KR20160084359A - A catalyst with a high efficiency - Google Patents
A catalyst with a high efficiency Download PDFInfo
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- KR20160084359A KR20160084359A KR1020160086147A KR20160086147A KR20160084359A KR 20160084359 A KR20160084359 A KR 20160084359A KR 1020160086147 A KR1020160086147 A KR 1020160086147A KR 20160086147 A KR20160086147 A KR 20160086147A KR 20160084359 A KR20160084359 A KR 20160084359A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 239000002245 particle Substances 0.000 claims abstract description 99
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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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
- 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
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J32/00—
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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Abstract
Description
본 발명은 고 효율 촉매에 관한 것이고, 보다 상세하게는 촉매 지지체의 구조를 변화시킴으로써 효율이 향상된 촉매에 관한 것이다. The present invention relates to a high efficiency catalyst, and more particularly to a catalyst having improved efficiency by changing the structure of the catalyst support.
촉매의 성능을 향상시키기 위하여 다양한 방법이 연구되고 있는데, 일반적으로는 촉매 지지체와 그 위에 분산되는 촉매 활성 입자간 상호작용을 제어하는 기술에 관한 것이다. 예를 들면, 촉매 지지체에 촉매 활성 입자가 아닌 다른 물질을 약간 도핑하여 조촉매로 사용하거나, 촉매 지지체 자체의 화학적 성질을 변형시켜 그 촉매 지지체에 분산되는 촉매 활성 입자의 촉매 성능을 높이는 연구 등이다.A variety of methods have been studied to improve the performance of the catalyst, and generally relates to techniques for controlling the interaction between the catalyst support and the catalytically active particles dispersed thereon. For example, research on increasing the catalytic performance of the catalytically active particles dispersed in the catalyst support by modifying the chemical properties of the catalyst support itself or by using the catalyst support as a cocatalyst by slightly doping a substance other than the catalytically active particles .
한편, 노출된 촉매 활성 입자의 표면적이 높을수록 촉매의 성능이 높아지므로, 같은 양의 촉매 활성 입자가 같은 성질의 촉매 지지체에 분산된다고 할 때, 촉매 활성 입자를 가능한 한 작은 입자로 분산시키는 것이 촉매의 성능을 높이는데 유리하다. 또한 촉매 지지체에 분산된 촉매 활성 입자들과 촉매 지지체와의 상호작용이 약하면, 촉매 활성 입자들은 촉매 지지체 표면에서 움직이게 되고 서로 뭉치는 소결 (sintering) 현상이 일어나며, 그만큼 촉매 활성 입자의 총 표면적이 감소하게 되어 촉매의 성능이 낮아진다. 또한, 같은 크기의 촉매 활성 입자라고 해도 입자의 모양에 따라 촉매 성능이 달라지기 때문에 촉매 활성 입자 자체의 형상 제어에 관한 연구가 활발히 진행되고 있다. 한편, 촉매 활성 입자의 형상 제어는 주로 낮은 온도에서 행해지는데, 고온 고압의 반응 환경에 적용되는 촉매의 경우엔 촉매 활성 입자의 형상이 상기 반응 조건에서 열역학적 평형 상태의 형상에 가까운 형상으로 변형되는 문제점이 있다. 예를 들면, 자동차등 내연기관 배기가스 정화용, 발전소, 소각로등 오염가스 배출원의 배기가스 정화용 촉매재료의 효율을 높이는데 적용할 수 있기 위해서는 고온 고압의 반응 환경에서도 촉매 활성 입자의 형상이 유지되어야 촉매의 효율성이 유지될 수 있다.On the other hand, the higher the surface area of the exposed catalytic active particles, the higher the performance of the catalyst. Therefore, when it is assumed that the same amount of catalytically active particles are dispersed in a catalyst support of the same nature, It is advantageous to enhance the performance of the system. Further, when the interaction between the catalytically active particles dispersed in the catalyst support and the catalyst support is weak, the catalytically active particles move on the surface of the catalyst support and sintering occurs, and the total surface area of the catalytically active particles decreases And the performance of the catalyst is lowered. In addition, since the catalytic performance varies depending on the shape of the particles even in the case of the catalytically active particles of the same size, studies on the shape control of the catalytically active particles themselves have been actively conducted. On the other hand, control of the shape of the catalytically active particles is mainly performed at a low temperature. In the case of a catalyst applied to a high-temperature and high-pressure reaction environment, the shape of the catalytically active particles is deformed into a shape close to the shape of the thermodynamic equilibrium state . For example, it is necessary to maintain the shape of the catalytically active particles even in a high-temperature and high-pressure reaction environment in order to be able to be applied to enhance the efficiency of exhaust gas purification catalyst materials for pollutant emission sources such as internal combustion engines, Can be maintained.
지금까지 촉매의 성능을 향상시키는 연구에는 촉매 활성 입자를 촉매 지지체에 가능한 한 작은 크기로 분산시키는 연구, 촉매 지지체 위에 분산된 입자들이 촉매 지지체와 강하게 상호작용하여 고온 고압의 반응 환경에서도 움직이지 않고 촉매 활성 입자들이 서로 만나 뭉치지 않도록 하는 연구, 촉매 활성 입자의 형상 자체를 제어하는 연구가 대부분이었다. 그러나, 이러한 촉매들은 촉매 지지체의 화학적 성질을 변형시키거나 조촉매 등 촉매 활성 입자와 다른 물질을 같이 분산하거나 촉매 활성 입자 자체의 형상을 제어하는 등의 번거로운 공정을 거쳐야 하는 문제점이 있다.Research to improve the performance of the catalyst has been carried out so far that studies on dispersing catalytically active particles into a catalyst support in a small size as much as possible have shown that the particles dispersed on the catalyst support strongly interact with the catalyst support, Research to prevent active particles from clumping together, and most research to control the shape of catalytically active particles themselves. However, these catalysts have a problem in that they require a complicated process such as modifying the chemical properties of the catalyst support, dispersing the catalytically active particles such as co-catalysts in the same manner, or controlling the shape of the catalytically active particles themselves.
본 발명은, 촉매 활성 입자의 분산성을 향상하기 위하여, 촉매 지지체의 화학적 성질을 변형시키거나 조촉매 등 촉매 활성 입자와 다른 물질을 같이 분산하거나 촉매 활성 입자 자체의 형상을 제어하는 등의 번거로운 공정을 거치는 대신, 촉매 지지체의 구조를 제어하여 촉매 활성 입자의 분산도를 높게 유지하고, 이를 통해 효율이 높은 촉매를 제공하고자 한다.DISCLOSURE OF THE INVENTION It is an object of the present invention to improve the dispersibility of catalytically active particles by modifying the chemical properties of the catalyst support or by dispersing other materials such as catalyst catalyst particles such as co-catalysts or controlling the shape of the catalytically active particles themselves , The structure of the catalyst support is controlled to maintain the degree of dispersion of the catalytically active particles at a high level, thereby providing a highly efficient catalyst.
본 발명은 촉매 활성 입자, 및 촉매 활성 입자를 지지하고 표면 곡률을 가지는 촉매 지지체 입자를 포함하는 촉매를 제공한다.The present invention provides a catalyst comprising catalytically active particles and catalyst support particles supporting the catalytically active particles and having surface curvature.
또한, 본 발명은 촉매 활성 입자, 및 바늘 형상을 특징으로 하는 표면 곡률을 가지는 촉매 지지체 입자를 포함하는 촉매를 제공한다. The present invention also provides a catalyst comprising catalytically active particles and catalyst support particles having a surface curvature characterized by a needle shape.
더욱 상세하게는, 본 발명은 감마 알루미나, 티타니아, 세리아로 이루어진 군 중에서 하나 이상을 선택하는 것을 특징으로 하는 촉매 지지체 입자를 포함하는 촉매를 제공한다.More particularly, the present invention provides a catalyst comprising catalyst support particles, characterized in that at least one of the group consisting of gamma alumina, titania, and ceria is selected.
더욱 더 상세하게는, 본 발명은 백금(Pt), 팔라듐(Pd), 금(Au), 은(Ag), 로듐(Rh)로 이루어진 군 중에서 하나 이상을 선택하는 것을 특징으로 하는 촉매 활성 입자를 포함하는 촉매를 제공한다. More particularly, the present invention relates to a method for producing a catalytically active particle characterized in that at least one selected from the group consisting of platinum (Pt), palladium (Pd), gold (Au), silver (Ag) ≪ / RTI >
더욱 더 상세하게는, 본 발명은 세륨(Ce), 철(Fe), 니켈(Ni), 구리(Cu), 망간(Mn), 텅스텐(W), 안티몬(Sb), 셀레늄(Se), 바나듐(V), 몰리브덴(Mo), 지르코늄(Zr) 및 바륨(Ba)로 이루어진 군 중에서 하나 이상을 선택하여 촉매 지지체 입자 또는 촉매 활성 입자에 도핑되는 것을 특징으로 하는 촉매를 제공한다.More particularly, the present invention relates to a process for the preparation of cerium (Ce), iron (Fe), nickel (Ni), copper (Cu), manganese (Mn), tungsten (W), antimony Wherein at least one selected from the group consisting of molybdenum (V), molybdenum (Mo), zirconium (Zr) and barium (Ba) is selected and doped into the catalyst support particles or the catalytically active particles.
더욱 더 상세하게는, 본 발명은 150~300℃에서 사용할 수 있고, 바람직하게는 200~250℃에서 사용할 수 있는 것을 특징으로 하는 촉매를 제공한다.More particularly, the present invention provides a catalyst which can be used at 150 to 300 ° C, preferably 200 to 250 ° C.
본 발명에 의하면 촉매 지지체의 화학적 특성을 변경하는 등의 복잡한 공정이 없이 촉매 지지체의 구조를 복잡하게 변형시킴으로써, 분산된 촉매입자가 구조적으로 움직이기 힘든 상태를 유지하여 촉매 지지체 위에 촉매 입자의 분산도 및 표면적을 높게 유지하도록 하여 촉매의 성능을 향상시킬 수 있다.According to the present invention, the structure of the catalyst support is complicatedly deformed without complicated processes such as changing the chemical properties of the catalyst support, so that the dispersed catalyst particles remain in a structurally difficult state, And the surface area thereof can be maintained at a high level, so that the performance of the catalyst can be improved.
도 1은 γ-알루미나(alumina)입자에 대한 투과전자현미경(TEM) 이미지이다(A: 판 모양, B: 바늘 모양).
도 2는 γ-알루미나(alumina)입자에 대한 모식도이다(A: 판 모양, B: 바늘 모양).
도 3은 백금(Pt) 나노입자가 증착된 γ-알루미나(alumina)입자에 대한 투과전자현미경(TEM) 이미지이다(A: 판 모양, B: 바늘 모양).
도 4은 백금(Pt) 나노입자가 증착된 γ-알루미나(alumina) 입자에 대한 모식도이다(A: 판 모양, B: 바늘 모양).
도 5는 촉매 성능 시험 결과를 나타낸 그래프이다.1 is a transmission electron microscope (TEM) image of a gamma-alumina particle (A: plate shape, B: needle shape).
Fig. 2 is a schematic diagram of γ-alumina particles (A: plate shape, B: needle shape).
3 is a transmission electron microscope (TEM) image (A: plate shape, B: needle shape) of γ-alumina particles on which platinum (Pt) nanoparticles are deposited.
Fig. 4 is a schematic diagram of gamma-alumina particles deposited with platinum (Pt) nanoparticles (A: plate shape, B: needle shape).
5 is a graph showing the results of the catalyst performance test.
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시 형태들을 설명한다.Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.
본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. The embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.
본 발명은, 촉매 지지체의 구조를 제어하여 촉매 활성 입자의 분산도를 높게 유지하고, 이를 통해 효율이 높은 촉매를 제공하고자 한다.The present invention aims at providing a highly efficient catalyst by controlling the structure of the catalyst support to keep the degree of dispersion of the catalytically active particles high.
본 발명의 일 측면은 촉매 활성 입자, 및 촉매 활성 입자를 지지하고 표면 곡률을 가지는 촉매 지지체 입자를 포함하는 촉매일 수 있다.One aspect of the present invention may be a catalyst comprising catalytically active particles and catalyst support particles supporting the catalytically active particles and having surface curvature.
촉매 활성 입자는 촉매 지지체가 이루는 표면 곡률 안에 들어가서 고정될 수 있는 크기이고 촉매 지지체 입자의 기공 등에 흡착되는 등의 상태로 존재할 수 있다. 촉매 활성 입자와 촉매 지지체 입자 사이의 상호 작용에 의하여 촉매 활성 입자와 촉매 지지체 입자 간의 결합이 유지될 수 있다. 상기 촉매 활성 입자의 소재로는 백금(Pt), 팔라듐(Pd), 금(Au), 은(Ag), 및 로듐(Rh)으로 이루어진 군중에서 하나 이상을 선택하여 사용할 수 있다. 상기 촉매 지지체 입자의 소재로는 감마 알루미나, 티타니아, 세리아로 이루어진 군 중에서 하나 이상을 선택하여 사용할 수 있고, 바람직하게는 감마 알루미나를 사용할 수 있다. The catalytically active particles may be present in such a state that they are of a size that can be set and fixed in the surface curvature formed by the catalyst support, adsorbed to the pores of the catalyst support particles and the like. The interaction between the catalytically active particles and the catalyst support particles can be maintained by the interaction between the catalytically active particles and the catalyst support particles. As the material of the catalytically active particles, at least one selected from the group consisting of platinum (Pt), palladium (Pd), gold (Au), silver (Ag), and rhodium (Rh) As the material of the catalyst support particles, at least one selected from the group consisting of gamma alumina, titania and ceria can be selected and gamma alumina can be preferably used.
또한 촉매 성능을 향상시키기 위하여, 촉매 지지체 입자 또는 촉매 활성 입자에 세륨(Ce), 철(Fe), 니켈(Ni), 구리(Cu), 망간(Mn), 텅스텐(W), 안티몬(Sb), 셀레늄(Se), 바나듐(V), 몰리브덴(Mo), 지르코늄(Zr) 및 바륨(Ba)으로 이루어진 군 중에서 하나 이상을 선택하여 도핑하여 사용할 수도 있다.(Ce), iron (Fe), nickel (Ni), copper (Cu), manganese (Mn), tungsten (W), and antimony (Sb) are added to the catalyst support particles or the catalytically active particles. At least one selected from the group consisting of selenium (Se), vanadium (V), molybdenum (Mo), zirconium (Zr), and barium (Ba)
촉매 지지체 입자는 표면 곡률을 가지는 것을 특징으로 한다. 구체적으로 촉매 지지체 입자는 바늘 형상 또는 로드 형상을 가질 수 있다. 하지만, 이에 한정되는 것은 아니고 입자 표면에 곡률을 가지는 것이라면 특정한 제한은 없다. 표면에 곡률을 가진다는 것은 판 형상처럼 평평한 부분을 가지지 않는다는 것을 의미한다. 촉매 지지체 입자의 표면곡률이 높으면 높을수록 지지체 입자 상에 증착된 촉매 활성 입자의 확산 장벽(diffusion barrier)이 증가되고, 이로 인하여 촉매 지지체 입자 상에 증착된 촉매 활성 입자의 확산이 억제되어, 당초에 촉매 활성 입자는 당초 증착된 상태를 그대로 유지할 수 있다.The catalyst support particles are characterized by having a surface curvature. Specifically, the catalyst support particles may have a needle shape or a rod shape. However, the present invention is not limited thereto, and there is no particular limitation as long as it has a curvature on the surface of the particles. Having curvature on the surface means that it does not have a flat part like a plate shape. The higher the surface curvature of the catalyst support particles, the greater the diffusion barrier of the catalytically active particles deposited on the support particles, and the diffusion of the catalytically active particles deposited on the catalyst support particles is suppressed, The catalytically active particles can be maintained in the originally deposited state.
반면에, 촉매 지지체 입자가 판 형상인 경우, 평평한 부분에서의 확산 장벽은 상대적으로 작기 때문에 평평한 부분에 증착된 촉매 활성 입자는 용이하게 확산되어 서로 뭉칠 수 있으며, 이로 인하여 촉매 활성 입자의 크기는 커지고, 촉매 활성 입자의 전체적인 비표면적이 감소할 수 있다. 이는 결국 촉매 효율의 저하를 초래할 수 있다.On the other hand, when the catalyst support particles are in the form of a plate, since the diffusion barrier in the flat portion is relatively small, the catalytically active particles deposited on the flat portion can easily diffuse and coalesce with each other, , The overall specific surface area of the catalytically active particles can be reduced. Which may result in a decrease in catalyst efficiency.
촉매 지지체 입자의 곡률 반경은 1~1000 nm 인 것이 바람직하다. 곡률 반경이 상기 범위보다 큰 경우에는 판 형상의 경우와 비교하여 촉매 효율 향상의 효과가 미미하고, 곡률 반경이 상기 범위보다 작은 경우에는 그러한 형상을 갖는 촉매 지지체를 제작하기에 어려움이 있다. 예를 들어, 촉매 지지체 입자가 바늘 형상 또는 로드 형상을 가지는 경우, 그 평균 직경은 1~100 nm 가 바람직한데, 평균 직경이 1nm 보다 작으면 촉매 지지체 제작이 어렵고, 100nm를 초과하면 증착되는 촉매입자의 양이 충분하지 못할 수 있다. 또한, 종횡비(aspect ratio)는 10~1000 가 바람직한데, 종횡비가 10보다 작으면 촉매 지지체 제작이 어렵고, 1000을 초과하면 증착되는 촉매입자의 양이 충분하지 못할 수 있다.The radius of curvature of the catalyst support particles is preferably 1 to 1000 nm. When the radius of curvature is larger than the above range, the effect of improving the catalytic efficiency is small compared with the case of the plate shape, and when the radius of curvature is smaller than the above range, it is difficult to produce the catalyst support having such a shape. For example, when the catalyst support particles have a needle shape or a rod shape, the average diameter is preferably 1 to 100 nm. When the average diameter is smaller than 1 nm, catalyst support is difficult to manufacture, May not be sufficient. In addition, the aspect ratio is preferably 10 to 1000. If the aspect ratio is less than 10, it is difficult to manufacture the catalyst support. If the aspect ratio exceeds 1000, the amount of the catalyst particles to be deposited may be insufficient.
본 발명에 따른 촉매는 바람직하게는 150~300℃에서 사용할 수 있고, 더욱 바람직하게는 200~250℃에서 사용할 수 있다. 예를 들면, 일산화탄소를 이산화탄소로 전환하는 경우 상기 온도 범위 내에서 전환 효율이 현저하게 향상될 수 있다. 본 발명에 따른 촉매는 150℃ 미만에서도 효율을 유지하며 작동할 수 있으나 촉매가 사용되는 실제 반응 환경은 고온 고압 환경인 경우가 많으며, 본 발명에 따른 촉매는 150℃이상에서 촉매 효율이 증가되며, 300℃를 초과하는 환경에서는 본 발명에 따른 촉매의 구조 및 분산도가 변형되어 촉매 효율이 감소 될 수 있다.The catalyst according to the present invention is preferably used at 150 to 300 ° C, more preferably 200 to 250 ° C. For example, when carbon monoxide is converted to carbon dioxide, the conversion efficiency can be remarkably improved within the above temperature range. The catalyst according to the present invention can operate at an efficiency of less than 150 ° C, but the actual reaction environment in which the catalyst is used is often a high temperature and high-pressure environment, and the catalyst according to the present invention has a catalyst efficiency of 150 ° C or higher, In an environment exceeding 300 ° C, the structure and dispersion degree of the catalyst according to the present invention may be modified to reduce the catalyst efficiency.
이하에서는 실시예 및 비교예를 들어 본 발명에 대하여 상세히 설명한다. 하지만 본 발명에 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the embodiments.
촉매 지지체 분말로 4g의 바늘모양 γ-알루미나(alumina, Alfa aesar, 평균 직경 4 nm, 평균길이 40 nm)를 준비하였다. 준비된 촉매 지지체 분말을 직경 10cm 인 테플론 컵에 담아 교반기(stirrer)로 분말을 휘저어 가며 아크플라즈마 증착법을 이용하여 백금(Pt) 나노입자 3wt% 를 γ-알루미나(alumina) 촉매 지지체 상에 증착하였다. 아크플라즈마 증착은 200 V, 1800 uF, 8815 shot의 조건에서 실시하였다.4 g of needle-shaped alumina (Alfa aesar, average diameter 4 nm,
[비교예][Comparative Example]
촉매 지지체 입자로 판 모양의 γ-알루미나(alumina, Aeroxide, 평균두께 10nm, 평균 폭 50 nm)를 사용한 점을 제외하고, 실시예와 동일한 방법에 따라 촉매를 제조하였다.The catalyst was prepared in the same manner as in Example except that plate-like? -Alumina (alumina, Aeroxide, average thickness 10 nm, average width 50 nm) was used as the catalyst support particles.
[평가][evaluation]
촉매지지체의 형상The shape of the catalyst support
투과전자현미경(TEM)을 사용하여 촉매 지지체로 사용한 γ-알루미나 (alumina) 입자의 형상을 관찰하였다. 도1 에 γ-알루미나(alumina) 입자에 대한 투과전자현미경(TEM) 이미지를 나타내었고, 도2 에는 γ-알루미나(alumina) 입자에 대한 모식도를 나타내었다. 도 1 및 도 2를 참조하면, 비교예의 경우 판 형상을 가지며(도 1(A), 도 2(A)), 실시예의 경우 바늘(또는 로드) 형상을 가짐(도 1(B), 도 2(B))을 확인할 수 있다.Transmission electron microscopy (TEM) was used to observe the shape of the γ-alumina particles used as the catalyst support. FIG. 1 shows a transmission electron microscope (TEM) image of γ-alumina particles, and FIG. 2 shows a schematic diagram of γ-alumina particles. 1 and 2, a comparative example has a plate shape (Figs. 1A and 2A) and a needle (or rod) shape in the embodiment (Figs. 1B and 2 (B)).
촉매 활성 입자가 흡착된 촉매 지지체The catalyst support on which the catalytically active particles are adsorbed
투과전자현미경(TEM)을 사용하여 Pt 나노입자가 흡착된 γ-알루미나 (alumina) 촉매 지지체의 미세 구조를 관찰하였다. 도 3에 비교예 및 실시예에 따른 백금(Pt) 나노입자(촉매 활성 입자)가 증착된 γ-알루미나(alumina) 촉매 지지체에 대한 투과전자현미경(TEM) 이미지를 나타내었고, 도 4에는 이에 대한 모식도를 나타내었다.The microstructure of the γ-alumina catalyst support on which the Pt nanoparticles were adsorbed was observed using a transmission electron microscope (TEM). FIG. 3 shows a transmission electron microscope (TEM) image of a γ-alumina catalyst support on which platinum (Pt) nanoparticles (catalytically active particles) according to Comparative Examples and Examples are deposited, and FIG. Fig.
도 3 및 도 4를 참조하면, 검은 점들이 증착된 백금(Pt) 나노입자들인데, 백금(Pt) 나노입자들의 크기를 비교해 보면, 비교예에 따라 판 형상 촉매 지지체에 증착된 백금(Pt) 입자들의 크기가(도 3(A)), 실시예에 따라 바늘 형상 촉매 지지체에 증착된 백금(Pt) 입자들(도 3(B))보다 크다는 점을 확인할 수 있다.Referring to FIGS. 3 and 4, platinum (Pt) nanoparticles deposited with black dots are compared. The size of platinum (Pt) nanoparticles is compared with that of platinum Pt deposited on a plate- It can be seen that the size of the particles (Fig. 3 (A)) is larger than the platinum (Pt) particles (Fig. 3 (B)) deposited on the needle shaped catalyst support according to the embodiment.
그 이유는, 플라즈마화하여 분산되는 입자의 당초 크기는 비슷하지만, 판 형상의 γ-알루미나(alumina) 의 경우 바늘 형상의 γ-알루미나(alumina) 에 비하여 확산장벽(diffusion barrier)이 작기 때문에 판 형상의 γ-알루미나(alumina) 에 증착된 백금(Pt) 입자들이 상대적으로 용이하게 확산하여 서로 만나 뭉쳤기 때문이다.The reason for this is that although the original size of the particles dispersed in plasma is similar, the plate-shaped γ-alumina has a smaller diffusion barrier than the needle-shaped γ-alumina, Of the platinum (Pt) particles deposited on the gamma-alumina were relatively easily diffused and clumped together.
이러한 결과로부터, 촉매 지지체가 동일한 물질로 이루어져 있더라도 그 표면의 곡률을 다르게 함으로써 촉매 활성 입자의 분산도를 변화시킬 수 있다는 점, 즉 촉매 지지체 입자의 표면 곡률이 높으면 높을수록 촉매 지지체 표면에 증착된 촉매 활성 입자들의 확산장벽이 높기 때문에 증착된 촉매 활성 입자들이 서로 뭉치기 어렵고 이로 인하여 촉매 활성 입자의 분산도는 높아진다는 점을 확인할 수 있다.From these results, it is found that even if the catalyst support is composed of the same material, the degree of dispersion of the catalytically active particles can be changed by changing the curvature of the surface thereof, that is, the higher the surface curvature of the catalyst support particles, It can be seen that since the diffusion barrier of the active particles is high, the catalytically active particles deposited are difficult to be aggregated and that the dispersion degree of the catalytically active particles becomes high.
촉매 성능 평가Catalyst performance evaluation
비교예 및 실시예에 따른 촉매에 대하여 촉매성능 시험을 실시하였으며, 그 결과를 도 5에 나타내었다. 촉매성능 시험은, 자동차 배기가스의 대표적 예인 일산화탄소 (CO)를 이산화탄소(CO2)로 변환시키는 반응효율을 측정함으로써 수행하였다. Catalyst performance tests were conducted on the catalysts of Comparative Examples and Examples, and the results are shown in FIG. The catalyst performance test was conducted by measuring the reaction efficiency of converting carbon monoxide (CO), which is a representative example of automobile exhaust gas, into carbon dioxide (CO 2 ).
도 5를 참조하면, 같은 양의 백금(Pt) 나노입자를 분산하였을 때, 바늘 모양 촉매 지지체 입자가 판 모양 촉매 지지체 입자보다 더 우수한 일산화탄소(CO) 산화율을 나타냄을 확인할 수 있다. 150~300℃, 특히 200~250℃의 범위에서 현저한 효과를 나타내고 있다. 이러한 촉매 성능의 차이는 촉매 지지체의 형태 차이로 인한 백금(Pt) 입자의 분산도 차이에 기인하는 것임을 알 수 있다. 따라서 동일한 물질을 사용하더라도 촉매 지지체의 구조를 다르게 하여 분산되는 촉매 활성 입자의 분산도를 조절함으로써 촉매의 효율을 향상시킬 수 있음을 확인할 수 있다.Referring to FIG. 5, it can be seen that when the same amount of platinum (Pt) nanoparticles are dispersed, the needle-like catalyst support particles exhibit a better carbon monoxide (CO) oxidation rate than the plate-like catalyst support particles. And exhibits remarkable effects in the range of 150 to 300 占 폚, particularly 200 to 250 占 폚. It can be seen that the difference in the catalytic performance is due to the difference in dispersion of the platinum (Pt) particles due to the difference in shape of the catalyst support. Therefore, even if the same material is used, it is possible to improve the efficiency of the catalyst by controlling the dispersion degree of the catalytically active particles dispersed by varying the structure of the catalyst support.
본 발명에서 사용한 용어는 특정한 실시예를 설명하기 위한 것으로, 본 발명을 한정하고자 하는 것이 아니다. 단수의 표현은 문맥상 명백하지 않는 한, 복수의 의미를 포함한다고 보아야 할 것이다. 포함하다 또는 가지다 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성 요소 또는 이들을 조합한 것이 존재한다는 것을 의미하는 것이지, 이를 배제하기 위한 것이 아니다. 본 발명은 상술한 실시 형태 및 첨부된 도면에 의해 한정되는 것이 아니며, 첨부된 특허청구범위에 의해 한정하고자 한다. 따라서, 특허청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 당 기술 분야의 통상의 지식을 가진 자에 의해 다양한 형태의 치환, 변형 및 변경이 가능할 것이며, 이 또한 본 발명의 범위에 속한다고 할 것이다.The terms used in the present invention are intended to illustrate specific embodiments and are not intended to limit the invention. The singular presentation should be understood to include plural meanings, unless the context clearly indicates otherwise. Or " an embodiment " means that there is a feature, a number, a step, an operation, an element, or a combination thereof described in the specification, and does not exclude it. The present invention is not limited by the above-described embodiment and the accompanying drawings, but is intended to be limited by the appended claims. Therefore, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. I will say.
Claims (8)
상기 촉매 활성 입자를 지지하며, 곡률반경이 1~1000nm인 표면 곡률을 가지고, 평균 직경이 1~100nm인 촉매 지지체 입자;를 포함하고,
상기 곡률 반경이 평균 직경의 1 내지 10배이고,
상기 촉매 지지체 입자는 바늘 형상 또는 로드 형상인 것을 특징으로 하는 촉매. Catalytically active particles; And
And catalyst support particles supporting the catalytically active particles and having a surface curvature with a radius of curvature of 1 to 1000 nm and an average diameter of 1 to 100 nm,
Wherein the radius of curvature is 1 to 10 times the average diameter,
Wherein the catalyst support particles are needle-like or rod-shaped.
The catalyst according to claim 1, wherein the catalyst is used at 200 to 250 ° C.
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