KR20230156189A - Method for producing a non-noble metal-based catalyst for decomposition of ammonia, and a non-noble metal-based catalyst for decomposition of ammonia prepared by the method - Google Patents
Method for producing a non-noble metal-based catalyst for decomposition of ammonia, and a non-noble metal-based catalyst for decomposition of ammonia prepared by the method Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 84
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title abstract description 6
- 239000010970 precious metal Substances 0.000 claims abstract description 47
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 101
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- 229910052684 Cerium Inorganic materials 0.000 claims description 35
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000012695 Ce precursor Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- -1 nickel-cerium ammonia Chemical compound 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000011363 dried mixture Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
본 발명은, 암모니아 분해용 비귀금속계 촉매의 제조방법, 및 이 제조방법으로 제조된 암모니아 분해용 비귀금속계 촉매에 관한 것으로서, 구체적으로는 니켈-세륨계의 암모니아 분해용 비귀금속계 촉매의 제조방법, 및 이 제조방법으로 제조된 암모니아 분해용 비귀금속계 촉매에 관한 것이다.The present invention relates to a method for producing a non-precious metal catalyst for decomposing ammonia, and to a non-precious metal catalyst for decomposing ammonia produced by this production method, and specifically to the production of a nickel-cerium-based non-precious metal catalyst for decomposing ammonia. It relates to a method and a non-noble metal-based catalyst for ammonia decomposition produced by this production method.
Description
본 발명은, 암모니아 분해용 비귀금속계 촉매의 제조방법, 및 이 제조방법으로 제조된 암모니아 분해용 비귀금속계 촉매에 관한 것으로서, 구체적으로는 니켈-세륨계의 암모니아 분해용 비귀금속계 촉매의 제조방법, 및 이 제조방법으로 제조된 암모니아 분해용 비귀금속계 촉매에 관한 것이다.The present invention relates to a method for producing a non-precious metal catalyst for decomposing ammonia, and to a non-precious metal catalyst for decomposing ammonia produced by this production method, and specifically to the production of a nickel-cerium-based non-precious metal catalyst for decomposing ammonia. It relates to a method and a non-noble metal-based catalyst for ammonia decomposition produced by this production method.
화석연료는 현재 가장 널리 사용되고 있는 자원이나, 이의 무분별한 사용에 따른 지구온난화 문제가 대두되고 있다. 이에, 청정에너지원의 연구 개발이 중요하게 여겨지고 있으며, 특히 수소의 생산 및 활용을 장려하고 있다. Fossil fuels are currently the most widely used resource, but the problem of global warming due to their indiscriminate use is emerging. Accordingly, research and development of clean energy sources is considered important, and the production and use of hydrogen is especially encouraged.
전 세계적으로 수소가 각광받는 이유는 연료전지를 수소로 운전하는 경우 환경친화적일 뿐만 아니라 기존 내연기관의 2~3배에 이르는 에너지 전환 효율을 기대할 수 있어 향후 수소는 연료전지를 통한 전기 생산, 자동차 분야, 선박 분야 등 다양한 분야에 적용될 것으로 예상되기 때문이다.The reason hydrogen is in the spotlight around the world is that when fuel cells are operated with hydrogen, not only is it environmentally friendly, but energy conversion efficiency can be expected to be 2 to 3 times that of existing internal combustion engines. In the future, hydrogen will be used for electricity production through fuel cells and automobiles. This is because it is expected to be applied to various fields, including industrial and ship fields.
한편, 암모니아는 액화 수소 대비 50% 이상 많은 용량의 수소를 저장할 수 있고 암모니아를 이용하는 수소추출 기술은 현재 유일한 Carbon-free 기술로, 온실가스 배출을 최소화할 수 있어 친환경적이라는 평가를 받고 있다. Meanwhile, ammonia can store more than 50% more hydrogen than liquefied hydrogen, and hydrogen extraction technology using ammonia is currently the only carbon-free technology and is evaluated as environmentally friendly as it can minimize greenhouse gas emissions.
암모니아는 아래의 반응식과 같이 질소와 수소만으로 분해가 가능하여, 화석연료의 분해를 통한 수소 생산과 달리 온실가스 배출과 같은 환경 문제를 야기하지 않아 적극적인 연구가 필요한 실정이다.Ammonia can be decomposed into only nitrogen and hydrogen as shown in the reaction equation below, and unlike hydrogen production through decomposition of fossil fuels, it does not cause environmental problems such as greenhouse gas emissions, so active research is needed.
2NH3 ↔ 3H2 + N2, △H = 46 kJ/mol 2NH3 ↔ 3H2 + N2, △H = 46 kJ/mol
암모니아 분해용 촉매는 다양한 금속을 사용하여 제조되고 있다. 특히 루테늄 함유 촉매 개발이 활발하게 진행되고 있으나 루테늄은 희귀금속으로 매장량이 타 광물 대비 매우 소량이어서 고갈 가능성이 높아 최근 가격 변동이 심하게 일어나고 있다. 따라서, 루테늄을 대체할 수 있는 매장량이 풍부하며 가격의 변동성이 적은 비귀금속을 활용하여 촉매를 개발하는 것이 향후 암모니아 분해용 촉매 개발 방향성이 될 것이다. Catalysts for ammonia decomposition are manufactured using various metals. In particular, the development of ruthenium-containing catalysts is actively progressing, but ruthenium is a rare metal and its reserves are very small compared to other minerals, so there is a high possibility of depletion, so recent price fluctuations have occurred. Therefore, developing catalysts using non-precious metals with abundant reserves and low price volatility that can replace ruthenium will be the direction of development of catalysts for ammonia decomposition in the future.
종래기술로서 일본등록특허 제5800719호는 수소 제조용 촉매, 및 이를 이용한 수소 제조방법에 관한 것으로 이산화규소를 지지체로 사용하는 촉매를 이용하여 암모니아로부터 수소를 제조하는 방법을 개시하고 있고, 일본공개특허 제2001-300314호에는 철-세리아 담체를 포함하는 암모니아 분해용 촉매를, 한국공개특허 제2008-0002881호에는 다공질 실리카 알루미나에 금속을 담지시킨 암모니아 분해용 촉매를 개시하고 있다. As a prior art, Japanese Patent No. 5800719 relates to a catalyst for producing hydrogen and a method for producing hydrogen using the same. It discloses a method of producing hydrogen from ammonia using a catalyst using silicon dioxide as a support, and Japanese Patent Publication No. No. 2001-300314 discloses a catalyst for ammonia decomposition containing an iron-ceria carrier, and Korean Patent Publication No. 2008-0002881 discloses a catalyst for ammonia decomposition in which a metal is supported on porous silica alumina.
실제 암모니아 분해 공정 온도는 550℃ ~ 600℃이나 종래의 촉매들은 550℃에서 암모니아 전환율이 낮기 때문에 550℃에서도 촉매 활성이 우수하고 암모니아 전환율이 높은 촉매 개발이 시급한 실정이다.The actual ammonia decomposition process temperature is 550°C to 600°C, but since conventional catalysts have a low ammonia conversion rate at 550°C, there is an urgent need to develop a catalyst with excellent catalytic activity and high ammonia conversion rate even at 550°C.
본 발명은, 상기와 같은 문제점, 즉 550℃ 이상의 온도에서 안정적이면서도 암모니아 분해 성능이 우수한 암모니아 분해용 비귀금속계 촉매의 제조방법, 및 이 제조방법으로 제조된 암모니아 분해용 비귀금속계 촉매를 제공하는 것을 그 목적으로 한다.The present invention provides a method for producing a non-precious metal catalyst for ammonia decomposition that is stable at a temperature of 550° C. or higher and has excellent ammonia decomposition performance to solve the above problems, and a non-precious metal catalyst for ammonia decomposition produced by this production method. It is for that purpose.
그러나, 본 발명이 해결하고자 하는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.
상기와 같은 목적을 달성하기 위하여, In order to achieve the above objectives,
본 발명의 암모니아 분해용 비귀금속계 촉매의 제조방법은,The method for producing a non-precious metal catalyst for ammonia decomposition of the present invention is,
(a) 니켈 및 세륨 전구체를 동시에 용매에 녹여 니켈-세륨 혼합 용액을 형성하는 단계; (a) dissolving nickel and cerium precursors simultaneously in a solvent to form a nickel-cerium mixed solution;
(b) 상기 (a) 단계의 혼합 용액에 촉매 지지체를 혼합 후, 증발기(evaporator)를 통해 용매를 제거하여 지지체에 니켈 및 세륨을 함침시키는 단계; (b) mixing the catalyst support with the mixed solution of step (a), removing the solvent through an evaporator, and impregnating the support with nickel and cerium;
(c) 상기 (b) 단계의 니켈 및 세륨이 함침된 지지체를 건조 후, 400℃ 내지 500℃ 미만에서 소성을 하는 단계:를 포함하는 1 step 촉매 제조방법인 것을 특징으로 한다.(c) drying the support impregnated with nickel and cerium in step (b) and then calcining it at 400°C to less than 500°C.
상기 (a) 단계의 니켈 및 세륨 전구체는 할로겐 원소를 포함하지 않는 화합물이며, 용매는 메탄올, 에탄올, 헥산, 톨루엔, 증류수, 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다.The nickel and cerium precursors in step (a) are compounds that do not contain a halogen element, and the solvent may be selected from the group consisting of methanol, ethanol, hexane, toluene, distilled water, and mixtures thereof.
상기의 제조방법으로 제조된 본 발명의 암모니아 분해용 비귀금속계 촉매는 니켈 및 세륨 금속원소를 포함하며, 하기 화학식 1로 표시되는 것을 특징으로 한다.The non-noble metal-based catalyst for ammonia decomposition of the present invention prepared by the above production method contains nickel and cerium metal elements and is characterized by being represented by the following formula (1).
Ni-Ce/X [화학식 1]Ni-Ce/X [Formula 1]
상기 화학식 1에서 X는 촉매 지지체이며, 상기 촉매 지지체로는 CeO2, ZrO2, TiO2, MgO, Al2O3, V2O5, Fe2O3, Co3O4, Ce-ZrOx, MgO-Al2O3, 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다. In Formula 1 , _ _ _ _ _ _ _ _ , MgO-Al 2 O 3 , and mixtures thereof.
또한, 상기 화학식 1에서 니켈과 세륨의 담지 함량은 전체 촉매 중량에 대해 10 내지 40중량% 비율로 담지될 수 있다. 바람직하게는 15 내지 25 중량% 비율로 담지될 수 있다. 이때의 니켈과 세륨의 중량비는 1:0.1 내지 1:3이며, 바람직하게는 1:0.5 내지 1:1.5 이다.Additionally, in Formula 1, the supported content of nickel and cerium may be 10 to 40% by weight based on the total weight of the catalyst. Preferably, it can be supported at a ratio of 15 to 25% by weight. At this time, the weight ratio of nickel and cerium is 1:0.1 to 1:3, preferably 1:0.5 to 1:1.5.
상기 본 발명의 암모니아 분해용 비귀금속계 촉매의 제조방법에 의하여 제조된 촉매는 파우더 타입, 펠렛 타입 등일 수 있다.The catalyst prepared by the method for producing a non-precious metal catalyst for ammonia decomposition of the present invention may be of powder type, pellet type, etc.
상기 본 발명의 니켈-세륨계 암모니아 분해용 비귀금속계 촉매에 의한 암모니아 전환율은 암모니아 분해용 촉매 온도 550℃ 이상에서 85% 이상을 나타내며, 특히 600℃ 이상에서는 100%를 나타낼 수 있다.The ammonia conversion rate by the nickel-cerium-based non-precious metal catalyst for ammonia decomposition of the present invention can be 85% or more at a catalyst temperature for ammonia decomposition of 550°C or higher, and in particular, can be 100% at 600°C or higher.
본 발명의 암모니아 분해용 비귀금속계 촉매는 비귀금속계 촉매로서 가격이 저렴하면서도 암모니아 분해용 촉매 온도 550℃ 이상에서 85% 이상을 나타내고, 특히 600℃ 이상에서는 100%의 우수한 암모니아 전환율을 나타내며, 이러한 상기 온도에서의 암모니아 전환율은 종래의 암모니아 분해용 비귀금속계 촉매에 비하여 효과가 우수한 것이며, 귀금속인 루테늄계 암모니아 분해용 촉매에 의한 암모니아 전환율과 거의 유사한 전환율을 나타냄으로써 비귀금속을 사용함에 따른 경제적인 장점이 있다. The non-noble metal-based catalyst for decomposing ammonia of the present invention is a non-precious metal-based catalyst that is inexpensive and exhibits an excellent ammonia conversion rate of 85% or more at a catalyst temperature of 550°C or higher, and especially 100% at 600°C or higher. The ammonia conversion rate at the above temperature is more effective than the conventional non-noble metal-based catalyst for decomposing ammonia, and shows a conversion rate almost similar to the ammonia conversion rate by a catalyst for decomposing ammonia based on ruthenium, which is a precious metal, making economical use of the non-precious metal. There is an advantage.
또한, 본 발명의 암모니아 분해용 비귀금속계 촉매의 제조방법은 니켈 및 세륨 전구체를 동시에 용매에 용해하여 제조하는 1 step 촉매 제조방법으로서 촉매의 제조가 간단하여 촉매 제조에 있어서도 경제적으로도 우수하다. In addition, the manufacturing method of the non-noble metal-based catalyst for ammonia decomposition of the present invention is a one-step catalyst manufacturing method in which nickel and cerium precursors are simultaneously dissolved in a solvent. The catalyst preparation is simple and is economically excellent in catalyst preparation.
도 1은 본 발명 실시예 1, 및 비교예 1과 비교예 2에 의하여 제조된 암모니아 분해용 비귀금속계 촉매에 의한 350℃ 내지 700℃의 촉매 온도에서의 암모니아 전환율을 나타낸 그래프이다.
도 2는 본 발명 실시예 1, 실시예 2, 및 실시예 3에 의하여 제조된 암모니아 분해용 비귀금속계 촉매에 의한 350℃ 내지 700℃의 촉매 온도에서의 암모니아 전환율을 나타낸 그래프이다.
도 3은 실시예 1 및 비교예 3에 의하여 제조된 암모니아 분해용 비귀금속계 촉매에 의한 350℃ 내지 700℃의 촉매 온도에서의 암모니아 전환율을 나타낸 그래프이다.
도 4는 실시예 1 및 비교예 1과 비교예 2에 의하여 제조된 암모니아 분해용 비귀금속계 촉매에 담지된 니켈 입자 크기를 나타낸 그래프이다.
도 5는 실시예 2 및 비교예 1과 비교예 2에 의하여 제조된 암모니아 분해용 비귀금속계 촉매 표면에 담지된 니켈 입자 크기를 나타낸 그래프이다.Figure 1 is a graph showing the ammonia conversion rate at a catalyst temperature of 350°C to 700°C by the non-noble metal-based catalyst for decomposing ammonia prepared in Example 1 of the present invention and Comparative Examples 1 and 2.
Figure 2 is a graph showing the ammonia conversion rate at a catalyst temperature of 350°C to 700°C by non-noble metal-based catalysts for ammonia decomposition prepared in Examples 1, 2, and 3 of the present invention.
Figure 3 is a graph showing the ammonia conversion rate at a catalyst temperature of 350°C to 700°C by the non-precious metal catalyst for ammonia decomposition prepared in Example 1 and Comparative Example 3.
Figure 4 is a graph showing the size of nickel particles supported on non-precious metal catalysts for ammonia decomposition prepared in Example 1 and Comparative Examples 1 and 2.
Figure 5 is a graph showing the size of nickel particles supported on the surface of a non-precious metal catalyst for decomposing ammonia prepared in Example 2 and Comparative Examples 1 and 2.
이하 본 발명의 암모니아 분해용 비귀금속계 촉매, 및 이의 제조방법을 상세히 설명한다. Hereinafter, the non-noble metal-based catalyst for ammonia decomposition of the present invention and its manufacturing method will be described in detail.
이하 설명에서 사용되는 용어에 있어서 다른 정의가 없다면 본 명세서에서 사용되는 모든 용어(기술 및 과학적 용어 포함)는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 공통적으로 이해될 수 있는 의미로 사용될 수 있으며, 또한 단수형은 특별히 문장에서 정의하지 않는 한 복수형도 포함된다.Unless there is another definition for terms used in the following description, all terms (including technical and scientific terms) used in this specification will be used with a meaning that can be commonly understood by those skilled in the art in the technical field to which the present invention pertains. Also, the singular form also includes the plural form unless specifically defined in the sentence.
본 발명의 암모니아 분해용 비귀금속계 촉매의 제조방법은,The method for producing a non-precious metal catalyst for ammonia decomposition of the present invention is,
(a) 니켈 및 세륨 전구체를 동시에 용매에 녹여 니켈-세륨 혼합 용액을 형성하는 단계; (a) dissolving nickel and cerium precursors simultaneously in a solvent to form a nickel-cerium mixed solution;
(b) 상기 (a) 단계의 혼합 용액에 촉매 지지체를 혼합 후, 증발기(evaporator)를 통해 용매를 제거하여 지지체에 니켈 및 세륨을 함침시키는 단계; (b) mixing the catalyst support with the mixed solution of step (a), removing the solvent through an evaporator, and impregnating the support with nickel and cerium;
(c) 상기 (b) 단계의 니켈 및 세륨이 함침된 지지체를 건조 후, 400℃ 내지 500℃ 미만에서 소성을 하는 단계:를 포함하는 1 step 촉매 제조방법인 것을 특징으로 한다.(c) drying the support impregnated with nickel and cerium in step (b) and then calcining it at 400°C to less than 500°C.
상기 (a) 단계의 니켈 및 세륨의 전구체는 할로겐 원소를 포함하지 않는 화합물이며, 바람직하게는 금속 질산화물 등이고, 구체적으로 질산니켈 6수화물, 및 질산세륨 6수화물 등이다.The precursor of nickel and cerium in step (a) is a compound that does not contain a halogen element, and is preferably a metal nitrate, such as nickel nitrate hexahydrate and cerium nitrate hexahydrate.
또한, 상기 (a) 단계의 용매는 메탄올, 에탄올, 헥산, 톨루엔, 증류수, 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다.Additionally, the solvent in step (a) may be selected from the group consisting of methanol, ethanol, hexane, toluene, distilled water, and mixtures thereof.
상기 용매의 사용량은 니켈 및 세륨의 전구체의 전체 합의 8 내지 15배(중량비)로 사용할 수 있다.The amount of the solvent used can be 8 to 15 times (weight ratio) the total sum of the nickel and cerium precursors.
상기 (a) 단계의 니켈 및 세륨 전구체의 사용량은, 전체 촉매 중량에 대하여 니켈과 세륨이 10 내지 40중량% 비율로 담지될 수 있는 양이고, 이때 상기 니켈 원소 및 세륨 원소의 중량비는 1:0.1 내지 1:3이며, 바람직하게는 1:0.5 내지 1:1.5 이다.The amount of nickel and cerium precursors used in step (a) is such that nickel and cerium can be supported at a ratio of 10 to 40% by weight based on the total weight of the catalyst, and the weight ratio of the nickel element and the cerium element is 1:0.1. to 1:3, preferably 1:0.5 to 1:1.5.
상기 (a) 단계의 니켈-세륨 혼합 용액은 상온에서 사용된 전구체가 완전히 용매에 녹을 때까지 일정 시간, 예를 들어 10분 내지 1시간 동안 교반하여 제조한다. The nickel-cerium mixed solution of step (a) is prepared by stirring at room temperature for a certain period of time, for example, 10 minutes to 1 hour, until the precursor used is completely dissolved in the solvent.
상기 (b) 단계의 증발기(evaporator)를 통한 용매의 제거는, 사용되는 용매를 상온에서 제거할 수 있는 특정의 속도로 특정 시간 동안 이루어질 수 있다. 예를 들어 10 내지 30 rpm의 속도로 약 5시간 내지 10시간 동안 이루어질 수 있다.Removal of the solvent through the evaporator in step (b) may be performed at a specific rate and for a specific time at which the solvent used can be removed at room temperature. For example, it can be done for about 5 to 10 hours at a speed of 10 to 30 rpm.
상기 (c) 단계의 니켈 및 세륨이 함침된 지지체의 건조는, 상기 (b) 단계의 증발기(evaporator) 내부에서 이루어지며, 이때의 온도 및 건조 시간은 약 40℃ 내지 60℃ 및 30분 내지 1시간이다.Drying of the nickel and cerium-impregnated support in step (c) is carried out inside the evaporator in step (b), and the temperature and drying time at this time are about 40°C to 60°C and 30 minutes to 1. It's time.
상기 (c) 단계의 소성 온도가 400℃ 내지 500℃ 미만을 벗어나는 경우 암모니아 전환율이 낮아지는 단점이 있다(비교예 1 및 2, 도 1 참조). 상기 소성 시간은 약 5시간 내지 10시간이다.If the calcination temperature in step (c) is below 400°C to 500°C, there is a disadvantage in that the ammonia conversion rate is lowered (see Comparative Examples 1 and 2 and FIG. 1). The firing time is about 5 to 10 hours.
한편, 본 발명의 상기 1 step 촉매 제조방법이란, 니켈 및 세륨을 모두 동시에 지지체에 함침시키는 방법을 말한다(실시예 1 참조). Meanwhile, the one-step catalyst preparation method of the present invention refers to a method of impregnating both nickel and cerium into a support at the same time (see Example 1).
상기 1 step 제조방법에 의하여 제조된 본 발명의 암모니아 분해용 비귀금속계 촉매는, 통상적인 제조방법인 2 step 제조방법, 즉 일차적으로 지지체에 하나의 금속을 함침시킨 후, 상기 금속이 포함된 지지체에 다시 이차적으로 두 번째 금속를 함침시키는 제조방법(비교예 3 참조)에 의하여 제조된 암모니아 분해용 촉매에 비하여 암모니아 전환율이 우수하다(도 2 참조).The non-noble metal-based catalyst for ammonia decomposition of the present invention manufactured by the above 1-step manufacturing method is a conventional 2-step manufacturing method, that is, first impregnating a support with a metal, and then impregnating a support with the metal. The ammonia conversion rate is superior to that of the ammonia decomposition catalyst manufactured by the manufacturing method of secondarily impregnating the catalyst with a second metal (see Comparative Example 3) (see FIG. 2).
상기와 같은 본 발명의 암모니아 분해용 비귀금속계 촉매의 제조방법에 의하여 제조된 본 발명의 암모니아 분해용 비귀금속계 촉매는, The non-noble metal-based catalyst for ammonia decomposition of the present invention manufactured by the method for producing the non-precious metal-based catalyst for ammonia decomposition of the present invention as described above,
니켈 및 세륨 금속원소를 포함하며, 하기 화학식 1로 표시되는 것을 특징으로 한다.It contains metal elements nickel and cerium, and is characterized by being represented by the following formula (1).
Ni-Ce/XNi-Ce/X
[화학식 1][Formula 1]
상기 화학식 1에서 X는 촉매 지지체이며, 상기 촉매 지지체로는 CeO2, ZrO2, TiO2, MgO, Al2O3, V2O5, Fe2O3, Co3O4, Ce-ZrOx, MgO-Al2O3, 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다. In Formula 1 , _ _ _ _ _ _ _ _ , MgO-Al 2 O 3 , and mixtures thereof.
또한, 상기 화학식 1에서 니켈과 세륨의 담지 함량은 전체 촉매 중량에 대해 10 내지 40중량% 비율로 담지될 수 있다. 바람직하게는 15 내지 25 중량% 비율로 담지될 수 있다. 이때의 니켈과 세륨의 중량비는 1:0.1 내지 1:3이며, 바람직하게는 1:0.5 내지 1:1.5이다.Additionally, in Formula 1, the supported content of nickel and cerium may be 10 to 40% by weight based on the total weight of the catalyst. Preferably, it can be supported at a ratio of 15 to 25% by weight. At this time, the weight ratio of nickel and cerium is 1:0.1 to 1:3, preferably 1:0.5 to 1:1.5.
또한, 상기 암모니아 분해용 비귀금속계 촉매에 포함된 Ni의 입자 크기는 7.5nm 미만이하 일 수 있고, 바람직하게는 7.0nm 이하 일 수 있다.Additionally, the particle size of Ni contained in the non-noble metal catalyst for ammonia decomposition may be less than 7.5 nm, and preferably less than 7.0 nm.
상기 암모니아 분해용 비귀금속계 촉매의 제조방법에 의하여 제조된 암모니아 분해용 비귀금속계 촉매는 파우더 타입, 펠렛 타입 등일 수 있다.The non-precious metal catalyst for ammonia decomposition produced by the method for producing a non-precious metal catalyst for ammonia decomposition may be of powder type, pellet type, etc.
상기 니켈-세륨계 암모니아 분해용 비귀금속계 촉매에 의한 암모니아 전환율은 암모니아 분해용 촉매 온도 550℃ 이상에서 85% 이상을 나타내며, 특히 600℃ 이상에서는 100%를 나타낼 수 있다.The ammonia conversion rate by the nickel-cerium-based non-precious metal catalyst for decomposing ammonia can be 85% or more at a catalyst temperature for ammonia decomposition of 550°C or higher, and in particular, can be 100% at 600°C or higher.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해할 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호 범위를 제한하고자 하는 것은 아니다. The present invention can be better understood by the following examples, which are for illustrative purposes only and are not intended to limit the scope of protection defined by the appended claims.
또한, 본 발명은 하기의 실시예에 한정되지 아니하며, 청구범위에서 청구하는 본 발명의 요지를 벗어나지 않는 범위에서 다양한 변형 실시가 가능하다. In addition, the present invention is not limited to the following examples, and various modifications and implementations are possible without departing from the gist of the present invention as claimed in the claims.
실시예 1: 니켈과 세륨의 중량비가 1:0.5로 포함된 암모니아 분해용 비귀금속계 촉매의 제조 (1 step, 및 소성 온도 400℃) Example 1: Preparation of a non-precious metal catalyst for ammonia decomposition containing nickel and cerium at a weight ratio of 1:0.5 (1 step, calcination temperature 400°C)
질산니켈 6수화물(Nickel(II) nitrate hexahydrate, Sigma Aldrich) 2.477 g와 질산세륨 6수화물(Cerium(III) nitrate hexahydrate, Sigma Aldrich) 0.775 g을 한꺼번에 순수(D.I. water) 50 mL의 용매와 혼합하여 혼합 용액을 제조한 후, 상온에서 약 20분 동안 상기 전구체의 알갱이가 보이지 않을 정도로 교반하였다. Mix 2.477 g of nickel(II) nitrate hexahydrate, Sigma Aldrich and 0.775 g of cerium nitrate hexahydrate (Cerium(III) nitrate hexahydrate, Sigma Aldrich) with 50 mL of pure water (D.I. water) as a solvent. After preparing the solution, it was stirred at room temperature for about 20 minutes to the extent that grains of the precursor were no longer visible.
그 후 상기 혼합 용액에 펠렛 타입의 γ-알루미나(Al2O3) 지지체(Alfa Aesar) 4.25 g을 투입하고 상온에서 20 rpm의 속도로 6시간 동안 증발기(evaporator)를 이용하여 상기 혼합 용액의 용매를 제거하여 상기 화합물 및 지지체의 혼합물을 얻었다.Afterwards, 4.25 g of pellet-type γ-alumina (Al 2 O 3 ) support (Alfa Aesar) was added to the mixed solution, and the solvent of the mixed solution was removed using an evaporator for 6 hours at a speed of 20 rpm at room temperature. was removed to obtain a mixture of the above compound and support.
용매 제거 후 증발기 내에서 상기 혼합물을 회수하지 않은 상태로 50℃에서 30분 동안 건조시킨다. 상기 건조된 혼합물을 증발기에서 회수하고 이를 400℃에서 6시간 동안 소성하여 암모니아 분해용 비귀금속계 촉매인 Al2O3의 지지체를 갖는 니켈 및 세륨 중량비가 1:0.5로 포함된 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 5 g을 얻었다. 이때 니켈 및 세륨 중량%는 전체 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 중 10 중량% 및 5 중량%로 포함된다. After removing the solvent, the mixture is dried in an evaporator at 50°C for 30 minutes without recovery. The dried mixture was recovered in an evaporator and calcined at 400°C for 6 hours to produce nickel-cerium-based ammonia containing nickel and cerium at a weight ratio of 1:0.5 with a support of Al 2 O 3 , a non-precious metal catalyst for ammonia decomposition. 5 g of non-precious metal catalyst for decomposition was obtained. At this time, nickel and cerium weight % are included in 10 weight % and 5 weight % of the total nickel-cerium-based non-precious metal catalyst for decomposing ammonia.
상기 얻어진 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 중 Ni 원자의 입자 크기는 5.3 nm이었다. (PANalytical社, X`Pert PRO-MPD로 분석한 회절 패턴을 Scherrer Equation으로 계산) The particle size of Ni atoms in the obtained non-precious metal catalyst for nickel-cerium-based ammonia decomposition was 5.3 nm. (PANalytical, diffraction pattern analyzed with X`Pert PRO-MPD calculated using Scherrer Equation)
실시예 2: 니켈과 세륨의 중량비가 1:1로 포함된 암모니아 분해용 비귀금속계 촉매의 제조 (1 step, 및 소성 온도 400℃)Example 2: Preparation of a non-precious metal catalyst for ammonia decomposition containing nickel and cerium at a weight ratio of 1:1 (1 step, calcination temperature 400°C)
질산니켈 6수화물(Nickel(II) nitrate hexahydrate, Sigma Aldrich) 2.477 g과 질산세륨 6수화물(Cerium(III) nitrate hexahydrate, Sigma Aldrich) 1.549 g을 사용한 것과 펠렛 타입의 γ-알루미나(Al2O3) 지지체(Alfa Aesar) 4 g을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 암모니아 분해용 비귀금속계 촉매를 제조하여 니켈 및 세륨 중량비가 1:1로 포함된 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 5 g을 얻었다. 이때 니켈 및 세륨 중량%는 전체 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 중 10 중량% 및 10 중량%로 포함된다. 2.477 g of nickel(II) nitrate hexahydrate, Sigma Aldrich, 1.549 g of cerium nitrate hexahydrate (Cerium(III) nitrate hexahydrate, Sigma Aldrich), and pellet-type γ-alumina (Al 2 O 3 ) A non-precious metal catalyst for ammonia decomposition was prepared in the same manner as in Example 1 except for using 4 g of support (Alfa Aesar), and a nickel-cerium ammonia decomposition ratio containing nickel and cerium at a weight ratio of 1:1 was prepared. 5 g of noble metal-based catalyst was obtained. At this time, nickel and cerium weight% are included in 10% by weight and 10% by weight of the total nickel-cerium based non-precious metal catalyst for decomposing ammonia.
상기 얻어진 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 중 Ni 원자의 입자 크기는 5.8 nm이었다. (PANalytical社, X`Pert PRO-MPD로 분석한 회절 패턴을 Scherrer Equation으로 계산) The particle size of Ni atoms in the obtained non-precious metal catalyst for decomposing nickel-cerium ammonia was 5.8 nm. (PANalytical, diffraction pattern analyzed with X`Pert PRO-MPD calculated using Scherrer Equation)
실시예 3: 니켈과 세륨의 중량비가 1:1.5로 포함된 암모니아 분해용 비귀금속계 촉매의 제조 (1 step, 및 소성 온도 400℃)Example 3: Preparation of a non-precious metal catalyst for ammonia decomposition containing nickel and cerium at a weight ratio of 1:1.5 (1 step, calcination temperature 400°C)
질산니켈 6수화물(Nickel(II) nitrate hexahydrate, Sigma Aldrich) 2.477 g과 질산세륨 6수화물(Cerium(III) nitrate hexahydrate, Sigma Aldrich) 2.324 g을 사용한 것과 펠렛 타입의 γ-알루미나(Al2O3) 지지체(Alfa Aesar) 3.75 g을 사용한 것 외에는 상기 실시예 1과 동일한 방법으로 암모니아 분해용 비귀금속계 촉매를 제조하여 니켈 및 세륨 중량비가 1:1.5로 포함된 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 5 g을 얻었다. 이때 니켈 및 세륨의 중량%는 전체 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 중 10 중량% 및 15 중량%로 포함된다. 2.477 g of nickel(II) nitrate hexahydrate, Sigma Aldrich, 2.324 g of cerium nitrate hexahydrate (Cerium(III) nitrate hexahydrate, Sigma Aldrich), and pellet-type γ-alumina (Al 2 O 3 ) A non-precious metal catalyst for ammonia decomposition was prepared in the same manner as in Example 1 except that 3.75 g of support (Alfa Aesar) was used, and a nickel-cerium based non-precious metal catalyst for ammonia decomposition containing nickel and cerium weight ratio of 1:1.5 was prepared. 5 g of catalyst was obtained. At this time, the weight percent of nickel and cerium is included in 10 weight percent and 15 weight percent of the total nickel-cerium-based non-precious metal catalyst for decomposing ammonia.
상기 얻어진 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 중 Ni 원자의 입자 크기는 7.3 nm이었다. (PANalytical社, X`Pert PRO-MPD로 분석한 회절 패턴을 Scherrer Equation으로 계산) The particle size of Ni atoms in the obtained non-precious metal catalyst for decomposing nickel-cerium ammonia was 7.3 nm. (PANalytical, diffraction pattern analyzed with X`Pert PRO-MPD calculated using Scherrer Equation)
비교예 1: 니켈과 세륨의 중량비가 1:0.5로 포함된 암모니아 분해용 비귀금속계 촉매의 제조 (1 step, 및 소성 온도 500℃) Comparative Example 1: Preparation of a non-precious metal catalyst for ammonia decomposition containing nickel and cerium at a weight ratio of 1:0.5 (1 step, calcination temperature 500°C)
소성 온도를 500℃에서 실시한 것을 제외하고는 상기 실시예 1과 같이 진행하여 암모니아 분해용 비귀금속계 촉매인 Al2O3의 지지체를 갖는 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 5 g을 얻었다. 5 g of a nickel-cerium-based non-noble metal catalyst for ammonia decomposition having a support of Al 2 O 3 , which is a non-noble metal catalyst for ammonia decomposition, was obtained in the same manner as in Example 1 except that the calcination temperature was carried out at 500°C. .
상기 얻어진 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 중 Ni 원자의 입자 크기는 7.5 nm이었다. (PANalytical社, X`Pert PRO-MPD로 분석한 회절 패턴을 Scherrer Equation으로 계산) The particle size of Ni atoms in the obtained non-precious metal catalyst for decomposing nickel-cerium ammonia was 7.5 nm. (PANalytical, diffraction pattern analyzed with X`Pert PRO-MPD calculated using Scherrer Equation)
비교예 2: 니켈과 세륨의 중량비가 1: 0.5로 포함된 암모니아 분해용 비귀금속계 촉매의 제조 (1 step, 및 소성 온도 700℃) Comparative Example 2: Preparation of a non-precious metal catalyst for ammonia decomposition containing nickel and cerium at a weight ratio of 1:0.5 (1 step, calcination temperature 700°C)
소성 온도를 700℃에서 실시한 것을 제외하고는 상기 실시예 1과 같이 진행하여 암모니아 분해용 비귀금속계 촉매인 Al2O3의 지지체를 갖는 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 5 g을 얻었다. 5 g of a nickel-cerium-based non-noble metal catalyst for ammonia decomposition having a support of Al 2 O 3 , a non-noble metal catalyst for ammonia decomposition, was obtained in the same manner as in Example 1 except that the calcination temperature was carried out at 700°C. .
상기 얻어진 니켈-세륨계 암모니아 분해용 비귀금속계 촉매 중 Ni 원자의 입자 크기는 9.6 nm이었다. (PANalytical社, X`Pert PRO-MPD로 분석한 회절 패턴을 Scherrer Equation으로 계산) The particle size of Ni atoms in the obtained non-precious metal catalyst for decomposing nickel-cerium ammonia was 9.6 nm. (PANalytical, diffraction pattern analyzed with X`Pert PRO-MPD calculated using Scherrer Equation)
비교예 3. 니켈과 세륨의 중량비가 1:0.5로 포함된 암모니아 분해용 비귀금속계 촉매의 제조 (2 step 및 소성 온도 400℃) Comparative Example 3. Preparation of a non-precious metal catalyst for ammonia decomposition containing nickel and cerium at a weight ratio of 1:0.5 (2 steps and calcination temperature 400°C)
우선 1단계로서, 질산 세륨 6수화물(Cerium(III) nitrate hexahydrate, Sigma Aldrich) 0.775 g을 순수(D.I. water) 50 mL와 혼합하여 용액을 제조한 후, 상온에서 약 20분 동안 전구체의 알갱이가 보이지 않을 정도로 교반하였다. 그 후 펠렛 타입의 γ-알루미나(Al2O3) 지지체(Alfa Aesar) 4.25 g을 상기 용액에 투입하고, 상온에서 6시간 동안 증발기(evaporator)를 이용하여 용액의 액상 성분을 제거하였다. 액상 성분이 제거된 지지체 및 세륨 전구체의 혼합물을 증발기 내에서 회수하지 않은 상태로 50℃에서 30분 동안 건조시킨다. 상기 건조가 이루어진 혼합물을 증발기에서 회수하고, 이를 900℃에서 4시간 동안 소성하여 최종적으로 지지체에 세륨 금속이 함유된 물질(Ce/Al2O3)을 얻었다.First, in the first step, a solution was prepared by mixing 0.775 g of Cerium(III) nitrate hexahydrate (Sigma Aldrich) with 50 mL of pure water (DI water), and no grains of the precursor were visible for about 20 minutes at room temperature. It was stirred to the extent that it was not stirred. Afterwards, 4.25 g of pellet-type γ-alumina (Al 2 O 3 ) support (Alfa Aesar) was added to the solution, and the liquid component of the solution was removed using an evaporator at room temperature for 6 hours. The mixture of the support and cerium precursor from which the liquid component has been removed is dried at 50° C. for 30 minutes without recovery in an evaporator. The dried mixture was recovered from the evaporator and calcined at 900°C for 4 hours to finally obtain a material containing cerium metal in the support (Ce/Al 2 O 3 ).
한편, 질산니켈 6수화물(Nickel(II) nitrate hexahydrate, Sigma Aldrich) 2.477 g을 순수(D.I. water) 50 mL와 혼합한 후, 상온에서 약 20분 동안 전구체의 알갱이가 보이지 않을 정도로 교반하여 질산니켈 6수화물 용액을 제조하였다. Meanwhile, 2.477 g of Nickel(II) nitrate hexahydrate (Sigma Aldrich) was mixed with 50 mL of pure water (D.I. water), and then stirred at room temperature for about 20 minutes to the point where no precursor grains were visible to obtain nickel nitrate 6. A hydrate solution was prepared.
2단계로서, 상기 제조된 질산니켈 6수화물 용액에 상기 1단계에서 제조된 5중량%의 세륨 금속이 함유된 지지체 물질(Ce/Al2O3)을 투입하여 혼합물을 제조한 후, 상온에서 6시간 동안 증발기(evaporator)를 이용하여 혼합물의 액상 성분을 제거하였다. 액상 성분이 제거된 상기 혼합물을 증발기 내에서 회수하지 않은 상태로 50℃에서 30분 동안 건조시킨다. 상기 건조가 이루어진 혼합물을 증발기에서 회수하고, 이를 400℃에서 6시간 동안 소성하여 최종적으로 지지체에 니켈 및 세륨 중량비가 1:0.5로 포함된 물질(Ni/Ce/Al2O3)를 얻었다.In the second step, a mixture was prepared by adding the support material (Ce/Al 2 O 3 ) containing 5% by weight of cerium metal prepared in step 1 to the nickel nitrate hexahydrate solution prepared above, and then incubated at room temperature for 6 hours. The liquid component of the mixture was removed using an evaporator for a period of time. The mixture from which the liquid component has been removed is dried at 50°C for 30 minutes without recovery in an evaporator. The dried mixture was recovered in an evaporator, and calcined at 400°C for 6 hours to finally obtain a material (Ni/Ce/Al 2 O 3 ) containing nickel and cerium in the support at a weight ratio of 1:0.5.
이상, 본 발명을 바람직한 실시예를 들어 상세하게 설명하였으나, 본 발명은 상기 실시예에 한정되지 않고, 본 발명의 기술적 사상의 범위 내에서 당 분야에서 통상의 지식을 가진 자에 의하여 여러 가지 변형이 가능하다.Above, the present invention has been described in detail with preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. possible.
Claims (6)
(b) 상기 (a) 단계의 혼합 용액에 촉매 지지체를 혼합 후, 증발기(evaporator)를 통해 용매를 제거하여 지지체에 니켈 및 세륨을 함침시키는 단계;
(c) 상기 (b) 단계의 니켈 및 세륨이 함침된 지지체를 건조 후, 400℃ 내지 500℃ 미만에서 소성을 하는 단계:를 포함하는 것을 특징으로 하는, 암모니아 분해용 비귀금속계 촉매의 제조방법(a) dissolving nickel and cerium precursors simultaneously in a solvent to form a nickel-cerium mixed solution;
(b) mixing the catalyst support with the mixed solution of step (a), removing the solvent through an evaporator, and impregnating the support with nickel and cerium;
(c) drying the support impregnated with nickel and cerium in step (b) and then calcining it at 400°C to less than 500°C. A method for producing a non-noble metal-based catalyst for decomposing ammonia, comprising:
상기 (a) 단계의 니켈 및 세륨 전구체는 할로겐 원소를 포함하지 않는 화합물이며, 용매는 메탄올, 에탄올, 헥산, 톨루엔, 증류수, 및 이들의 혼합물로 이루어진 군에서 선택되는 것을 특징으로 하는, 암모니아 분해용 비귀금속계 촉매의 제조방법According to paragraph 1,
The nickel and cerium precursors in step (a) are compounds that do not contain halogen elements, and the solvent is selected from the group consisting of methanol, ethanol, hexane, toluene, distilled water, and mixtures thereof. Method for producing non-precious metal catalysts
상기 (a) 단계의 니켈 및 세륨 전구체의 사용량은, 전체 촉매 중량에 대하여 니켈과 세륨이 10 내지 40중량% 비율로 담지될 수 있는 양이고, 이때 상기 니켈 원소 및 세륨 원소의 중량비는 1:0.1 내지 1:3인 것을 특징으로 하는, 암모니아 분해용 비귀금속계 촉매의 제조방법According to paragraph 1,
The amount of nickel and cerium precursors used in step (a) is such that nickel and cerium can be supported at a ratio of 10 to 40% by weight based on the total weight of the catalyst, and the weight ratio of the nickel element and the cerium element is 1:0.1. Method for producing a non-precious metal catalyst for ammonia decomposition, characterized in that the ratio is 1:3.
상기 (a) 단계의 니켈-세륨 혼합 용액은 상온에서 사용된 니켈 및 세륨 전구체가 완전히 용매에 녹을 때까지 교반하여 제조하고,
상기 (b) 단계의 증발기(evaporator)를 통한 용매의 제거는, 사용되는 용매를 상온에서 10 내지 30 rpm의 속도로 5시간 내지 10시간 동안 이루어지며,
상기 (c) 단계의 니켈 및 세륨이 함침된 지지체의 건조는, 상기 (b) 단계의 증발기(evaporator) 내부에서 이루어지며, 이때의 온도 및 건조 시간은 약 40℃ 내지 60℃ 및 30분 내지 1시간인 것을 특징으로 하는, 암모니아 분해용 비귀금속계 촉매의 제조방법According to paragraph 1,
The nickel-cerium mixed solution in step (a) is prepared by stirring at room temperature until the nickel and cerium precursors used are completely dissolved in the solvent,
The removal of the solvent through the evaporator in step (b) is carried out at room temperature and at a speed of 10 to 30 rpm for 5 to 10 hours,
Drying of the nickel and cerium-impregnated support in step (c) is carried out inside the evaporator in step (b), and the temperature and drying time at this time are about 40°C to 60°C and 30 minutes to 1. Method for producing a non-precious metal catalyst for ammonia decomposition, characterized in that the time
Ni-Ce/X
[화학식 1]
상기 화학식 1에서 X는 촉매 지지체이고,
상기 화학식 1에서 니켈과 세륨의 담지 함량은 전체 촉매 중량에 대해 10 내지 40중량% 비율이며, 이때의 니켈과 세륨의 중량비는 1:0.1 내지 1:3인 것을 특징으로 하는, 암모니아 분해용 비귀금속계 촉매.A non-noble metal-based catalyst for decomposing ammonia, produced by the production method of any one of claims 1 to 4 and represented by the following formula (1),
Ni-Ce/X
[Formula 1]
In Formula 1, X is a catalyst support,
In Formula 1, the supported content of nickel and cerium is 10 to 40% by weight based on the total catalyst weight, and the weight ratio of nickel and cerium at this time is 1:0.1 to 1:3. Non-precious metal for ammonia decomposition system catalyst.
상기 촉매 지지체로는 CeO2, ZrO2, TiO2, MgO, Al2O3, V2O5, Fe2O3, Co3O4, Ce-ZrOx, MgO-Al2O3, 및 이들의 혼합물로 이루어진 군에서 선택되는 것을 특징으로 하는, 암모니아 분해용 비귀금속계 촉매.
According to clause 5,
The catalyst support includes CeO 2 , ZrO 2 , TiO 2 , MgO, Al 2 O 3 , V 2 O 5 , Fe 2 O 3 , Co 3 O 4 , Ce-ZrO x , MgO-Al 2 O 3 , and these. A non-precious metal catalyst for ammonia decomposition, characterized in that it is selected from the group consisting of a mixture of.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001300314A (en) | 2000-04-26 | 2001-10-30 | Kinya Adachi | Manufacture of catalyst for ammonia regeneration type hydrogen production and modification condition |
| KR20080002881A (en) | 2007-10-26 | 2008-01-04 | 즈도케미 쇼쿠바이 가부시키가이샤 | Ammonia decomposition catalyst and process for decomposition of ammonia using the catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001300314A (en) | 2000-04-26 | 2001-10-30 | Kinya Adachi | Manufacture of catalyst for ammonia regeneration type hydrogen production and modification condition |
| KR20080002881A (en) | 2007-10-26 | 2008-01-04 | 즈도케미 쇼쿠바이 가부시키가이샤 | Ammonia decomposition catalyst and process for decomposition of ammonia using the catalyst |
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