KR20070075044A - Catalyst for the removal of nitrogen oxides with reducing agent and its preparation method - Google Patents
Catalyst for the removal of nitrogen oxides with reducing agent and its preparation method Download PDFInfo
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- KR20070075044A KR20070075044A KR1020060003315A KR20060003315A KR20070075044A KR 20070075044 A KR20070075044 A KR 20070075044A KR 1020060003315 A KR1020060003315 A KR 1020060003315A KR 20060003315 A KR20060003315 A KR 20060003315A KR 20070075044 A KR20070075044 A KR 20070075044A
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- silver
- catalyst
- reducing agent
- nitrogen oxide
- alumina
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000003638 chemical reducing agent Substances 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004332 silver Substances 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000460 chlorine Substances 0.000 claims abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 229910052878 cordierite Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical group [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims 1
- 229910001923 silver oxide Inorganic materials 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004976 chemiluminescence spectroscopy Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27B—SAWS FOR WOOD OR SIMILAR MATERIAL; COMPONENTS OR ACCESSORIES THEREFOR
- B27B17/00—Chain saws; Equipment therefor
- B27B17/08—Drives or gearings; Devices for swivelling or tilting the chain saw
- B27B17/083—Devices for arresting movement of the saw chain
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B01J35/56—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
Abstract
Description
도 1은 실시예 1 및 비교예 1에 따른 촉매의 NOx 전환율을 나타낸 그래프로 도1a는 은 담지 함량이 4중량% 인 것이고, 도1b는 은 담지 함량이 7중량%인 것이다.1 is a graph showing the NOx conversion rate of the catalysts according to Example 1 and Comparative Example 1, Figure 1a is a 4% by weight silver support, Figure 1b is a 7% by weight silver support.
도 2는 실시예 2 및 비교예 2에 따른 촉매의 NOx 전환율을 나타낸 그래프로 도2a는 은 담지 함량이 2중량%이고, 도2b는 4중량%, 도 2c는 6중량%인 것이다.Figure 2 is a graph showing the NOx conversion rate of the catalyst according to Example 2 and Comparative Example 2, Figure 2a is a silver loading content of 2% by weight, Figure 2b is 4% by weight, Figure 2c is 6% by weight.
도 3은 실시예 3 및 비교예 3에 따른 촉매의 NOx 전환율 그래프이다.3 is a graph of NOx conversion rate of the catalyst according to Example 3 and Comparative Example 3.
본 발명은 기체 및 액체 상태의 탄화수소를 연료로 연소하는 고정 및 이동 배출원의 배가스에 포함된 질소산화물을 제거하기 위한 촉매의 제조방법에 관한 것으로서, 상세하게는 배가스의 이동경로에 촉매를 설치하고 촉매 전단에 환원제를 분사하여 질소산화물이 환원제와 촉매에 의해 질소로 환원되는 장치에 적용되는 촉매의 제조방법에 관한 것이다.The present invention relates to a method for preparing a catalyst for removing nitrogen oxides contained in the flue gas of a fixed and mobile exhaust source for burning gaseous and liquid hydrocarbons as fuel. The present invention relates to a method for producing a catalyst which is applied to a device in which a nitrogen oxide is reduced to nitrogen by a reducing agent and a catalyst by injecting a reducing agent in the front end.
미국특허공보 제5993764호에는 환원제로 프로판과 제올라이트 촉매를 이용한 질소산화물을 질소로 환원시키는 방법이 개시되어 있으나, 제올라이트 촉매는 최대 활성이 낮고 장기 내구성에 문제가 있어 상용화되지 못하고 있다.US Patent No. 5993764 discloses a method of reducing nitrogen oxides to nitrogen using propane and zeolite catalysts as reducing agents, but zeolite catalysts are not commercialized due to their low maximum activity and long-term durability.
미국특허공보 제5824621호및 6284211호는 환원제로 에탄올과 은촉매를 이용하여 질소산화물을 질소로 환원시켜 제거하는 방법이 개시되어 있으며, 은촉매는 제올라이트 촉매에 비하여 최대활성이 높고 장기 내구성에 문제가 없어 상용화단계에 이르고 있지만, 은촉매의 경우도 에탄올이 아닌 프로필렌 또는 경유 등을 환원제로 사용할 경우 최대 활성이 떨어지며 사용가능한 온도범위도 좁아지게 된다.U.S. Pat. Although the commercialization stage has been reached, even in the case of silver catalyst, when propylene or diesel oil is used instead of ethanol as a reducing agent, the maximum activity decreases and the usable temperature range is narrowed.
본 발명은 기체 및 액체 상태의 탄화수소를 연소하는 고정 및 이동 배출원의 배가스에 포함된 질소산화물을 제거하기 위한 촉매 및 촉매의 제조방법을 제공하는 것이다.The present invention provides a catalyst and a method for producing the catalyst for removing nitrogen oxides contained in the exhaust gas of a fixed and mobile exhaust source for burning gaseous and liquid hydrocarbons.
상세하게는 환원제 존재 시 질소산화물을 질소로 환원시키는 높은 활성과 적용 가능한 온도범위가 넓은 촉매 및 촉매의 제조방법을 제공하는 것이다.In detail, the present invention provides a catalyst having a high activity and a wide temperature range applicable to reducing nitrogen oxides to nitrogen in the presence of a reducing agent.
이에, 본 발명의 발명자는 상기와 같은 문제점을 해결하기 위하여 예의 노력한 결과, 알루미나와 담체에 은(Ag)과 함께 염소를 담지한 촉매물질을 포함시켜 질소산화물 저감용 촉매를 제조함으로써 질소산화물의 제거효율을 높일 수 있음을 확 인하였다.Accordingly, the inventors of the present invention have made intensive efforts to solve the above problems, and as a result, a catalyst for reducing nitrogen oxides was prepared by including a catalyst material carrying chlorine together with silver (Ag) in alumina and a carrier to remove nitrogen oxides. It was confirmed that the efficiency can be increased.
따라서, 본 발명은 알루미나 담체에 은(Ag) 및 염소가 담지된 질소산화물 저감용 촉매를 제공하는 데 그 목적이 있다. Accordingly, an object of the present invention is to provide a catalyst for reducing nitrogen oxides in which silver (Ag) and chlorine are supported on an alumina carrier.
본 발명은 알루미나 등의 담지체에 은 촉매성분 및 염소가 담지된 새로운 질소산화물 환원촉매를 제공하는 것이다.The present invention provides a new nitrogen oxide reduction catalyst having a silver catalyst component and chlorine supported on a support such as alumina.
본 발명의 또 다른 과제는 보다 효과적으로 질소산화물을 환원시킬 수 있는 새로운 질소산화물 제거촉매를 제공하는 것이다.Another object of the present invention is to provide a novel nitrogen oxide removal catalyst that can reduce nitrogen oxides more effectively.
본 발명은 기체 및 액체 상태의 탄화수소를 연료로 연소하는 고정 및 이동 배출원의 배가스에 포함된 질소산화물을 제거하기 위한 촉매 및 이의 제조방법에 관한 것으로서, 보다 상세하게는 담체에 은(Ag) 및 염소성분이 담지된 촉매를 코팅한 지지체로 구성되는 것을 특징으로 하는 환원제를 이용한 질소산화물 저감 촉매 및 그의 제조방법에 관한 것이다.BACKGROUND OF THE
본 발명을 상세히 설명하면 다음과 같다. The present invention is described in detail as follows.
본 발명에 따른 질소산화물 저감용 촉매는, 분말상 담체에, 특히 알루미나 담체에 은과 염소성분이 담지된 촉매를 의미하는 것으로, 상기 알루미나 담체는 질소산화물의 용이한 처리를 위하여 무결정형, 감마형, 세타형 또는 예타형의 결정구조를 갖는 것이 바람직하며, 사용양태는 전술한 결정구조를 갖는 알루미나 담체를 허니컴(honeycomb) 성형체 또는 실리콘 성형체, 바람직하게는 코디어라이트 (Cordierite) 허니컴 성형체와 같은 지지체에 코팅시켜 사용하게 된다.The catalyst for reducing nitrogen oxides according to the present invention refers to a catalyst in which silver and chlorine are supported on a powder carrier, particularly an alumina carrier. The alumina carrier is amorphous, gamma type, for easy treatment of nitrogen oxides. It is preferable to have the crystal structure of theta form or theta form, and the use mode is that the alumina carrier having the crystal structure described above is applied to a support such as a honeycomb molded body or a silicone molded body, preferably a Cordierite honeycomb molded body. Coated and used.
본 발명에 따른 은으로 사용 가능한 물질은 환원상태의 은(Ag), 염화은(AgCl), 질산은(AgNO3), 황산은(Ag2SO4) 또는 이들의 혼합물을 사용할 수 있으며, 그 사용량은 알루미나 담체의 중량 기준으로 은 함량이 0.1 내지 10 중량%가 되도록 사용하는 것이 바람직하다. 이는 상기 은의 함량이 0.1 중량% 미만일 경우 촉매작용을 담당하는 은의 절대량이 작게 되어 촉매의 성능이 현저히 감소되고, 10중량%를 초과하면 반응에 불리한 금속 은으로 존재하게 되어 촉매의 성능이 현저히 감소하게 된다.The material usable as silver according to the present invention may be reduced silver (Ag), silver chloride (AgCl), silver nitrate (AgNO 3 ), silver sulfate (Ag 2 SO 4 ) or a mixture thereof, the amount of which is used alumina It is preferable to use so that the silver content is 0.1 to 10% by weight based on the weight of the carrier. This means that when the content of silver is less than 0.1% by weight, the absolute amount of silver responsible for the catalysis becomes small, which significantly reduces the performance of the catalyst. do.
상기 염소성분이 담지되는 양에서는 제한이 되지 않지만, 은성분이 담지된 알루미늄 담지체 또는 은 성분이 담지된 알루미늄 담지체를 코팅한 성형체를 pH 3~6.5로 조절된 염산수용액에 담근 후, 450~600℃에서 소성하여 제조한다. 상기 염산수용액의 pH는 그 범위를 제한할 필요는 없으나, 3~6.5로 조절된 염산수용액을 사용할 경우 질소산화물 환원 촉매의 성능이 보다 우수하였으며, 소성온도도 상기의 범위를 가질 때 촉매 활성이 보다 우수하였다. 알루미늄 담지체를 염산수용액으로 딥코팅한 후 소성하는 경우 제조된 염소 및 은성분을 담지한 알루미늄 담지체는 다시 성형체에 워시코팅(wash coating)하여 제조한다.The amount of the chlorine component supported is not limited, but after the aluminum carrier supporting the silver component or the molded article coated with the aluminum carrier supporting the silver component is immersed in an aqueous hydrochloric acid solution adjusted to pH 3 to 6.5, 450 to 600 It is prepared by baking at 占 폚. The pH of the aqueous hydrochloric acid solution does not need to limit the range, but when the hydrochloric acid aqueous solution adjusted to 3 to 6.5 is used, the performance of the nitrogen oxide reduction catalyst is better, and the catalytic activity is higher when the firing temperature also has the above range. Excellent. When the aluminum carrier is dip-coated with an aqueous hydrochloric acid solution and calcined, the aluminum carrier carrying the produced chlorine and silver components is again prepared by wash coating on the molded body.
이하는 본 발명에 따른 질소산화물 환원촉매의 제조방법에 대하여 상세히 살핀다. The following is a detailed look at the method for producing a nitrogen oxide reduction catalyst according to the present invention.
본 발명에 따른 질소산화물 환원촉매의 제조방법은 하기의 단계를 포함하여 이루어진다.The method for preparing a nitrogen oxide reduction catalyst according to the present invention comprises the following steps.
탈이온 증류수에 알루미나를 첨가하여 볼밀하여 균일한 알루미나 슬러리를 제조하는 단계;Adding alumina to deionized distilled water to obtain a uniform alumina slurry by ball milling;
상기 슬러리를 실리콘 카바이드 또는 코디어라이트 허니컴 성형체에 코팅한 후 건조 또는 건조와 소성하는 단계;Coating the slurry on silicon carbide or cordierite honeycomb molded bodies and then drying or drying and baking the slurry;
건조 또는 소성된 허니컴 성형체를 은 전구체용액에 함침한 후 상온에서 건조 또는 건조와 소성하는 단계; 및Impregnating the dried or calcined honeycomb molded body with the silver precursor solution and drying or calcining at room temperature; And
상기 은 성분이 담지된 성형체를 염산수용액에 함침하여 코팅한 후, 건조 및 소성하는 단계.Coating the molded product on which the silver component is supported by impregnation with an aqueous hydrochloric acid solution, and then drying and calcining.
본 발명에 따른 질소산화물 저감용 환원촉매의 제조 방법은 탈이온 증류수에 알루미나를 첨가한 다음 습식 볼밀을 이용하여 균일한 알루미나 슬러리를 제조하고, 상기 슬러리를 실리콘 카바이드 또는 코디어라이트 허니컴 성형체에 코팅한 다음상온에서 건조하는 단계를 가지며, 필요시에는 건조하고 소성로에서 건조 및 소성하는 단계를 가지는 것도 좋다. 상기 건조 또는 소성된 허니컴 성형체를 염화은(AgCl), 질산은(AgNO3), 황산은(Ag2SO4) 또는 이들의 혼합물 수용액에 함침한 후 상온에서 건조시킨다. 필요에 의해서 건조 후 소성로에서 건조 및 소성하는 단계를 포함할 수 도 있다. 다음으로, 건조 또는 소성된 은성분이 담지된 성형체를 pH 3~6.5로 조절된 염산수용액에 담그어 충분한 시간동안 코팅한 후, 다시 건조한 후, 소성로에 투입한 후 상온에서 서서히 온도를 승온시키면서 80~150℃에서 1 내지 5 시간 건조한 다음, 다시 서서히 승온하여 450~600℃에서 1 내지 5시간 소성하여 제조한다. 또한 Ag화합물을 pH 3~6.5로 조절된 염산수용액에 투입하여 용해한 후, 알루미나를 코팅한 성형체를 투입하여 코팅한 다음 상기의 조건에서 건조 소성하여 제조하는 것도 가능하다.In the method for preparing a reduction catalyst for reducing nitrogen oxides according to the present invention, alumina is added to deionized distilled water and a uniform alumina slurry is prepared using a wet ball mill, and the slurry is coated on a silicon carbide or cordierite honeycomb molded body. Next, the step of drying at room temperature, if necessary, may be dried, and the step of drying and firing in a kiln. The dried or calcined honeycomb molded body is impregnated with silver chloride (AgCl), silver nitrate (AgNO 3 ), silver sulfate (Ag 2 SO 4 ), or a mixture thereof, and then dried at room temperature. It may also include the step of drying and firing in the kiln after drying if necessary. Next, the molded product bearing the dried or calcined silver component was coated in an aqueous hydrochloric acid solution adjusted to pH 3 to 6.5, coated for a sufficient time, and then dried again, then put into a firing furnace and gradually heated up at room temperature at 80 to 150 ° C. After drying for 1 to 5 hours at a temperature, the temperature is gradually increased again to bake at 450 to 600 ° C for 1 to 5 hours. In addition, the Ag compound is dissolved in an aqueous solution of hydrochloric acid adjusted to pH 3 ~ 6.5, dissolved, and then coated with alumina-coated molded body and then dried and calcined under the above conditions.
이하, 본 발명을 실시예에 의하여 더욱 상세히 설명하고자 한다. 그러나, 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 이들 실시예에 의하여 본 발명의 범위가 한정되지는 않는다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for illustrating the present invention more specifically, and the scope of the present invention is not limited to these examples.
[실시예 1] Example 1
촉매의 제조Preparation of the catalyst
감마 알루미나 파우더[Al-1, 표면적 : 210m2/gr, 기공부피:0.5cc/gr, 비중:0.8g/cc] 와 초산 및 2차 증류수를 혼합한 다음, 습식 볼밀을 이용하여 24시간 분쇄하여 균일한 알루미나 슬러리를 제조하였다. 습식 볼밀을 통해 분쇄한 알루미나의 평균 입자크기가 2 내지 8 마이크로미터가 되도록 하였다.Gamma alumina powder [Al-1, surface area: 210m 2 / gr, pore volume: 0.5cc / gr, specific gravity: 0.8g / cc], acetic acid and secondary distilled water are mixed, and then pulverized using a wet ball mill for 24 hours. A homogeneous alumina slurry was prepared. The average particle size of the alumina ground through a wet ball mill was adjusted to 2 to 8 micrometers.
상기 제조한 알루미나 슬러리에 2.5x2.5x2.5cm 크기, 400 cpsi의 코디어라이트 허니컴을 와시코팅(washcoat)하여 알루미나의 담지량이 0.244 g/cm3이 되도록 코팅한 다음, 소성로에서 투입하여 상온에서 120℃까지 분당 5℃로 승온한 다음, 120℃에서 2시간 건조한 후, 120℃에서 550℃까지 분당 5℃로 승온한 후, 550℃에서 3 시간 소성하였다.Wash coating the cordierite honeycomb of 2.5x2.5x2.5cm size and 400 cpsi to the prepared alumina slurry to coat the alumina supporting amount to be 0.244 g / cm 3 , and then put it in a calcination furnace to obtain 120 at room temperature. After heating up to 5 degreeC per minute, and drying at 120 degreeC for 2 hours, after heating up at 120 degreeC to 550 degreeC at 5 degreeC per minute, it baked at 550 degreeC for 3 hours.
다음 상기 소성된 알루미나 담지 코디어라이트 건조체를 질산은을 용해하여 제조한 용액에 함침하여, 은이 알루미나 중량 대비 4.0 및 7.0중량%가 되게 함침한 후, 상기의 알루미나 와시코팅 조건과 동일하게 소성하였다.Next, the calcined alumina-supported cordierite dried body was impregnated into a solution prepared by dissolving silver nitrate, and the silver was impregnated to 4.0 and 7.0 wt% based on the weight of alumina, and then calcined in the same manner as in the alumina wash coating.
이후 은이 담지된 성형체를 pH 5.0으로 희석된 염산수용액에 20초간 잠시 함침하였다. 함침된 성형체는 다시 상기의 알루미나 와시코팅 조건과 같이 소성하여 최종적으로 염소와 은이 담지된 성형체를 제조하였다.Thereafter, the silver-supported molded body was impregnated for 20 seconds in an aqueous hydrochloric acid solution diluted to pH 5.0. The impregnated molded body was calcined again under the alumina washer coating conditions to finally prepare a molded body bearing chlorine and silver.
촉매의 성능 평가Performance Evaluation of Catalyst
상기 제조한 허니컴 촉매는 실제 자동차 배가스와 유사한 조성을 가지는 모델 반응가스 혼합물을 이용하여 질소산화물 저감 테스트를 수행하였다. 허니컴 촉매를 스테인레스스틸로 만들어진 반응기 안에 고정하였으며, 촉매의 전단과 후단에 열전대를 위치하였다. 반응기의 온도는 반응기를 원통형 소성로를 이용하여 정밀하게 조절하였다. The honeycomb catalyst prepared above was subjected to a nitrogen oxide reduction test using a model reaction gas mixture having a composition similar to that of an actual vehicle exhaust gas. The honeycomb catalyst was fixed in a reactor made of stainless steel, and thermocouples were placed at the front and rear of the catalyst. The temperature of the reactor was precisely controlled by using a cylindrical kiln.
각각의 반응가스는 질량유량계를 사용하여 정밀하게 유량을 조절하였으며, 이때 반응물의 공간속도는 50,000 hr-1이었다. 환원제는 디젤을 가장 잘 모사하는 것으로 알려진 프로필렌을 사용하였으며, 환원제/NOx의 몰비를 5로 유지하였다. Each reaction gas was precisely controlled using a mass flow meter, and the space velocity of the reactants was 50,000 hr −1 . The reducing agent used propylene, best known to mimic diesel, and maintained a molar ratio of reducing agent / NOx at 5.
상기 반응가스기로 유입되는 배가스의 조성을 표1에 나타내었다.Table 1 shows the composition of the exhaust gas flowing into the reaction gas machine.
[표 1]TABLE 1
반응기 전단과 후단의 배출가스의 농도는 반응장치와 직접 연결된 화학발광법 또는 적외선분광법을 채택한 정량 정밀 가스분석기를 사용하여 NO, NO2, THC, CO, N2O를 연속적으로 측정하였고, 그 결과는 도 1a 및 도 1b에 나타내었다.The concentrations of exhaust gas at the front and rear of the reactor were continuously measured NO, NO 2 , THC, CO, N 2 O using a quantitative precision gas analyzer adopting chemiluminescence or infrared spectroscopy directly connected to the reactor. Are shown in FIGS. 1A and 1B.
[비교예 1] Comparative Example 1
상기 실시예 1에서 촉매 제조 시 염산수용액을 담지하지 않은 것을 제외하고는 실시예 1과 동일하게 진행하였다. 그 결과는 실시예1의 결과와 함께 도 1a 및 도 1b에 나타내었다.In Example 1, the catalyst was prepared in the same manner as in Example 1, except that the aqueous hydrochloric acid solution was not supported. The results are shown in FIGS. 1A and 1B together with the results of Example 1. FIG.
도 1, 2에 나타난 바와 같이 알루미나 담지체에 은 촉매가 담지되고 또한 염소가 담지된 실시예의 경우에는 질소산화물의 활성도가 450 ℃근처에서 최대 활성도인 80%~88% 내외의 우수한 촉매특성을 나타내었고, 전체적인 온도범위에서 매우 우수한 촉매활성을 나타내었음을 알 수 있다. 그러나 비교예와 같이 염소성분을 담지하지 않은 경우는 염소원소를 담지한 경우와 대비시 최대활성온도 부근에서는 10~20%정도로 활성도가 낮았으며, 온도범위 전체에 걸쳐서 최대 50%정도 촉매활성이 낮은 결과를 보여주었다.As shown in FIGS. 1 and 2, in the case where the silver catalyst is supported on the alumina support and the chlorine is supported, the activity of nitrogen oxide shows excellent catalytic properties of about 80% to 88% of the maximum activity near 450 ° C. It can be seen that the catalytic activity was excellent in the whole temperature range. However, in the case of not carrying the chlorine component as in the comparative example, the activity was low at around 10 to 20% near the maximum activity temperature compared to the case of carrying the chlorine element, and the catalytic activity was low at the maximum of 50% over the entire temperature range. Showed results.
[실시예 2]Example 2
상기 실시예 1에서와 같이 제조하되, 사용된 알루미나는 감마 알루미나 파우더[Al-2, 표면적 : 274m2/gr, 기공부피:0.5cc/gr, 비중:0.6g/cc]를 사용하였으며, 은이 알루미나 중량 대비 2.0, 4.0 및 6.0중량%가 되게 함침한 후, 실시예1의 알루미나 와시코팅 조건과 동일하게 소성하였다.Prepared as in Example 1, the alumina used was gamma alumina powder [Al-2, surface area: 274m 2 / gr, pore volume: 0.5cc / gr, specific gravity: 0.6g / cc], silver is alumina After impregnation to 2.0, 4.0 and 6.0% by weight based on the weight, it was calcined in the same manner as in the alumina wash coating of Example 1.
이후 은이 담지된 성형체를 pH 5.5로 희석된 염산수용액에 20초간 잠시 함침하였다. 함침된 성형체는 다시 실시예1의 알루미나 와시코팅 조건과 같이 소성하여 최종적으로 염소와 은이 담지된 성형체를 제조하였고, 촉매 성능 평가는 실시예 1의 방법과 동일하게 진행하여 그 결과는 도 1a 및 도 1b에 나타내었다.Thereafter, the silver-supported molded body was impregnated for 20 seconds in an aqueous hydrochloric acid solution diluted to pH 5.5. The impregnated molded body was calcined again in the same manner as in the alumina wash coating conditions of Example 1 to finally prepare a molded product loaded with chlorine and silver, and the catalyst performance evaluation was performed in the same manner as in Example 1, and the results are shown in FIGS. 1A and FIG. Shown in 1b.
[비교예 2] Comparative Example 2
상기 실시예 2에서 금속 담지 시 염산수용액을 담지하지 않은 것을 제외하고는 실시예 2와 동일하게 진행하였고 촉매 성능 평가 결과는 실시예2의 결과와 함께 도 2a, 도 2b 및 도 2c에 나타내었다.In Example 2, the same procedure as in Example 2 was carried out except that the aqueous solution of hydrochloric acid was not supported. The results of the catalyst performance evaluation are shown in FIGS. 2A, 2B, and 2C together with the results of Example 2.
도 2a 내지 2c에 나타난 바와 같이 알루미나 담지체에 은 촉매가 담지되고 또한 염소가 담지된 실시예의 경우에는 염소가 담지되는 않은 경우에 비해 반응온도 전 영역에서 질소산화물에 대한 높은 활성을 보임을 알 수 있다.As shown in FIGS. 2A to 2C, the silver catalyst supported on the alumina carrier and the chlorine supported example showed higher activity against nitrogen oxides in the entire reaction temperature region than when chlorine was not supported. have.
[실시예 3]Example 3
상기 실시예 2에서와 같이 제조하되, 질산은 수용액을 이용하여 은이 알루미나 중량 대비 2.0중량%가 되게 성형체를 함침한 후, 실시예 1의 알루미나 와시코팅 조건과 동일하게 소성하였다.Prepared as in Example 2, using a silver nitrate aqueous solution was impregnated so that the silver is 2.0% by weight based on the weight of alumina, and then calcined in the same manner as the alumina wash coating of Example 1.
이후 은이 담지된 성형체를 pH 5.5로 희석된 염산수용액에 20초간 잠시 함침하였다. 함침된 성형체는 다시 실시예1의 알루미나 와시코팅 조건과 같이 소성하여 최종적으로 염소와 은이 담지된 성형체를 제조하였고, 촉매 성능 평가는 실시예 1과 동일하게 진행하여 그 결과는 도3에 나타내었다.Thereafter, the silver-supported molded body was impregnated for 20 seconds in an aqueous hydrochloric acid solution diluted to pH 5.5. The impregnated molded body was calcined again in the same manner as in the alumina wash coating conditions of Example 1 to finally prepare a molded body loaded with chlorine and silver, and catalyst performance evaluation was performed in the same manner as in Example 1, and the results are shown in FIG. 3.
[비교예 3] Comparative Example 3
상기 실시예 2와 같이 제조하되, 질산은 수용액에 함침하기 전에 알루미나가 코팅된 성형체를 pH 5.5로 희석된 염산수용액에 20초간 잠시 함침하였다. 함침된 성형체는 다시 실시예1의 알루미나 와시코팅 조건과 같이 소성하였으며, 이후에 질산은 수용액을 이용하여 은이 알루미나 중량 대비 2.0중량%가 되게 성형체를 함침한 후, 실시예1의 알루미나 와시코팅 조건과 동일하게 소성하였다. 그 결과는 실시예3의 결과와 함께 도 3에 나타내었다. Prepared as in Example 2, the alumina-coated molded body was impregnated for 20 seconds in an aqueous hydrochloric acid solution diluted to pH 5.5 before impregnating silver nitrate aqueous solution. The impregnated molded body was calcined again under the alumina washer coating conditions of Example 1, and after impregnating the molded body so that silver was 2.0% by weight based on the weight of the alumina using an aqueous solution of silver nitrate, the same as the alumina washer coating condition of Example 1 Fired. The results are shown in Figure 3 together with the results of Example 3.
도 3에서 알 수 있듯이 은을 먼저 담지한 후 염소를 담지한 촉매의 경우 최고 88%의 NOx 전환율을 보이는 반면에, 염소를 먼저 담지한 후 은을 담지한 촉매의 경우에는 최고 전환율이 77%로 약 10% 낮은 성능을 보이는 것을 알 수 있다.As can be seen in FIG. 3, the catalyst which supports silver first and then chlorine supports NOx conversion of up to 88%, while the catalyst that supports chlorine first and silver supports 77% of the highest conversion. It can be seen that the performance is about 10% lower.
상기의 결과로부터 확인된 바와 같이 본 발명의 촉매성분인 염소를 은이 담지된 촉매에 담지하였을 때 질소산화물 저감 효율이 현저히 증대되었음을 알 수 있다. 또한 염소를 먼저 담지하고 은을 나중에 담지한 촉매보다 은을 먼저 담지하고 염소를 나중에 담지한 촉매가 현저히 높은 성능을 보임을 알 수 있다.As confirmed from the above results, it can be seen that nitrogen oxide reduction efficiency was remarkably increased when chlorine, which is a catalyst component of the present invention, was supported on a silver-supported catalyst. In addition, it can be seen that a catalyst loaded with silver first and then later loaded with chlorine has a significantly higher performance than a catalyst loaded with chlorine first and silver later.
본 발명에 따른 은성분과 염소성분이 담지된 촉매는 질소산화물의 절감효과가 매우 우수하였으며, 기존의 촉매에 비하여 넓은 온도범위에서 우수한 촉매활성을 나타내는 것을 알 수 있었다.Silver and chlorine-containing catalyst according to the present invention was very excellent in the effect of reducing the nitrogen oxides, it was found that exhibits excellent catalytic activity in a wide temperature range compared to the existing catalyst.
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| KR101160399B1 (en) * | 2010-02-02 | 2012-06-26 | 주식회사 젬백스앤카엘 | A Coating Method Of MMOMethan Mono-Oxygenase Catalyst For Reduction Of Nitrogen Oxides And A Supporting Body Using The Same |
| WO2014158009A1 (en) | 2013-03-29 | 2014-10-02 | 고려대학교 산학협력단 | Nanocatalyst filter and production method for same |
| US11071946B2 (en) | 2013-03-29 | 2021-07-27 | Korea University Research And Business Foundation | Nano-catalyst filter and production method for same |
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| CN114100641A (en) * | 2021-12-14 | 2022-03-01 | 宁波市海智材料产业创新研究院 | AgCl/Al2O3Preparation method of catalyst, catalyst and application |
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| JPH0952047A (en) * | 1995-08-17 | 1997-02-25 | Sekiyu Sangyo Kasseika Center | Catalyst for contact reducing nitrogen oxide |
| JPH09168720A (en) * | 1995-12-20 | 1997-06-30 | Tosoh Corp | Removing method for nitrogen oxide |
| JP3924341B2 (en) | 1997-01-24 | 2007-06-06 | 財団法人石油産業活性化センター | Method for catalytic reduction of nitrogen oxides |
| JPH09239271A (en) * | 1996-03-05 | 1997-09-16 | Hino Motors Ltd | Exhaust gas purifying catalyst and its production |
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| US20030118960A1 (en) * | 2001-12-21 | 2003-06-26 | Balmer-Millar Mari Lou | Lean NOx aftertreatment system |
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| KR101160399B1 (en) * | 2010-02-02 | 2012-06-26 | 주식회사 젬백스앤카엘 | A Coating Method Of MMOMethan Mono-Oxygenase Catalyst For Reduction Of Nitrogen Oxides And A Supporting Body Using The Same |
| WO2014158009A1 (en) | 2013-03-29 | 2014-10-02 | 고려대학교 산학협력단 | Nanocatalyst filter and production method for same |
| US11071946B2 (en) | 2013-03-29 | 2021-07-27 | Korea University Research And Business Foundation | Nano-catalyst filter and production method for same |
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