KR100783620B1 - A method for improving mass-transfer into catalyst matrix - Google Patents
A method for improving mass-transfer into catalyst matrix Download PDFInfo
- Publication number
- KR100783620B1 KR100783620B1 KR1020060030956A KR20060030956A KR100783620B1 KR 100783620 B1 KR100783620 B1 KR 100783620B1 KR 1020060030956 A KR1020060030956 A KR 1020060030956A KR 20060030956 A KR20060030956 A KR 20060030956A KR 100783620 B1 KR100783620 B1 KR 100783620B1
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- catalyst matrix
- matrix
- carrier
- catalyst composite
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000011159 matrix material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims description 23
- -1 polyethylene Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 239000011268 mixed slurry Substances 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical class CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Images
Classifications
-
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
본 발명은 세공형성 첨가물질을 포함하여 혼합슬러리를 제조한 후, 이를 담체에 침적시키고, 소성함으로써, 세공형성 첨가물질 (주형물질)로부터 거대세공을 구성하여, 거대세공 및 미세세공이 망상구조를 형성하도록 촉매 매트릭스를 형성하는 방법에 관한 것으로, 이에 의해 촉매 매트릭스에서 물질전달이 개선되는 효과를 얻을 수 있어, 차량 배출 배기가스는 촉매 매트릭스 내부로 침투가 용이하여 높은 정화능을 발휘할 수 있다.According to the present invention, after preparing a mixed slurry including a pore-forming additive, it is deposited on a carrier and calcined to form macropore from the pore-forming additive (template), whereby macropore and micropore form a network structure. The present invention relates to a method of forming a catalyst matrix so that the substance can be improved in the catalyst matrix, so that the vehicle exhaust gas can easily penetrate into the catalyst matrix and exhibit high purification ability.
촉매 매트릭스, 망상구조 Catalyst Matrix, Network Structure
Description
도 1은 본 발명에 의한 세공형성 첨가제가 적용된 경우 망상구조를 보이는 전자현미경 사진들이며,1 is an electron micrograph showing a network structure when the pore-forming additive according to the present invention is applied,
도 2는 본 발명에 따른 망상구조 형성에 의하여 촉매복합재 전환효율이 개선되는 것을 보이는, HC, CO 및 NOx 전환율 측정도이다.Figure 2 is a measurement of HC, CO and NOx conversion rate, showing that the catalyst composite conversion efficiency is improved by forming a network structure according to the present invention.
본 발명은 촉매 매트릭스(matrix)에서의 물질전달 개선방법에 관한 것이고, 상세하게는 담체에 코팅된 촉매 매트릭스 내부 공간에 망상구조의 확대 세공을 형성하여, 상기 촉매 매트릭스 표면을 유동하는 물질이 내부 공간에 용이하게 전달되도록 하기 위한, 촉매 매트릭스 내에서의 물리적 개선방법을 제공하는 것이다.The present invention relates to a method for improving mass transfer in a catalyst matrix, and more particularly, to form a network enlarged pore in a catalyst matrix inner space coated on a carrier, so that a material flowing through the surface of the catalyst matrix is formed in the inner space. It is to provide a method for physical improvement in the catalyst matrix to facilitate delivery to the catalyst.
'다기능성'(polyfunctional) 촉매라 불리는 촉매는 내연기관으로부터의 배기 가스 처리에 사용된다. 다기능성 촉매란, 배기가스에 존재하는 탄화수소, 일산화탄소의 산화뿐 아니라, 배기가스에 존재하는 질소산화물의 환원을 수행하는 것을 의미하며, 삼원촉매로 이해될 수 있다.Catalysts called 'polyfunctional' catalysts are used for the treatment of exhaust gases from internal combustion engines. The multifunctional catalyst means not only oxidation of hydrocarbons and carbon monoxide present in the exhaust gas, but also reduction of nitrogen oxides present in the exhaust gas, and can be understood as a three-way catalyst.
다기능성 촉매는 슬러리 상태의 촉매복합재가 벌집모양의 세라믹 하니컴에 코팅, 건조되고, 소성된 형상으로 완성된다. 이때, 촉매복합재를 이루는 다양한 물질들, 예를 들면 소량의 귀금속, 상기 귀금속을 담지하는 지지체, 조촉매 및 보조재료를 총칭하여 워시코트(washcoat)라 칭한다. 이러한 워시코트는 통상 슬러리 상태로 하니컴에 도포된다. The multifunctional catalyst is coated with a honeycomb ceramic honeycomb in a slurry-like catalyst composite, dried, and finished in a fired shape. In this case, various materials constituting the catalyst composite material, for example, a small amount of precious metal, a support carrying the precious metal, a promoter and an auxiliary material are collectively called a washcoat. This washcoat is usually applied to the honeycomb in a slurry state.
본 명세서에서, 혼동을 줄이기 위하여, 워시코트 또는 촉매복합재는 동일한 의미로 사용되며, 상기 워시코트가 코팅되는 피코팅체는 담체라고 정의되며, 상기 담체에 코팅된 워시코트를 촉매 매트릭스라 정의한다. 따라서, 촉매 매트릭스 상에는 차량 배기가스가 통과되며, 상기 배기가스 중 탄화수소 및 일산화탄소는 산화반응에 의하여, 질소산화물은 환원반응에 의하여 무해한 물질로 전환되어 외부로 방출된다. 본 명세서에서 차량 배출 배기가스는 촉매 매트릭스 내부로 전달되어야 할 대표적인 물질로 표현될 수 있다.In the present specification, in order to reduce confusion, a washcoat or a catalyst composite material is used in the same sense, and the coated body to which the washcoat is coated is defined as a carrier, and the washcoat coated on the carrier is defined as a catalyst matrix. Accordingly, vehicle exhaust gas is passed on the catalyst matrix, and hydrocarbons and carbon monoxide in the exhaust gas are converted into harmless substances by the oxidation reaction and released into the outside by the reduction reaction. In the present specification, the vehicle exhaust exhaust gas may be represented as a representative material to be delivered into the catalyst matrix.
촉매 매트릭스 표면을 유동하는 배기가스는 가능한 한 매트릭스 내부까지 침투되어 매트릭스를 구성하는 촉매복합재와 반응하여야 양호한 정화효율을 달성할 수 있다. 이러한 물질전달은 배기가스 공간속도, 공간온도 및 촉매 매트릭스 물리적 상태, 특히 세공 분포를 포함한 인자들에 따라 좌우된다. Exhaust gas flowing through the surface of the catalyst matrix must penetrate as far as possible into the matrix and react with the catalyst composite constituting the matrix to achieve good purification efficiency. This mass transfer depends on factors including exhaust gas velocity, space temperature and catalyst matrix physical state, in particular pore distribution.
촉매 매트릭스 내에서의 신속한 반응을 기대하기 위하여는 물질전달이 빠르 도록 촉매 매트릭스를 구성하고 있는 입자간 사이 공간은 가능한 커야하며, 세공내 물질전달 저항이 최소가 되도록 가능한 다공성 입자는 가능한 작아야 한다. 그러나, 작은 입자들로 인한 워시코트 조밀화는 밀도 증가로 이어져 워시코트가 담체에 코팅되어 소성된 후, 촉매 매트릭스 표면에 크랙이 발생되는 문제가 있었다.In order to expect a rapid reaction in the catalyst matrix, the space between the particles constituting the catalyst matrix should be as large as possible for rapid mass transfer, and the porosity particles should be as small as possible to minimize the material transfer resistance in the pores. However, the washcoat densification due to the small particles leads to an increase in density, so that after the washcoat is coated on the carrier and calcined, cracks occur on the surface of the catalyst matrix.
본 발명자는 상기의 문제점을 인식하고, 촉매 매트릭스의 물리적 구조를 변화시켜주도록, 즉 거대 세공 및 미세 세공이 망상구조를 이루며 공존하도록 촉매 매트릭스를 제조하는 방법에 의하여, 촉매 매트릭스 내에서의 물질전달 개선방법을 개발하였다. The inventors have recognized the above problems and improved the material transfer in the catalyst matrix by a method of preparing the catalyst matrix to change the physical structure of the catalyst matrix, that is, the macropores and micropores coexist in a network. The method was developed.
따라서, 본 발명의 목적은 촉매 매트릭스 내의 유체흐름에 대한 확산저항을 제어하여 물질전달을 개선하고자 하는 것이다. Accordingly, it is an object of the present invention to improve the mass transfer by controlling the diffusion resistance to fluid flow in the catalyst matrix.
상기 목적을 달성하기 위하여, 본 발명은 촉매복합재 및 미세 및 거대 세공형성용 첨가제를 포함하는 혼합물을 형성하는 단계; 상기 혼합물을 담체에 침적하는 단계; 및 상기 담체를 소성하여 작은 입자들이 망상구조를 이뤄 거대세공이 잘 발달된 촉매 매트릭스가 형성되는 단계를 포함하는, 촉매 매트릭스에서의 물질전달 개선방법을 제공한다. In order to achieve the above object, the present invention comprises the steps of forming a mixture comprising a catalyst composite and additives for forming fine and macroporous; Depositing the mixture on a carrier; And calcining the carrier to form a catalyst matrix in which small particles form a network and thus well developed macropores.
본 발명에 있어서, 세공형성 첨가제는 기포발생이 가능한 유기물질, 바람직 하게는 계면활성제, 또는 고분자 물질, 바람직하게는 폴리에틸렌 또는 폴리우레탄 폼 자체이거나 상기 고분자 물질을 소성하여 수득한 탄소나노튜브와 같은 탄소체일 수 있다.In the present invention, the pore-forming additive is an organic material capable of generating bubbles, preferably a surfactant, or a carbon material such as carbon nanotubes obtained by firing the polymer material or a polymer material, preferably polyethylene or polyurethane foam itself. Can be a sieve.
구체적으로는, 음이온성 계면활성제, 비이온성 계면활성제 및 폴리에틸렌 글리콜에서 선택된 첨가제를 촉매복합재에 첨가하여 소성에 의해 거대세공을 형성함으로써, 촉매복합재에 의한 미세세공과 망상구조로 연결하여 촉매 매트릭스를 구성하는 것이다. Specifically, additives selected from anionic surfactants, nonionic surfactants and polyethylene glycol are added to the catalyst composite to form macropores by firing, thereby connecting the micropore by the catalyst composite to the network structure to form a catalyst matrix. It is.
음이온계 계면활성제로는, 에톡시카르복실레이트, 에톡시화 지방산, 사르코시네이트, 포스페이트 에스테르, 알콜 술페이트, 알콜 에테르 술페이트 및 술페이트화 알칸올아미드 에톡실레이트와 같은 술페이트, 술포숙시네이트, 알킬벤젠 술포네이트 또는 알킬 나프탈렌술포네이트와 같은 술포네이트를 들 수 있다.Anionic surfactants include sulfates such as ethoxycarboxylates, ethoxylated fatty acids, sarcosinates, phosphate esters, alcohol sulfates, alcohol ether sulfates and sulfated alkanolamide ethoxylates, sulfosuccisates. Sulfonates such as acetates, alkylbenzene sulfonates or alkyl naphthalenesulfonates.
비이온성 계면활성제로는, 아세틸렌계 계면활성제, 알콜 에톡실레이트, 알칸올아미드, 아민 산화물, 에톡시화 알칸올아미드, 장쇄 에톡시화 아민, 에틸렌 산화물/프로필렌 산화물 공중합체, 소르비탄 유도체, 에틸렌 글리콜, 프로필렌 글리콜,Examples of nonionic surfactants include acetylene surfactants, alcohol ethoxylates, alkanolamides, amine oxides, ethoxylated alkanolamides, long chain ethoxylated amines, ethylene oxide / propylene oxide copolymers, sorbitan derivatives, ethylene glycol, Propylene glycol,
글리세롤, 폴리글리세릴 에스테르 및 이의 에톡시화 유도체, 알킬아민, 알킬이미다졸린, 에톡시화 오일 및 알킬페놀 에톡실레이트를 들 수 있다. Glycerol, polyglyceryl esters and ethoxylated derivatives thereof, alkylamines, alkylimidazolines, ethoxylated oils and alkylphenol ethoxylates.
사용되는 첨가제의 양은, 촉매복합재의 중량에 대하여 일반적으로 0.1 중량% 내지 1.0 중량%일 수 있다. 1.0 중량% 이상인 경우에는, 첨가재 발열에 의하여 귀금속이 소결되어 활성이 저하될 수 있기 때문에 바람직하지 않다.The amount of the additive used may be generally 0.1% by weight to 1.0% by weight based on the weight of the catalyst composite. When it is 1.0 weight% or more, since a noble metal is sintered by an additive heat_generation | fever and activity may fall, it is unpreferable.
한편, 촉매복합재는 공지된 구성이며, 예를 들면 촉매 복합재는 백금 성분, 및 임의적으로 백금 이외의 백금족 금속 성분을 포함한다. 백금 이외의 임의적 백금족 금속 성분은 팔라듐, 로듐, 루테늄, 이리듐, 및 오스뮴 성분들로 이루어진 군으로부터 선택될 수 있다. 백금 이외의 바람직한 백금족 금속 성분은 팔라듐, 로듐, 및 이들의 혼합물로 이루어진 군으로부터 선택된다. 상기 촉매복합재는 또한 고표면적의 내화성 산화물 지지체로 만들어진 지지체를 포함한다. 지지체는 알On the other hand, the catalyst composite material has a known configuration, for example, the catalyst composite material includes a platinum component, and optionally a platinum group metal component other than platinum. Optional platinum group metal components other than platinum may be selected from the group consisting of palladium, rhodium, ruthenium, iridium, and osmium components. Preferred platinum group metal components other than platinum are selected from the group consisting of palladium, rhodium, and mixtures thereof. The catalyst composite also includes a support made of a high surface area refractory oxide support. Support is egg
루미나, 실리카, 티타니아, 및 지르코니아 화합물로 이루어진 군으로부터 선택될 수 있다. 유용한 고표면적 지지체에는 1종 이상의 내화성 산화물이 포함된다. 이 산화물에는, 예를 들면 실리카 및 금속 산화물(예: 알루미나), 및 혼합 산화물 형태(예: 실리카-알루미나, 무정형 또는 결정성의 알루미노실리케이트, 알루미나-지르코니아, 알루미나-크로미아, 알루미나-세리아 등)이 포함된다. 바람직하게는, 지지체는 알루미나, 실리카, 실리카-알루미나, 알루미노-실리케이트, 알루미나-지르코니아, 알루미나-크로미아, 및 알루미나-세리아로 이루어진 군으로부터 선택된 활성화된 화합물이다. 더욱 바람직하게는, 지지체는 활성화된 알루미나이다. It may be selected from the group consisting of lumina, silica, titania, and zirconia compounds. Useful high surface area supports include one or more refractory oxides. These oxides include, for example, silica and metal oxides (such as alumina), and mixed oxide forms (such as silica-alumina, amorphous or crystalline aluminosilicates, alumina-zirconia, alumina-chromia, alumina-ceria, etc.). This includes. Preferably, the support is an activated compound selected from the group consisting of alumina, silica, silica-alumina, alumino-silicate, alumina-zirconia, alumina-chromia, and alumina-ceria. More preferably, the support is activated alumina.
한편, 선택적으로 촉매복합재는 또한 NOx 흡착 성분을 포함한다. 바람직하게는, NOx 흡착 성분은 알칼리토 금속 성분, 알칼리 금속 성분, 및 희토류 금속 성분으로 이루어진 군으로부터 선택된다. 예를 들면, NOx 흡착 성분은 칼슘, 스트론튬 및 바륨의 산화물, 칼륨, 나트륨, 리튬 및 세슘의 산화물, 및 세륨, 란탄, 프라세오디뮴 및 네오디뮴의 산화물로 이루어진 군으로부터 선택된다. On the other hand, optionally, the catalyst composite also includes a NOx adsorption component. Preferably, the NOx adsorption component is selected from the group consisting of alkaline earth metal components, alkali metal components, and rare earth metal components. For example, the NOx adsorption component is selected from the group consisting of oxides of calcium, strontium and barium, oxides of potassium, sodium, lithium and cesium, and oxides of cerium, lanthanum, praseodymium and neodymium.
상기 촉매복합재는 임의의 적합한 방법으로 만들 수 있다. 바람직한 방법은 1종 이상의 수용성 또는 수분산성 백금 성분의 용액, 및 상기 용액을 미분된 고표면적 내화성 산화물의 혼합물에 흡수시키고, 백금이 아닌 백금족 금속 성분은, 사용시 동일하거나 상이한 내화성 산화물 입자상에 지지될 수 있다. The catalyst composite can be made by any suitable method. A preferred method is to absorb a solution of one or more water soluble or water dispersible platinum components, and the solution into a mixture of finely divided high surface area refractory oxides, wherein the platinum group metal component other than platinum can be supported on the same or different refractory oxide particles in use. have.
상기 지지된 백금 및 기타 성분들을 물에 가하고, 바람직하게는 분쇄하여 슬러리(촉매복합재)를 형성한다. 한편, 본 발명에 의한 첨가제는 상기 촉매복합재에 첨가되어 혼합슬러리를 형성한다. 이때, 첨가되는 양은 촉매복합재의 중량에 대하여 일반적으로 0.1중량% 내지 1.0 중량%일 수 있다.The supported platinum and other components are added to water and preferably milled to form a slurry (catalyst composite). On the other hand, the additive according to the present invention is added to the catalyst composite to form a mixed slurry. In this case, the amount added may be generally 0.1% to 1.0% by weight based on the weight of the catalyst composite material.
상기 혼합슬러리를 분쇄하여 실질적으로 모든 고상물이 평균 직경으로 입도 10마이크로미터 미만이 되게 한다. The mixed slurry is milled so that substantially all solids are less than 10 micrometers in particle size on average.
담체 상에 상기 혼합슬러리를 침적시키기 위해, 적절한 양의 혼합슬러리가 담체 상에 존재할 때까지, 필요하다면 중간에 건조시키면서, 담체를 혼합슬러리에 1회 이상 침지시킬 수 있다. 바람직하게는 전형적 세라믹 허니콤 담체에 대해 약 5 내지 30 중량%의 혼합 슬러리가 포함될 수 있다. In order to deposit the mixed slurry on the carrier, the carrier may be immersed one or more times in the mixed slurry, if necessary, with intermediate drying if necessary until an appropriate amount of mixed slurry is present on the carrier. Preferably from about 5 to 30% by weight of the mixed slurry may be included relative to the typical ceramic honeycomb carrier.
본 발명의 마지막 단계에서의 소성단계는, 통상 공기 중에서 수행되는 것이나, 산화 또는 환원 분위기와 같은 제어된 대기 중에서 수행되는 소성단계를 배제하는 것은 아니다. 실제로 소성온도는 400℃ 내지 700℃에서 수행된다.The firing step in the last step of the invention is usually carried out in air, but does not exclude the firing step carried out in a controlled atmosphere such as an oxidizing or reducing atmosphere. In practice the firing temperature is carried out at 400 ° C to 700 ° C.
실시예 Example
공지된 배기가스 정화용 코팅 슬러리(워시코트, 촉매복합재)에 폴리에틸렌을 소성하여 수득한 탄소체(평균직경 50 nm)를 상기 촉매복합재의 중량에 대하여 0.5 중량% 투여하였다. 상기 혼합슬러리를 분쇄하여 고상물이 평균직경으로 입도 10 마이크로미터 미만이 되도록 밀링하였다. 코오디어라이트 담체(size: 105.7*115, CPSI 400)에 상기 혼합슬러리를 침지하여 꺼낸 후, 실온에서 약 5시간 건조하였다. 상기 담체를 450℃에서 하소하여 본 발명에 의한 측정 담체를 완성하였다.A carbon body (average diameter of 50 nm) obtained by calcining polyethylene in a known exhaust gas purification coating slurry (wash coat, catalyst composite material) was administered to 0.5 wt% based on the weight of the catalyst composite material. The mixed slurry was ground and milled so that the solids had an average diameter of less than 10 micrometers. The mixed slurry was immersed out in a cordierite carrier (size: 105.7 * 115, CPSI 400), and dried at room temperature for about 5 hours. The carrier was calcined at 450 ° C. to complete the measurement carrier according to the invention.
비교예Comparative example
상기 실시예에서 탄소체 첨가를 제외하고는 동일하게 실시하여 비교 담체를 완성하였다.A comparative carrier was completed in the same manner as in the above example except for adding a carbon body.
실험예 1Experimental Example 1
도 1(a) 및 (b)는 각각 실시예 및 비교예 담체들의 촉매 매트릭스 단면 촬영이다. 도 1(a)에 의하면, 세공형성 첨가제에 의해 거대세공이 형성되며, 거대세공은 촉매복합재에 의한 형성된 미세세공과 망상구조를 형성하고 있음을 확인할 수 있는 한편, 도 1(b)에 의하면 촉매 매트릭스 단면은 촉매복합재에 의해서 형성된 매우 작은 입자들로 조밀하게 형성되어 배기가스 전달이 용이하지 아니한 구조임을 확인할 수 있다.1 (a) and (b) are cross-sectional photographs of catalyst matrices of the carriers of Examples and Comparative Examples, respectively. According to Figure 1 (a), it can be seen that the macropore is formed by the pore-forming additive, the macropore forms the fine pores and the network structure formed by the catalyst composite material, while the catalyst according to Figure 1 (b) The matrix cross section is densely formed of very small particles formed by the catalyst composite material, and it can be confirmed that the exhaust gas is not easily delivered.
실험예 2Experimental Example 2
도 2(a) 및 (b)는 각각 실시예 및 비교예 담체들을 대상으로 측정한 탄화수소(HC), CO 및 질소산화물 전환율을 도시한 것이다. 이에 의하면 세공형성 첨가물질에 의하여 거대세공이 미세세공과 함께 망상구조를 형성하는 촉매 매트릭스에서의 전환율을 단순히 미세세공에 의해 형성된 촉매 매트릭스와 대비하여 상당히 높은 것으로 측정되었다.2 (a) and (b) show the conversion of hydrocarbon (HC), CO and nitrogen oxides measured for the carriers of Examples and Comparative Examples, respectively. According to this, the conversion rate in the catalyst matrix in which the macropores form a network together with the micropores by the pore-forming additive material was measured to be considerably high compared to the catalyst matrix formed by the micropores.
본 발명은 세공형성 첨가물질을 포함하여 혼합슬러리를 제조한 후, 이를 담체에 침적시키고, 소성함으로써, 세공형성 첨가물질 (주형물질)로부터 거대세공을 구성하여, 간단한 방법으로 거대세공 및 미세세공이 망상구조를 형성하도록 촉매 매트릭스를 구성하는 방법에 관한 것이다. 이에 의해 본 발명은 촉매 매트릭스에서 물질전달이 개선되는 효과를 얻을 수 있어, 차량 배출 배기가스는 촉매 매트릭스 내부로 침투가 용이하여 높은 정화능을 발휘할 수 있다.According to the present invention, after preparing a mixed slurry including the pore-forming additive material, it is deposited on a carrier and calcined to form a macropore from the pore-forming additive material (template), thereby producing macropore and micropore by a simple method. A method of constructing a catalyst matrix to form a network structure. As a result, the present invention can obtain the effect of improving the material transfer in the catalyst matrix, the vehicle exhaust gas can easily penetrate into the catalyst matrix can exhibit a high purification ability.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020060030956A KR100783620B1 (en) | 2006-04-05 | 2006-04-05 | A method for improving mass-transfer into catalyst matrix |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020060030956A KR100783620B1 (en) | 2006-04-05 | 2006-04-05 | A method for improving mass-transfer into catalyst matrix |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20070099771A KR20070099771A (en) | 2007-10-10 |
KR100783620B1 true KR100783620B1 (en) | 2007-12-07 |
Family
ID=38804961
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020060030956A KR100783620B1 (en) | 2006-04-05 | 2006-04-05 | A method for improving mass-transfer into catalyst matrix |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR100783620B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101394287B1 (en) * | 2011-12-13 | 2014-05-13 | 한국에너지기술연구원 | Method to improve catalytic activities by employing network-typed pore structure in formed-catalyst |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR960021150A (en) * | 1994-12-08 | 1996-07-18 | 볼프강 메르크·라인하르트 헤르만 | Shell catalyst, preparation method thereof and use thereof |
US6440378B1 (en) | 1997-12-22 | 2002-08-27 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gases, a method of producing the same, and a method of purifying exhaust gases |
KR20060085302A (en) * | 2005-01-21 | 2006-07-26 | 삼성에스디아이 주식회사 | Support for fuel gas reforming catalyst with excellent heat and mass transfer characteristics and manufacturing method thereof |
-
2006
- 2006-04-05 KR KR1020060030956A patent/KR100783620B1/en active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR960021150A (en) * | 1994-12-08 | 1996-07-18 | 볼프강 메르크·라인하르트 헤르만 | Shell catalyst, preparation method thereof and use thereof |
US6440378B1 (en) | 1997-12-22 | 2002-08-27 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gases, a method of producing the same, and a method of purifying exhaust gases |
KR20060085302A (en) * | 2005-01-21 | 2006-07-26 | 삼성에스디아이 주식회사 | Support for fuel gas reforming catalyst with excellent heat and mass transfer characteristics and manufacturing method thereof |
Also Published As
Publication number | Publication date |
---|---|
KR20070099771A (en) | 2007-10-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102483435B1 (en) | Nitrous oxide removal catalysts for exhaust systems | |
US10472290B2 (en) | Honeycomb structure and production method for said honeycomb structure | |
US10953395B2 (en) | Honeycomb structure and production method for said honeycomb structure | |
JP4845795B2 (en) | Exhaust gas purification filter and manufacturing method thereof | |
JP6073805B2 (en) | Thermally stable catalyst support with barium sulfate | |
JP2016502929A (en) | Hollow microsphere catalyst support and method for producing the same | |
JP2016528025A (en) | Integrated support for emission control catalyst | |
JP2022526899A (en) | Layered three-metal catalyst article and method for manufacturing catalyst article | |
JP2011506095A (en) | Catalytic soot filter manufacturing and system | |
KR20100106496A (en) | Passivation-free coating process for catalytic soot filters | |
JP7228065B2 (en) | Catalyst-coated gasoline particulate filter and its manufacturing method | |
US20190178128A1 (en) | Titania-doped zirconia as platinum group metal support in catalysts for treatment of combustion engine exhausts streams | |
JP2019516541A (en) | Exhaust gas purification filter | |
JP4470554B2 (en) | Method for producing exhaust gas purification catalyst | |
JP5789715B2 (en) | Low-temperature oxidation catalyst with remarkable hydrophobicity for the oxidation of organic pollutants | |
JP6949019B2 (en) | Honeycomb structure and method for manufacturing the honeycomb structure | |
JP2004154766A (en) | Ceramic catalyst body | |
KR100783620B1 (en) | A method for improving mass-transfer into catalyst matrix | |
JP2007136357A (en) | Manufacturing method of catalyst for purification of exhaust gas | |
JP2003251201A (en) | Method for forming porous coating layer | |
JP6807447B2 (en) | Exhaust gas purification catalyst carrier and exhaust gas purification catalyst | |
JP2000271443A (en) | Production of exhaust gas cleaning catalyst | |
JP6985842B2 (en) | Honeycomb catalyst | |
JP2023545789A (en) | Three-way conversion catalyst article | |
RU2021121111A (en) | STRUCTURED MONOLITHIC CATALYST FOR REDUCING NOx EMISSIONS IN EXHAUST GAS COMPOSITION, METHOD FOR PRODUCING CATALYST AND ITS APPLICATION |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E90F | Notification of reason for final refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20121203 Year of fee payment: 6 |
|
FPAY | Annual fee payment |
Payment date: 20131203 Year of fee payment: 7 |
|
FPAY | Annual fee payment |
Payment date: 20141203 Year of fee payment: 8 |
|
FPAY | Annual fee payment |
Payment date: 20151203 Year of fee payment: 9 |
|
FPAY | Annual fee payment |
Payment date: 20161205 Year of fee payment: 10 |
|
FPAY | Annual fee payment |
Payment date: 20171204 Year of fee payment: 11 |
|
FPAY | Annual fee payment |
Payment date: 20181203 Year of fee payment: 12 |
|
FPAY | Annual fee payment |
Payment date: 20191203 Year of fee payment: 13 |