KR100408503B1 - Catalyst for purifying exhaus gas of vehicle - Google Patents
Catalyst for purifying exhaus gas of vehicle Download PDFInfo
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- KR100408503B1 KR100408503B1 KR1019960029845A KR19960029845A KR100408503B1 KR 100408503 B1 KR100408503 B1 KR 100408503B1 KR 1019960029845 A KR1019960029845 A KR 1019960029845A KR 19960029845 A KR19960029845 A KR 19960029845A KR 100408503 B1 KR100408503 B1 KR 100408503B1
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- catalyst
- platinum
- rhodium
- exhaust gas
- zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- 239000010948 rhodium Substances 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 16
- 238000000746 purification Methods 0.000 claims abstract description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052680 mordenite Inorganic materials 0.000 claims description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 69
- 230000003197 catalytic effect Effects 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000003915 air pollution Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- XZXAIFLKPKVPLO-UHFFFAOYSA-N cobalt(2+);dinitrate;hydrate Chemical compound O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XZXAIFLKPKVPLO-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- -1 diamine dichloroplatinum hydrate Chemical class 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- B01J35/56—
Abstract
Description
본 발명은 자동차 배기가스 정화용 촉매에 관한 것으로서, 보다 상세하게는 고온의 희박연소 분위기하에서도 자동차에서 발생하는 질소산화물에 대하여 탁월한 정화능력을 갖는 촉매에 관한 것이다.The present invention relates to a catalyst for automobile exhaust gas purification, and more particularly, to a catalyst having excellent purification ability against nitrogen oxides generated in automobiles even under a high temperature lean burn atmosphere.
최근들어 전세계적으로 환경에 대한 관심이 높아지면서 환경오염 문제가 국가적인 차원에서 관리되고 있다. 환경오염은 크게 대기 오염, 수질 오염, 토양 오염 등으로 대별될 수 있다.Recently, due to the increasing interest in the environment, environmental pollution is being managed at the national level. Environmental pollution can be roughly classified into air pollution, water pollution, and soil pollution.
이중, 대기 오염을 일으키는 대기 오염물질은 대개의 경우 연소체로부터 배출된다. 따라서, 대기오염은 연소체의 배출시설 구조와 조작 방법, 그리고 외부 기상조건 등에 의해 피해의 경중이 결정된다. 이러한 연소체로서 대표적인 것이 자동차이다.Of these, air pollutants that cause air pollution are usually emitted from combustion bodies. Therefore, air pollution is determined by the structure of the combustion facility, the operation method, and external weather conditions. A typical example of such a combustion body is an automobile.
자동차는 다른 배출시설과는 달리 움직이면서 오염물질을 배출하는 특징을가지고 있는데, 생활수준의 향상에 따라 자동차 사용이 급속하게 증가하고 있어서 자동차의 배기가스로 인한 대기오염 문제는 날로 심각해지고 있다.Unlike other emission facilities, automobiles emit pollutants while moving, and the use of automobiles is increasing rapidly with the improvement of living standards, so the air pollution problem caused by the exhaust of automobiles is getting serious.
자동차 배기가스 중의 주요 유해 성분은 탄화수소 (HC), 일산화탄소 (CO), 질소산화물 (NOx) 등이다. 이중 특히 질소산화물은 태양광선의 작용을 받아 공기 중의 산소와 결합하여 오존을 생성하는데, 지상의 오존 농도가 높아지면 (오존경보 발생기준: 0.12ppm) 호흡기 질환을 유발될 뿐 아니라 체내 단백질의 변성과 지방의 과산화 반응과 같은 생체 화학적 반응의 원인이 된다.The main harmful components in automobile exhaust gases are hydrocarbons (HC), carbon monoxide (CO) and nitrogen oxides (NO x ). Of these, nitrogen oxides, in particular, combine with oxygen in the air under the action of sunlight to produce ozone. When the ozone concentration on the ground becomes higher (0.12 ppm of ozone alarms), it causes respiratory diseases as well as degeneration of protein in the body. It causes biochemical reactions such as fat peroxidation.
자동차 배기가스를 줄이는 방법은 크게 연료개선, 엔진개량, 배기가스 처리로 대별된다. 이중,배기가스 처리 방법의 경우, 촉매를 이용하는 것이 가장 효과적이다.Reduction of automobile exhaust gas is largely classified into fuel improvement, engine improvement, and exhaust gas treatment. In the case of the exhaust gas treatment method, it is most effective to use a catalyst.
현재, 자동차 배기가스를 정화하기 위한 촉매로는 3원 촉매가 가장 대표적인데, 허니콤에 코팅되어 있는 γ-알루미나에 백금, 팔라듐, 로듐 등이 담지된 형태이다. 이러한 3원 촉매는 엔진의 공연비 (공기/연료 비)가 14.7인 이상적인 상태에서는 유해 3원 가스인 탄화수소, 일산화탄소, 질소산화물에 대해 높은 정화율을 나타내고 있다.Currently, ternary catalysts are the most representative catalysts for purifying automobile exhaust gas, in which γ-alumina coated on honeycomb is loaded with platinum, palladium, rhodium, and the like. These three-way catalysts exhibit high purification rates for hydrocarbons, carbon monoxide and nitrogen oxides, which are hazardous three-way gases, under ideal conditions with an air-fuel ratio (air / fuel ratio) of 14.7.
그러나, 3원 촉매는 공연비가 14.7이 넘는 영역, 즉 상대적으로 과잉 공기를 사용하는 희박연소 영역에서는 질소산화물에 대한 정화능력이 상실되므로 통상의 3원 촉매를 사용할 수 없다는 문제점이 있다. 특히, 공연비가 18 내지 26인 산소과잉 영역에서 작동되는 희박연소 엔진이 사용되는 추세인데, 이러한 조건하에서 탄화수소와 일산화탄소는 산화 반응에 의해 쉽게 정화되지만 질소산화물을 무해한 질소 (N2)로 환원시키기는 어렵다. 따라서, 희박연소 영역에서 발생되는 질소산화물을 환원시키기 위한 촉매가 개발되어 사용되고 있다.However, the three-way catalyst has a problem in that a conventional three-way catalyst cannot be used in the region where the air-fuel ratio is more than 14.7, that is, the purification ability for nitrogen oxide is lost in the lean combustion region using relatively excess air. In particular, lean combustion engines operating in an oxygen-rich region with an air-fuel ratio of 18 to 26 are used. Under these conditions, hydrocarbons and carbon monoxide are easily purified by oxidation, but reducing nitrogen oxides to harmless nitrogen (N 2 ) it's difficult. Therefore, a catalyst for reducing nitrogen oxide generated in the lean burn region has been developed and used.
현재 사용되고 있는 질소산화물 환원용 촉매는 대부분 저온 영역 (400℃ 이하)에서만 좋은 활성을 나타내는 단점이 있다. 그 예로서, 제올라이트에 백금, 로듐 또는 팔라듐 등의 활성제를 단독으로 또는 2 성분 이상으로 담지시킨 것을 들 수 있다. 상기 촉매에 있어서, 로듐은 질소산화물의 환원력이 우수하고 질소산화물에 대한 흡착력이 뛰어나며, 백금은 저온에서 일산화탄소와 탄화수소를 산화시켜 제거하며 질소산화물에 대한 촉매 반응성을 향상시키는 역할을 한다.Nitrogen oxide reduction catalysts currently used have the disadvantage of showing good activity only in the low temperature region (400 ℃ or less). Examples thereof include those in which zeolite is supported by an active agent such as platinum, rhodium or palladium alone or in two or more components. In the catalyst, rhodium is excellent in reducing power of nitrogen oxides and excellent adsorptive power to nitrogen oxides, platinum serves to oxidize and remove carbon monoxide and hydrocarbons at low temperatures and to improve catalytic reactivity to nitrogen oxides.
그러나, 탄화수소가 질소산화물에 대한 촉매 활성을 촉진시키므로 백금이 다량 존재할 경우 다량의 탄화수소가 산화되기 때문에 온도가 상승할수록 질소산화물에 대한 촉매활성이 급격하게 떨어진다는 문제점이 있다. 즉, 약 250℃ 부근에서 최고의 활성을 나타내다가 400℃ 이상의 고온에서는 활성이 급격하게 저하된다. 그런데, 자동차는 운행중 엔진의 온도가 200 내지 600℃의 범위에 이르므로 이러한 종래의 촉매를 이용하여 질소 산화물을 정화하는데는 한계가 있다.However, since hydrocarbons promote catalytic activity for nitrogen oxides, when a large amount of platinum is present, a large amount of hydrocarbons are oxidized, and thus there is a problem in that catalytic activity for nitrogen oxides drops rapidly as temperature increases. That is, it exhibits the highest activity in the vicinity of about 250 ° C., but drops rapidly at a high temperature of 400 ° C. or higher. By the way, since the temperature of the engine is in the range of 200 to 600 ℃ while driving the vehicle there is a limit to purify the nitrogen oxide using such a conventional catalyst.
또한, 상기 촉매는 활성제로서 고가의 귀금속을 사용하기 때문에 촉매의 제조 단가가 상승하므로 비경제적이며, 제조 방법에 있어서도 종래에는 제올라이트에 백금, 로듐 및 팔라듐을 차례로 이온교환시키는 다단계 공정에 의해 제조되었는데, 이는 공정의 진행상 번거로울 뿐 아니라 제조 단가면에서도 불리하다.In addition, the catalyst is expensive because the production cost of the catalyst is increased because expensive precious metals are used as the activator, and in the manufacturing method, the catalyst is conventionally manufactured by a multi-step process in which ion, platinum, rhodium, and palladium are ion-exchanged sequentially. This is not only troublesome in the progress of the process, but also disadvantageous in terms of manufacturing cost.
그러므로, 이러한 한계를 극복할 수 있는 새로운 촉매의 개발이 요구되고 있다.Therefore, the development of a new catalyst that can overcome this limitation is required.
이외에도, 보일러 등과 같은 산업 설비에서 발생되는 질소산화물을 환원시켜 정화하기 위한 촉매의 개발도 요구되고 있다.In addition, the development of a catalyst for reducing and purifying nitrogen oxides generated in industrial facilities such as boilers is also required.
본 발명이 이루고자 하는 기술적 과제는 고온의 희박연소 분위기 하에서도 질소산화물에 대한 정화율이 매우 우수하고 가격도 저렴한 자동차 배기가스 정화용 촉매를 제공하는 것이다.SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a catalyst for purifying automobile exhaust gas, which has a very high purification rate and low cost for nitrogen oxide even in a high temperature lean burn atmosphere.
도 1은 온도 변화에 따른 질소산화물 정화율을 도시한 그래프이다.1 is a graph showing the nitrogen oxide purification rate with temperature change.
본 발명의 기술적 과제는 백금, 로듐 및 코발트가 담지된 제올라이트 담체가 허니콤에 담지되어 있는 것을 특징으로 하는 자동차 배기가스 정화용 촉매가 제공된다.The technical problem of the present invention is to provide a catalyst for purification of automobile exhaust gas, characterized in that the zeolite carrier loaded with platinum, rhodium and cobalt is supported on a honeycomb.
상기 본 발명의 촉매에 있어서, 상기 제올라이트는 바람직하게는 모데나이트이다.In the catalyst of the present invention, the zeolite is preferably mordenite.
또한, 상기 본 발명에 따른 촉매는, 바람직하게는 상기 제올라이트를 기준으로 하여 백금 0.5 내지 10중량%, 로듐 0.5 내지 7중량% 및 코발트 3 내지 17중량%를 함유한다.In addition, the catalyst according to the present invention preferably contains 0.5 to 10% by weight of platinum, 0.5 to 7% by weight of rhodium and 3 to 17% by weight of cobalt based on the zeolite.
본 발명의 촉매는 활성제로서 귀금속인 백금, 로듐 이외에 천이금속인 코발트를 추가로 포함함으로써 고온의 희박연소 분위기하에서도 촉매 활성이 우수하다. 또한, 고가인 백금의 함유량을 감소시킬 수 있으므로 제조 단가가 저렴해지는 효과를 얻을 수 있다.The catalyst of the present invention further contains cobalt, which is a transition metal, in addition to platinum and rhodium, which are noble metals, as the activator, so that the catalyst is excellent in a high temperature lean-burn atmosphere. In addition, since the content of expensive platinum can be reduced, the production cost can be reduced.
본 발명에 따른 자동차 배기가스 정화용 촉매는 통상의 제조방법, 예를 들면 a) 디아민디클로로백금 수화물, 질산로듐 용액 및 질산코발트 수화물을 제올라이트와 혼합하여 혼합물을 제조하는 단계; b) 상기 혼합물을 열처리하여 분말을 형성하는 단계; c) 상기 분말을 알루미나 및 탈이온수와 혼합하여 슬러리를 형성하는 단계; d) 상기 슬러리를 허니콤에 담지하는 단계; e) 상기 허니콤 담지체를 열처리하는 단계를 포함하는 제조방법에 따라 제조될 수 있다.The catalyst for automobile exhaust gas purification according to the present invention may be prepared by a conventional method, for example, a) preparing a mixture by mixing diamine dichloroplatinum hydrate, rhodium nitrate solution, and cobalt nitrate hydrate with zeolite; b) heat treating the mixture to form a powder; c) mixing the powder with alumina and deionized water to form a slurry; d) supporting the slurry in honeycomb; e) it may be prepared according to a manufacturing method comprising the step of heat-treating the honeycomb carrier.
전술한 자동차 배기가스 정화용 촉매의 제조 방법에서, 단계 a)에 있어서, 상기 제올라이트는 바람직하게는 모데나이트이다. 또한, 상기 디아민디클로로백금 수화물에서의 백금의 첨가량, 질산로듐 용액에서의 로듐의 첨가량 및 질산코발트 수화물에서의 코발트의 첨가량은 상기 제올라이트를 기준으로 하여 각각 0.5 내지 10중량%, 0.5 내지 7중량% 및 3 내지 17중량%이다.In the above-described method for producing a catalyst for automobile exhaust gas purification, in step a), the zeolite is preferably mordenite. Further, the amount of platinum added in the diaminedichloroplatinum hydrate, the amount of rhodium added in the rhodium nitrate solution, and the amount of cobalt added in the cobalt nitrate hydrate were 0.5 to 10% by weight, 0.5 to 7% by weight, respectively, based on the zeolite, and 3 to 17% by weight.
상기 단계 b)에 있어서는, 400 내지 600℃에서 2 내지 3시간 동안 열처리를 실시한다. 또한, 상기 단계 e)에 있어서는, 400 내지 700℃에서 2 내지 4시간 동안 열처리를 실시한다.In step b), heat treatment is performed at 400 to 600 ° C. for 2 to 3 hours. In addition, in the step e), the heat treatment is carried out at 400 to 700 ℃ for 2 to 4 hours.
이렇게 제조된 촉매는 백금 및 로듐 이외에 천이 금속인 코발트를 더 포함함으로써 고온에서도 질소산화물에 대하여 우수한 촉매 활성을 유지하므로 전체적인 질소산화물 정화효율이 개선될 수 있다. 또한, 백금 첨가량을 제한함으로써 경제적인 측면에서도 유용하며, 종래의 제조방법에서와는 달리 백금, 로듐 및 코발트를 제올라이트에 동시에 함침시키기 때문에 제조 공정을 단순화시킬 수 있는 잇점이있다.The catalyst thus prepared further includes cobalt, which is a transition metal, in addition to platinum and rhodium, thereby maintaining excellent catalytic activity against nitrogen oxides even at high temperatures, thereby improving overall nitrogen oxide purification efficiency. In addition, it is useful in terms of economics by limiting the amount of platinum added, and unlike the conventional manufacturing method, since the platinum, rhodium and cobalt are impregnated in the zeolite at the same time, the manufacturing process can be simplified.
이하, 실시예를 들어 본 발명을 보다 상세히 설명하고자 하나, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
실시예 1Example 1
디아민디클로로백금 수화물 [Pt(NH3)2Cl2xH2O] 26.31g, 질산로듐 [Rh(NO3)3] 용액 31.58㎖ 및 질산코발트 수화물 [Co(NO3)26H2O 7.7953g을 300㎖의 증류수가 담긴 비이커에 넣고 30분간 교반하면서 용해시켰다. 이때, 침전이 없는지를 확인한 다음, 여기에 모데나이트 30g을 첨가하였다. 이어서, 2시간 동안 교반한 다음, 상기 반응물이 들어있는 비이커를 핫 플레이트 (hot plate) 위에 놓고 60℃의 온도에서 교반하에 수분을 건조시켰다. 다음으로, 500℃에서 3시간 동안 열처리하여 분말을 제조하였다. 상기 분말 40g을 알루미나 졸 (알루미나 함량: 20%) 48g 및 탈이온수 100g과 함께 볼 밀 반응기에 넣고 30시간 동안 반응시켜서 슬러리를 제조하였다. 허니콤 중량을 기준으로 하여 20중량%가 되도록 상기 슬러리를 허니콤 (40×40×100㎜)에 담지한 다음, 600℃에서 4시간 동안 열처리하여 촉매인 5%Pt/5%Co/5%Rh/모르데나이트 (a)를 제조하였다.26.31 g of diaminedichloroplatinum hydrate [Pt (NH 3 ) 2 Cl 2 xH 2 O], 31.58 mL of rhodium nitrate [Rh (NO 3 ) 3 ] solution and 7.7953 g of cobalt nitrate hydrate [Co (NO 3 ) 26H 2 O 300 It was added to a beaker containing ㎖ distilled water and dissolved with stirring for 30 minutes. At this time, after confirming that there is no precipitation, 30 g of mordenite was added thereto. Then, after stirring for 2 hours, the beaker containing the reaction was placed on a hot plate and the moisture was dried under stirring at a temperature of 60 ° C. Next, a powder was prepared by heat treatment at 500 ° C. for 3 hours. 40 g of the powder was added together with 48 g of alumina sol (alumina content: 20%) and 100 g of deionized water into a ball mill reactor to react for 30 hours to prepare a slurry. The slurry was soaked in a honeycomb (40 × 40 × 100mm) to 20% by weight based on the weight of the honeycomb, and then heat-treated at 600 ° C. for 4 hours to provide 5% Pt / 5% Co / 5% as a catalyst. Rh / mordenite (a) was prepared.
상기 제조된 촉매에 대한 활성 평가를 하기의 가스 분위기 하에서 실시하여 그 결과를 도 1에 나타내었다:Activity evaluation for the prepared catalyst was carried out under the following gas atmosphere and the results are shown in FIG. 1:
NO 500ppm, C3H6800ppm, O28%, CO 0.2%, CO214%, H2O 10%,500 ppm NO, C 3 H 6 800 ppm, O 2 8%, CO 0.2%, CO 2 14%, H 2 O 10%,
공간 속도: 40,000h-1.Space velocity: 40,000 h -1 .
실시예 2 및 3Examples 2 and 3
실시예 1에서와 동일한 방법으로 촉매 10%Pt/5%Co/5%Rh/모르데나이트 (b) 및 촉매 15%Pt/5%Co/5%Rh/모르데나이트 (c)를 제조한 다음, 실시예 1에서와 동일하게 촉매 활성을 평가하여 그 결과를 도 1에 나타내었다.A catalyst 10% Pt / 5% Co / 5% Rh / mordenite (b) and a catalyst 15% Pt / 5% Co / 5% Rh / mordenite (c) were prepared in the same manner as in Example 1 Next, the catalyst activity was evaluated in the same manner as in Example 1, and the results are shown in FIG. 1.
비교예 1Comparative Example 1
디아민디클로로백금 수화물 [Pt(NH3)2Cl2xH2O] 55.55g을 300㎖의 증류수가 담긴 비이커에 넣고 30분간 교반하면서 용해시키는 것을 제외하고는 실시예 1에서와 동일한 방법으로 촉매 15%Pt/모르데나이트 (d)를 제조한 다음, 실시예 1에서와 동일하게 촉매 활성을 평가하여 그 결과를 도 1에 나타내었다.Catalyst 15% in the same manner as in Example 1 except that 55.55 g of diaminedichloroplatinum hydrate [Pt (NH 3 ) 2 Cl 2 xH 2 O] was added to a beaker containing 300 ml of distilled water and dissolved with stirring for 30 minutes. After preparing Pt / mordenite (d), the catalytic activity was evaluated in the same manner as in Example 1, and the results are shown in FIG. 1.
비교예 2Comparative Example 2
디아민디클로로백금 수화물 [Pt(NH3)2Cl2xH2O] 88.24g 및 질산로듐 [Rh(NO3)3] 용액 31.58㎖을 300㎖의 증류수가 담긴 비이커에 넣고 30분간 교반하면서 용해시키는 것을 제외하고는 실시예 1에서와 동일한 방법으로 촉매 15%Pt/모르데나이트 (d)를 제조한 다음, 실시예 1에서와 동일하게 촉매 활성을 평가하여 그 결과를 도 1에 나타내었다.88.24 g of diaminedichloroplatinum hydrate [Pt (NH 3 ) 2 Cl 2 xH 2 O] and 31.58 ml of rhodium nitrate [Rh (NO 3 ) 3 ] solution were placed in a beaker containing 300 ml of distilled water and dissolved for 30 minutes with stirring. Except for the preparation of the catalyst 15% Pt / mordenite (d) in the same manner as in Example 1, the catalyst activity was evaluated in the same manner as in Example 1 and the results are shown in FIG.
도 1로부터 알 수 있듯이, 종래의 자동차 배기가스 정화용 촉매 (d 및 e)는 저온에서의 활성은 매우 탁월하나 온도가 상승함에 따라 소정온도 (약 250℃)부터는 촉매활성이 급격하게 저하된다.As can be seen from Fig. 1, the catalysts d and e for automobile exhaust gas purification in the prior art have excellent activity at low temperatures, but the catalyst activity drops rapidly from a predetermined temperature (about 250 DEG C) as the temperature rises.
즉, 백금을 함유하고 있기 때문에 저온에서의 활성은 양호하나 질소산화물에 대한 촉매 활성에 기여하는 탄화수소를 산화시킴으로써 고온에서 촉매활성이 급격하게 저하되는 결과가 초래되는 것이다.That is, since platinum is contained, the activity at low temperatures is good, but the oxidation of hydrocarbons, which contributes to the catalytic activity to nitrogen oxides, results in a rapid decrease in catalytic activity at high temperatures.
반면에, 본 발명에 따른 자동차 배기가스 정화용 촉매 (촉매 a, b 및 c)에 있어서는 백금의 함유량을 제한하여 저온에서 탄화수소가 산화되는 것을 억제하고 코발트를 첨가함으로써 고온에서 질소산화물에 대한 촉매활성을 개선하였다. 따라서, 저온에서의 촉매 활성은 종래의 촉매보다는 약간 낮지만 온도가 상승하여도 촉매 활성이 급격하게 저하되지 않기 때문에 전체적인 질소산화물 정화율이 개선된다.On the other hand, in the catalyst for purification of automobile exhaust gas according to the present invention (catalysts a, b and c), the content of platinum is limited to inhibit the oxidation of hydrocarbons at low temperatures and the addition of cobalt improves catalytic activity against nitrogen oxides at high temperatures. Improved. Therefore, the catalytic activity at low temperature is slightly lower than the conventional catalyst, but the catalytic activity is not drastically reduced even when the temperature is raised, so that the overall nitrogen oxide purification rate is improved.
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| KR100489135B1 (en) * | 2002-09-02 | 2005-05-17 | 현대자동차주식회사 | Mat for catalytic converter |
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| JPH08173761A (en) * | 1994-12-26 | 1996-07-09 | Tosoh Corp | Method for removing nitrogen oxide |
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| JPH02233145A (en) * | 1989-03-07 | 1990-09-14 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| JPH03249948A (en) * | 1990-02-26 | 1991-11-07 | Nippon Shokubai Co Ltd | Catalyst for purifying exhaust gas from diesel engine |
| JPH0463140A (en) * | 1990-06-30 | 1992-02-28 | Res Dev Corp Of Japan | Zeolite catalyst |
| JPH06154611A (en) * | 1992-07-03 | 1994-06-03 | Sakai Chem Ind Co Ltd | Catalyst for decomposition of nitrous oxide |
| JPH06182213A (en) * | 1992-12-16 | 1994-07-05 | Nissan Motor Co Ltd | Catalyst for purification of exhaust gas |
| JPH0788335A (en) * | 1993-09-22 | 1995-04-04 | Nippon Steel Corp | Method for denitrating low-temperature waste gas |
| JPH08173761A (en) * | 1994-12-26 | 1996-07-09 | Tosoh Corp | Method for removing nitrogen oxide |
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| KR100489135B1 (en) * | 2002-09-02 | 2005-05-17 | 현대자동차주식회사 | Mat for catalytic converter |
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