. In addition, the impregnated product may be vacuum dried. Out of the above range, if the drying time is short or the drying temperature is low, the solvent does not evaporate sufficiently, so that the residual solvent evaporates during the catalyst calcination, and there is a disadvantage that it can act as another variable affecting the distribution of the active material of the catalyst, However, if the drying time is too long, the physical properties of the support may be affected.
즉, 본 발명의 일 실시예에 따른 액상유기수소운반체(LOHC) 탈수소화용 촉매 제조방법은 간단한 용액 함침법만으로도 넓은 표면적을 갖는 지지체 상에 촉매금속을 고르게 분포시킬 수 있으므로, 촉매금속 간에 엉김현상(sintering)이 억제되는 바, 기존 촉매에 비해 적은 양의 활성금속으로도 우수한 촉매 활성이 안정적으로 유지되면서도 수소 전환율이 높아 수소 생산의 효율을 크게 향상시킬 수 있다.That is, in the method for preparing a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) according to an embodiment of the present invention, the catalyst metal can be evenly distributed on a support having a large surface area only by a simple solution impregnation method, so agglomeration between catalyst metals ( sintering) is suppressed, and excellent catalytic activity is stably maintained even with a small amount of active metal compared to conventional catalysts, and the hydrogen conversion rate is high, thereby greatly improving the efficiency of hydrogen production.
이하 실시예를 통해 본 발명을 보다 구체적으로 설명한다. 하기 실시예는 본 발명의 이해를 돕기 위한 예시에 불과하며, 본 발명의 범위가 이에 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following examples. The following examples are only examples to help the understanding of the present invention, and the scope of the present invention is not limited thereto.
실시예 1Example 1
지지체는 SiO2계열의 산화물을 포함하는 KIT 계열 중에서도 복수의 메조기공을포함하는 KIT-6의 준비과정은 하기와 같다.The preparation process of KIT-6 including a plurality of mesopores among the KIT-based supports including SiO 2 based oxides is as follows.
구체적으로, 수용액 내부에서 마이셀을 형성시켜 3차원 메조포러스 실리카 구조체를 만들어주는 구조 유도제로 플루로닉 p123 공중합체 16.0g을 약 150mL의 증류수에 섞은 후 증류수에 완전히 녹을 때까지 교반하였다. 이어서 37% 염산 수용액 25mL를 428mL의 증류수와 섞은 후 내부 온도를 35
상기 제조된 지지체로부터 촉매금속 전구체 용액을 함침하는 과정은 하기와 같다. The process of impregnating the catalyst metal precursor solution from the prepared support is as follows.
구체적으로, 제조된 지지체 KIT-6 5g을 80도 오븐에서 일정시간 건조 후, 촉매금속 전구체로써 Pt 전구체인 Chloroplatinic acid hexahydrate (H2PtCl6·6H2O) 약 0.1g을 50 mL정도의 탈이온수(Deionized water)에 녹인 후 일구 플라스크에 건조된 KIT-6 분말과 함께 섞어 슬러리를 제조하였다. 상기의 슬러리는 Rotary evaporator에서 약 2시간 동안 약한 진공상태에서 상온 교반하여 지지체 분말과 백금 전구체의 균일하게 섞일 수 있도록 함. 2시간 이후 고진공 상태로 높여주어 약 10~30분 동안 용매를 완전히 증발시켰다. 용매가 증발되어 촉매금속이 담지된 지지체 분말은 건조용 오븐에서 추가로 80℃로 12시간 이상 건조 시켰다. 건조가 완료된 촉매금속이 담지된 지지체 분말은 1℃/분의 승온 속도로 450도에서 3시간 동안 소성하여 액상유기수소운반체(LOHC) 탈수소화용 촉매를 합성 완료하였다.Specifically, after drying 5 g of the prepared support KIT-6 in an oven at 80° C. for a certain period of time, as a catalyst metal precursor, about 0.1 g of Chloroplatinic acid hexahydrate (H 2 PtCl 6 .6H 2 O), a Pt precursor, was added to 50 mL of deionized water. (Deionized water) and mixed with dried KIT-6 powder in a one-neck flask to prepare a slurry. The slurry is stirred at room temperature in a low vacuum for about 2 hours in a rotary evaporator so that the support powder and the platinum precursor can be uniformly mixed. After 2 hours, it was raised to a high vacuum state to completely evaporate the solvent for about 10 to 30 minutes. The solvent is evaporated and the catalyst metal is supported on the support powder. It was further dried at 80 °C for more than 12 hours in a drying oven. The dried catalyst metal-supported support powder was calcined at 450° C. for 3 hours at a temperature increase rate of 1° C./min to complete the synthesis of a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC).
실시예 2Example 2
상기 실시예 1과 비교하였을 때, 촉매금속 전구체로써 Pt 전구체인 Tetraammineplatinum(II) nitrate ([Pt(NH3)4](NO3)2)를 사용한 것을 제외하고, 실시예 1과 동일하게 액상유기수소운반체(LOHC) 탈수소화용 촉매를 제조하였다.When compared with Example 1, as a catalyst metal precursor Tetraammineplatinum(II) nitrate ([Pt(NH 3 ) 4 ](NO 3 ) 2 ) Liquid organic in the same manner as in Example 1, except that A catalyst for hydrogen carrier (LOHC) dehydrogenation was prepared.
비교예comparative example
종래 사용되는 알루미나 기반 탈수소화 촉매인 Pt(1)/ γ-Al2O3 를 사용하였다.Pt(1)/γ-Al 2 O 3 , which is a conventionally used alumina-based dehydrogenation catalyst, was used.
실험예 1 - 반응속도 및 공간속도에 따른 액상유기수소운반체(LOHC) 탈수소화용 촉매의 전환율과 수소생성속도 비교Experimental Example 1 - Comparison of conversion rate and hydrogen production rate of catalyst for dehydrogenation of liquid organic hydrogen carrier (LOHC) according to reaction rate and space velocity
상기 실시예 1에 따라 액상유기수소운반체(LOHC) 탈수소화용 촉매를 제조하고, 공간속도를 고정한 반응온도에 따른 액상유기수소운반체(LOHC)의 전환율 및 이에 따른 수소생성속도를 측정하고, 그 결과를 도 1에 나타내었다. 또한, 반응 온도를 고정한 공간속도에 따른 액상유기수소운반체(LOHC)의 전환율 및 이에 따른 수소생성속도를 측정하고, 그 결과를 도 2a 와 도 2b에 나타내었다.A catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) was prepared according to Example 1, the conversion rate of the liquid organic hydrogen carrier (LOHC) according to the reaction temperature at which the space velocity was fixed, and the hydrogen production rate accordingly were measured, and the result was measured 1 is shown. In addition, the conversion rate of the liquid organic hydrogen carrier (LOHC) according to the space velocity at which the reaction temperature was fixed and the hydrogen production rate accordingly were measured, and the results are shown in FIGS. 2A and 2B.
상기 도 1을 참고하면, 반응속도가 증가함에 따라, 수소생성속도는 조금씩 꾸준히 증가함에 따라 전환율 또한 증가하는 것을 확인할 수 있었다. 또한, 도 2a와 도 2b를 참고하면, 반응온도가 300℃ 또는 340℃가 고정되었을 때, 공간속도가 증가함에 따라 수소생성속도는 증가하는 반면, 전환율은 대체적으로 감소하는 것을 확인할 수 있다.Referring to FIG. 1 , as the reaction rate increased, the hydrogen production rate gradually increased, and it was confirmed that the conversion rate also increased. In addition, referring to FIGS. 2A and 2B , when the reaction temperature is fixed at 300° C. or 340° C., it can be seen that the hydrogen production rate increases as the space velocity increases, whereas the conversion rate generally decreases.
상기 경향을 검토해보면, 반응 온도가 증가함에 따라 전환율이 증가하고, 공간속도는 대체적으로 낮을 때 전환율이 높다는 것을 확인할 수 있었다.Examining the above trends, it was confirmed that the conversion rate increased as the reaction temperature increased, and the conversion rate was high when the space velocity was generally low.
한편, 실시예 2에 따른 액상유기수소운반체(LOHC) 탈수소화용 촉매를 상기 실시예 1과 동일하게 상기 전환율과 수소생성속도를 측정한 결과(도 3, 도 4a, 및 도 4b), 상기 실시예 1의 경향과 유사한 것을 확인할 수 있었다.On the other hand, as a result of measuring the conversion rate and hydrogen production rate of the catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) according to Example 2 in the same manner as in Example 1 (FIGS. 3, 4A, and 4B), the Example Similar to the trend of 1 was confirmed.
즉, 본 발명의 일 실시예에 따라 제조된 액상유기수소운반체(LOHC) 탈수소화용 촉매는 내부기공인 메조기공을 복수로 포함하고 있어 지지체의 표면적이 매우 넓어 촉매금속이 상기 지지체 상에 고르게 분포할 수 있으므로, 촉매금속 간에 엉김현상(sintering)이 억제되는 바, 기존 촉매에 비해 적은 양의 활성금속으로도 우수한 촉매 활성이 안정적으로 유지되면서도 수소 전환율이 높아 수소 생산의 효율을 크게 향상시킬 수 있다는 것을 확인할 수 있었다.That is, the catalyst for liquid organic hydrogen carrier (LOHC) dehydrogenation prepared according to an embodiment of the present invention includes a plurality of mesopores, which are internal pores, and the surface area of the support is very wide, so that the catalyst metal is evenly distributed on the support. Therefore, sintering between catalyst metals is suppressed, and excellent catalytic activity is stably maintained even with a small amount of active metal compared to conventional catalysts, and the hydrogen conversion rate is high, so that the efficiency of hydrogen production can be greatly improved. could check
실험예 2 - 액상유기수소운반체(LOHC) 탈수소화용 촉매의 내구성 평가Experimental Example 2 - Evaluation of durability of catalyst for dehydrogenation of liquid organic hydrogen carrier (LOHC)
상기 실시예 1에 따라 액상유기수소운반체(LOHC) 탈수소화용 촉매를 제조하고, 공간속도와 반응온도를 고정한 채 촉매 사용시간을 늘려 촉매내구성을 평가하고 그 결과를 도 5에 나타내었다.A catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) was prepared according to Example 1, and the catalyst durability was evaluated by increasing the catalyst usage time while fixing the space velocity and the reaction temperature, and the results are shown in FIG. 5 .
이를 참고하면, 실시예 1에 따른 액상유기수소운반체(LOHC) 탈수소화용 촉매를 긴 시간동안 사용하더라도 전환율이 95% 이상을 유지하고 있다는 것을 확인할 수 있었다.Referring to this, it was confirmed that the conversion rate was maintained at 95% or more even when the catalyst for dehydrogenation of the liquid organic hydrogen carrier (LOHC) according to Example 1 was used for a long time.
한편, 실시예 2에 따른 액상유기수소운반체(LOHC) 탈수소화용 촉매를 상기 실시예 1과 동일하게 상기 촉매 내구성을 평가한 결과(도 6), 상기 실시예 1의 경향과 유사하다는 것을 확인할 수 있었다.On the other hand, as a result of evaluating the catalyst durability of the liquid organic hydrogen carrier (LOHC) dehydrogenation catalyst according to Example 2 in the same manner as in Example 1 ( FIG. 6 ), it was confirmed that the trend was similar to that of Example 1. .
즉, 본 발명의 일 실시예에 따라 제조된 액상유기수소운반체(LOHC) 탈수소화용 촉매는 내부기공인 메조기공을 복수로 포함하고 있어 지지체의 표면적이 매우 넓어 촉매금속이 상기 지지체 상에 고르게 분포할 수 있으므로, 촉매금속 간에 엉김현상(sintering)이 억제되는 바, 수소 전환율이 높아 수소 생산의 효율을 크게 향상시킬 수 있으면서도 기존 촉매에 비해 적은 양의 활성금속으로도 우수한 촉매 활성이 안정적으로 오랫동안 유지된다는 것을 확인할 수 있었다.That is, the catalyst for liquid organic hydrogen carrier (LOHC) dehydrogenation prepared according to an embodiment of the present invention includes a plurality of mesopores, which are internal pores, and the surface area of the support is very wide, so that the catalyst metal is evenly distributed on the support. Therefore, sintering between catalyst metals is suppressed, and the hydrogen conversion rate is high, so the efficiency of hydrogen production can be greatly improved, and excellent catalytic activity is stably maintained for a long time even with a small amount of active metal compared to conventional catalysts. could confirm that
실험예 3 - 액상유기수소운반체(LOHC) 탈수소화용 촉매의 전환률 비교Experimental Example 3 - Comparison of conversion rates of catalysts for dehydrogenation of liquid organic hydrogen carrier (LOHC)
상기 실시예 1, 실시예 2 및 비교예에 따라 액상유기수소운반체(LOHC) 탈수소화용 촉매를 제조하고, 공간속도를 고정한 반응온도에 따른 액상유기수소운반체(LOHC)의 전환율을 각각 측정하고, 그 결과를 도 7에 나타내었다. 또한, 반응 온도를 고정한 공간속도에 따른 액상유기수소운반체(LOHC)의 전환율을 각각 측정하고, 그 결과를 도 8a 와 도 8b에 나타내었다.A catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) was prepared according to Examples 1, 2 and Comparative Examples, and the conversion rate of the liquid organic hydrogen carrier (LOHC) according to the reaction temperature at a fixed space velocity was measured, respectively, and the The results are shown in FIG. 7 . In addition, the conversion rate of the liquid organic hydrogen carrier (LOHC) according to the space velocity at a fixed reaction temperature was measured, respectively, and the results are shown in FIGS. 8A and 8B .
상기 도 7을 참고하면, 실시예 1은 온도가 증가함에도 전환율을 85% 이상 유지, 실시예 2는 300℃ 이상의 온도 조건부터 전환율이 85% 이상 유지된다는 것을 확인할 수 있었다. 반면, 기존 알루미나 기반 촉매인 비교예는 전환율이 대부분의 온도 조건에서 70% 미만인 것을 확인할 수 있다.Referring to FIG. 7 , it was confirmed that Example 1 maintained a conversion rate of 85% or more despite an increase in temperature, and Example 2 maintained a conversion rate of 85% or more from a temperature condition of 300° C. or more. On the other hand, it can be seen that the comparative example, which is an existing alumina-based catalyst, has a conversion rate of less than 70% under most temperature conditions.
또한, 도 8a와 도 8b를 참고하면, 반응온도가 300℃ 또는 340℃가 고정되었을 때, 공간속도가 증가함에 따라 어느 공간속도 조건에서도 실시예 1 및 실시예 2의 전환율이 비교예보다 높았고, 그 중에서도, 실시예 2의 전환율이 실시예 1의 전환율보다 높은 것을 확인할 수 있었다.In addition, referring to Figures 8a and 8b, when the reaction temperature was fixed at 300 °C or 340 °C, the conversion rates of Examples 1 and 2 were higher than those of Comparative Examples under any space velocity conditions as the space velocity increased, Among them, it was confirmed that the conversion rate of Example 2 was higher than the conversion rate of Example 1.
즉, 본 발명의 일 실시예에 따라 제조된 액상유기수소운반체(LOHC) 탈수소화용 촉매는 내부기공인 메조기공을 복수로 포함하고 있어 지지체의 표면적이 매우 넓어 촉매금속이 상기 지지체 상에 고르게 분포할 수 있으므로, 촉매금속 간에 엉김현상(sintering)이 억제되는 바, 기존 촉매에 비해 적은 양의 활성금속으로도 우수한 촉매 활성이 안정적으로 유지되면서도 수소 전환율이 높아 수소 생산의 효율을 크게 향상시킬 수 있다는 것을 확인할 수 있었다.That is, the catalyst for liquid organic hydrogen carrier (LOHC) dehydrogenation prepared according to an embodiment of the present invention includes a plurality of mesopores, which are internal pores, and the surface area of the support is very wide, so that the catalyst metal is evenly distributed on the support. Therefore, sintering between catalyst metals is suppressed, and excellent catalytic activity is stably maintained even with a small amount of active metal compared to conventional catalysts, and the hydrogen conversion rate is high, so that the efficiency of hydrogen production can be greatly improved. could check
Claims (17)
상기 지지체 상에 담지된 촉매금속;을 포함하는 액상유기수소운반체(Liquid organic hydrogen carrier; LOHC) 탈수소화용 촉매.a support having a three-dimensional skeleton and including a plurality of mesopores formed by the skeleton; and
A catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) comprising a catalyst metal supported on the support.
상기 지지체는 TiO2, SiO2, ZrO2, Al203, SnO2, Ta2O5, HfO2, La2O3, V2O5, CeO2, Fe2O3, Cr2O3, MoO3, ZnO, MgO, 및 WO3 로 이루어진 군에서 선택된 1종 이상의 산화물을 포함하는 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매.According to claim 1,
The support is TiO 2 , SiO 2 , ZrO 2 , Al 2 O 3 , SnO 2 , Ta 2 O 5 , HfO 2 , La 2 O 3 , V 2 O 5 , CeO 2 , Fe 2 O 3 , Cr 2 O 3 , MoO 3 , ZnO, MgO, and WO 3 comprising at least one oxide selected from the group consisting of a liquid organic hydrogen carrier (LOHC) catalyst for dehydrogenation.
상기 지지체는 KIT(Korea Advanced Institute of Sience and Technology, KAIST) 계열, MCM(Mobil Composition of Matter) 계열, SBA(Santa Babara Amorphous) 계열, AMS (Anionic-surfactant-templated mesoporous silica)계열, FSM (Folded sheets mechanism) 계열, FDU (Fudan University) 계열, KSW (Kagami memorial lab, Materials Science and Technology, Waseda University) 계열, CMI (Chimie des Materiaux Inorganiques) 계열, IBN (Institute of Bioengineering and Nanotechnology) 계열, MSU (Michigan State University) 계열, TUD (Delft University of Technology) 계열, 및 HMS(Hexagonal Mesoporous Silica) 계열로 이루어진 군으로부터 선택되는 1종 이상의 계열인 것인 액상유기수소운반체(LOHC)탈수소화용 촉매.According to claim 1,
The support is KIT (Korea Advanced Institute of Sience and Technology, KAIST) series, MCM (Mobil Composition of Matter) series, SBA (Santa Babara Amorphous) series, AMS (Anionic-surfactant-templated mesoporous silica) series, FSM (Folded sheets) mechanism), FDU (Fudan University), KSW (Kagami memorial lab, Materials Science and Technology, Waseda University), CMI (Chimie des Materiaux Inorganiques), IBN (Institute of Bioengineering and Nanotechnology), MSU (Michigan State) University) series, TUD (Delft University of Technology) series, and HMS (Hexagonal Mesoporous Silica) series, which is one or more series selected from the group consisting of a liquid organic hydrogen carrier (LOHC) catalyst for dehydrogenation.
상기 지지체는 KIT-6인 것인 액상유기수소운반체(LOHC)탈수소화용 촉매.4. The method of claim 3,
The support is a liquid organic hydrogen carrier (LOHC) catalyst for dehydrogenation of KIT-6.
상기 메조기공의 직경은 4 ~ 11nm 인 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매.According to claim 1,
Catalyst for dehydrogenation of liquid organic hydrogen carrier (LOHC) that the diameter of the mesopores is 4 ~ 11nm.
상기 지지체의 표면적은 600~850m2/g인 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매.According to claim 1,
The surface area of the support is 600 ~ 850 m 2 /g of liquid organic hydrogen carrier (LOHC) catalyst for dehydrogenation.
상기 지지체에 포함된 복수의 메조기공의 기공부피는 0.5~1.5cm3/g인 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매.According to claim 1,
The pore volume of the plurality of mesopores included in the support is 0.5-1.5 cm 3 /g of a liquid organic hydrogen carrier (LOHC) catalyst for dehydrogenation.
상기 촉매금속은 레늄(Re), 주석(Sn), 망간(Mn), 아연(Zn), 마그네슘(Mg), 바나듐(V), 세륨(Ce), 란다넘(La), 이트륨(Y), 사마륨(Sm), 가돌리늄(Gd), 나트륨(Na), 칼륨(K), 세슘(Cs), 루비늄(Rb), 루테늄(Ru), 니켈(Ni), 로듐(Rh), 이리듐(Ir), 코발트(Co), 철(Fe), 백금(Pt), 크롬(Cr), 팔라듐(Pd) 및 구리(Cu)로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매.According to claim 1,
The catalyst metal is rhenium (Re), tin (Sn), manganese (Mn), zinc (Zn), magnesium (Mg), vanadium (V), cerium (Ce), randanium (La), yttrium (Y), Samarium (Sm), gadolinium (Gd), sodium (Na), potassium (K), cesium (Cs), rubinium (Rb), ruthenium (Ru), nickel (Ni), rhodium (Rh), iridium (Ir) , cobalt (Co), iron (Fe), platinum (Pt), chromium (Cr), palladium (Pd) and liquid organic hydrogen carrier (LOHC) comprising at least one selected from the group consisting of copper (Cu) Catalysts for dehydrogenation.
상기 촉매금속은 탈수소화용 촉매 전체 중량을 기준으로 0.5~10중량%의 함량으로 담지된 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매.According to claim 1,
The catalyst for dehydrogenation of the liquid organic hydrogen carrier (LOHC) is that the catalyst metal is supported in an amount of 0.5 to 10% by weight based on the total weight of the catalyst for dehydrogenation.
상기 액상유기수소운반체(LOHC)는 메틸사이클로헥산(Methylcylohexane; MCH), 퍼하이드로-벤질톨루엔 (Perhydro-benzyltoluene), 퍼하이드로-디벤질톨루엔(Perhydro-dibenzyltoluene), 바이사이클로헥실-디사이클로헥실 메탄(Bicyclohexyl-Dicyclohexyl methane), 사이클로헥산(Cyclohexane), 데칼린(Decalin), 4-아미노-피퍼리딘(4-amino-piperidine), 2-메틸퍼하이드로린돌(2-methylperhydrolindole), N-메틸퍼하이드로린돌(N-methylperhydrolindole), 및 도데카하이드로-N-에틸카바졸(Dodecahydro-N-ethylcarbazole)로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매.According to claim 1,
The liquid organic hydrogen carrier (LOHC) is methylcyclohexane (Methylcylohexane; MCH), perhydro-benzyltoluene (Perhydro-benzyltoluene), perhydro-dibenzyltoluene (Perhydro-dibenzyltoluene), bicyclohexyl-dicyclohexyl methane ( Bicyclohexyl-Dicyclohexyl methane), cyclohexane, decalin, 4-amino-piperidine, 2-methylperhydrolindole, N-methylperhydrolindole ( A liquid organic hydrogen carrier (LOHC) catalyst for dehydrogenation comprising at least one selected from the group consisting of N-methylperhydrolindole), and dodecahydro-N-ethylcarbazole (Dodecahydro-N-ethylcarbazole).
함침된 결과물을 건조시켜 상기 지지체 상에 촉매금속이 담지된 촉매를 얻는 단계;를 포함하는 액상유기수소운반체(Liquid organic hydrogen carrier; LOHC) 탈수소화용 촉매 제조방법.impregnating a catalyst metal precursor solution into a support having a three-dimensional skeleton and including a plurality of mesopores formed by the skeleton; and
A method for preparing a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC), comprising: drying the impregnated product to obtain a catalyst having a catalyst metal supported thereon on the support.
상기 지지체는 TiO2, SiO2, ZrO2, Al203, SnO2, Ta2O5, HfO2, La2O3, V2O5, CeO2, Fe2O3, Cr2O3, MoO3, ZnO, MgO, 및 WO3 로 이루어진 군에서 선택된 1종 이상의 산화물을 포함하는 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매 제조방법.12. The method of claim 11,
The support is TiO 2 , SiO 2 , ZrO 2 , Al 2 O 3 , SnO 2 , Ta 2 O 5 , HfO 2 , La 2 O 3 , V 2 O 5 , CeO 2 , Fe 2 O 3 , Cr 2 O 3 , MoO 3 , ZnO, MgO, and WO 3 A method for preparing a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) comprising at least one oxide selected from the group consisting of.
상기 지지체는 KIT(Korea Advanced Institute of Sience and Technology, KAIST) 계열, MCM(Mobil Composition of Matter) 계열, SBA(Santa Babara Amorphous) 계열, AMS (Anionic-surfactant-templated mesoporous silica)계열, FSM (Folded sheets mechanism) 계열, FDU (Fudan University) 계열, KSW (Kagami memorial lab, Materials Science and Technology, Waseda University) 계열, CMI (Chimie des Materiaux Inorganiques) 계열, IBN (Institute of Bioengineering and Nanotechnology) 계열, MSU (Michigan State University) 계열, TUD (Delft University of Technology) 계열, 및 HMS(Hexagonal Mesoporous Silica) 계열로 이루어진 군으로부터 선택되는 1종 이상인 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매 제조방법.12. The method of claim 11,
The support is KIT (Korea Advanced Institute of Sience and Technology, KAIST) series, MCM (Mobil Composition of Matter) series, SBA (Santa Babara Amorphous) series, AMS (Anionic-surfactant-templated mesoporous silica) series, FSM (Folded sheets) mechanism), FDU (Fudan University), KSW (Kagami memorial lab, Materials Science and Technology, Waseda University), CMI (Chimie des Materiaux Inorganiques), IBN (Institute of Bioengineering and Nanotechnology), MSU (Michigan State) University) series, TUD (Delft University of Technology) series, and HMS (Hexagonal Mesoporous Silica) series, which is at least one selected from the group consisting of a liquid organic hydrogen carrier (LOHC) catalyst manufacturing method for dehydrogenation.
상기 지지체는 KIT-6인 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매 제조방법.14. The method of claim 13,
The method for preparing a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC) is that the support is KIT-6.
상기 촉매금속은 레늄(Re), 주석(Sn), 망간(Mn), 아연(Zn), 마그네슘(Mg), 바나듐(V), 세륨(Ce), 란다넘(La), 이트륨(Y), 사마륨(Sm), 가돌리늄(Gd), 나트륨(Na), 칼륨(K), 세슘(Cs), 루비늄(Rb), 루테늄(Ru), 니켈(Ni), 로듐(Rh), 이리듐(Ir), 코발트(Co), 철(Fe), 백금(Pt), 크롬(Cr), 팔라듐(Pd) 및 구리(Cu)로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매 제조방법.12. The method of claim 11,
The catalyst metal is rhenium (Re), tin (Sn), manganese (Mn), zinc (Zn), magnesium (Mg), vanadium (V), cerium (Ce), randanium (La), yttrium (Y), Samarium (Sm), gadolinium (Gd), sodium (Na), potassium (K), cesium (Cs), rubinium (Rb), ruthenium (Ru), nickel (Ni), rhodium (Rh), iridium (Ir) , cobalt (Co), iron (Fe), platinum (Pt), chromium (Cr), palladium (Pd) and liquid organic hydrogen carrier (LOHC) comprising at least one selected from the group consisting of copper (Cu) A method for preparing a catalyst for dehydrogenation.
상기 촉매금속은 탈수소화용 촉매 전체 중량을 기준으로 0.5~10중량%의 함량으로 담지된 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매 제조방법.12. The method of claim 11,
The catalyst metal is supported in an amount of 0.5 to 10% by weight based on the total weight of the catalyst for dehydrogenation.
상기 함침된 결과물을 80~120℃의 온도에서 12~24시간 동안 건조시키는 것인 액상유기수소운반체(LOHC) 탈수소화용 촉매 제조방법.12. The method of claim 11,
A method for preparing a catalyst for dehydrogenation of a liquid organic hydrogen carrier (LOHC), wherein the impregnated product is dried at a temperature of 80 to 120° C. for 12 to 24 hours.
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