KR101241421B1 - Palladium basedautomotive catalyst with asymmetric structure and manufacturing method thereof - Google Patents
Palladium basedautomotive catalyst with asymmetric structure and manufacturing method thereof Download PDFInfo
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- KR101241421B1 KR101241421B1 KR1020100127654A KR20100127654A KR101241421B1 KR 101241421 B1 KR101241421 B1 KR 101241421B1 KR 1020100127654 A KR1020100127654 A KR 1020100127654A KR 20100127654 A KR20100127654 A KR 20100127654A KR 101241421 B1 KR101241421 B1 KR 101241421B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
Abstract
본 발명은 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매 및 그 제조방법에 관한 것으로, 더욱 상세하게는 담체, 전술한 담체의 외표면에 형성되는 제1코팅층 및 전술한 제1코팅층의 외표면에 형성되는 제2코팅층으로 이루어지며, 담체의 외표면에 제1코팅액을 도포하는 제1코팅단계, 전술한 제1코팅액 도포된 담체의 외표면에 제2코팅액을 도포하는 제2코팅단계 및 전술한 제2코팅액이 도포된 담체를 80 내지 120℃의 온도로 가열하여 수분을 제거하는 건조단계 및 전술한 건조단계를 거친 담체를 500 내지 600℃의 온도로 가열하여 소성하는 소성단계를 통해 제조된다.The present invention relates to a catalyst for a palladium-based gasoline automobile having an asymmetric structure and a method of manufacturing the same, and more particularly, to a carrier, a first coating layer formed on the outer surface of the carrier described above, and an outer surface of the first coating layer described above. The first coating step of applying a first coating liquid to the outer surface of the carrier, the second coating step of applying the second coating liquid to the outer surface of the carrier coated with the above-described first coating liquid and the above-described second 2 is coated through a drying step of removing the moisture by heating the carrier to which the coating liquid is applied to a temperature of 80 to 120 ℃ and a firing step of heating the carrier after the above-described drying step to a temperature of 500 to 600 ℃.
Description
본 발명은 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매 및 그 제조방법에 관한 것으로, 더욱 상세하게는 담체의 외표면에 팔라듐의 함량이 차이나는 제1코팅층 및 제2코팅층을 형성하여 정화효율이 향상된 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매 및 그 제조방법에 관한 것이다.
The present invention relates to a catalyst for a palladium-based gasoline automobile having an asymmetric structure and a method of manufacturing the same, and more particularly, to form a first coating layer and a second coating layer having a different palladium content on the outer surface of the carrier to improve purification efficiency. The present invention relates to a catalyst for a palladium-based gasoline automobile having an asymmetric structure and a method of manufacturing the same.
본 발명은 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매 및 그 제조방법에 관한 것으로, 더욱 상세하게는 담체의 외표면에 팔라듐의 함량이 차이나는 제1코팅층 및 제2코팅층을 형성하여 정화효율이 향상된 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매 및 그 제조방법에 관한 것이다.The present invention relates to a catalyst for a palladium-based gasoline automobile having an asymmetric structure and a method of manufacturing the same, and more particularly, to form a first coating layer and a second coating layer having a different palladium content on the outer surface of the carrier to improve purification efficiency. The present invention relates to a catalyst for a palladium-based gasoline automobile having an asymmetric structure and a method of manufacturing the same.
일반적으로 자동차의 연료로는 원유를 정제하는 과정에서 얻어지는 가솔린 및 디젤이 가장 널리 사용되는데, 이러한 가솔린 및 디젤의 경우는 환경오염을 유발하는 탄소를 다량 함유한 배기가스를 배출하고 있다.In general, gasoline and diesel obtained in the process of refining crude oil are most widely used as fuels for automobiles. In the case of gasoline and diesel, exhaust gas containing a large amount of carbon causing environmental pollution is emitted.
이러한 배기가스를 정화하기 위해 백금, 팔라듐 또는 로듐등의 귀금속류가 함유된 촉매가 활발히 연구되고 있으며, 이러한 귀금속류가 함유된 촉매는 내열, 내구성 및 촉매의 성능을 향상시키기 위해 많은 첨가물들이 첨가되어지고 있다.Catalysts containing precious metals such as platinum, palladium or rhodium have been actively studied to purify these exhaust gases, and many additives have been added to catalysts containing such precious metals to improve heat resistance, durability and catalyst performance. .
내연기관의 배출가스에 대한 방출기준이 각국 정부에 의해 정해져 있으며 또한 이에 대한 모니터링도 그 기준이 정해져 있는데, 배출가스에 대한 모니터링 기준을 만족시키기 위하여 사용되는 기술이 조촉매제의 산소저장능력을 이용하는 것이다. 그러나 종래의 자동차 촉매는 산소저장능력이 있는 세리아 또는 세리아 복합산화물만을 주로 사용하기 때문에, 세리아나 세리아 복합산화물들의 산소저장능력이 자동차 배기가스 중 탄화수소의 산화반응력을 저하시켜 탄화수소의 정화능을 감소시키는 문제점이 있었다.Emission standards for internal combustion engines are set by governments, and monitoring standards are set. The technology used to satisfy the monitoring standards for emissions is to use the oxygen storage capacity of the promoter. . However, since the conventional automotive catalyst mainly uses only ceria or ceria composite oxides having oxygen storage capacity, the oxygen storage capacity of ceria or ceria composite oxides reduces the oxidation reaction of hydrocarbons in automobile exhaust gas, thereby reducing the hydrocarbon purification ability. There was a problem.
또한, 최근에는 배기가스에 대한 규제가 강화됨에 따라, 종래에 사용되던 자동차용 촉매보다 월등한 정화효율을 나타내면서 전술한 문제점이 발생하지 않는 자동차 배기가스 촉매의 제조가 요구되고 있다.
In addition, in recent years, as regulations on exhaust gas are tightened, it is required to manufacture automobile exhaust gas catalysts which exhibit superior purification efficiency than conventionally used automobile catalysts and do not cause the above-mentioned problems.
본 발명의 목적은 코팅성분의 함량이 서로 다른 두개의 코팅층을 담채 표면에 비대칭으로 형성하여 초기 열중량의 감소로 인해 정화효율이 향상된 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매를 제공하는 것이다.It is an object of the present invention to provide a catalyst for a palladium-based gasoline vehicle having an asymmetrical structure having improved purification efficiency due to a reduction in initial thermal weight by forming an asymmetrical surface on two surfaces of two coating layers having different coating components.
본 발명의 다른 목적은 두개의 코팅층에 함유되는 팔라듐의 함유량을 달리하여 초기 일산화탄소, 탄화수소의 반응성이 향상된 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매를 제공하는 것이다.Another object of the present invention is to provide a palladium-based gasoline automobile catalyst having an asymmetric structure with improved reactivity of initial carbon monoxide and hydrocarbon by varying the content of palladium contained in the two coating layers.
본 발명의 목적은 담체, 상기 담체의 외표면에 형성되는 제1코팅층 및 상기 제1코팅층의 외표면에 형성되는 제2코팅층을 포함하는 것을 특징으로 하는 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매를 제공함에 의해 달성된다.An object of the present invention is a catalyst for a palladium-based gasoline automobile having an asymmetric structure comprising a carrier, a first coating layer formed on the outer surface of the carrier and a second coating layer formed on the outer surface of the first coating layer. By providing.
본 발명의 바람직한 특징에 따르면, 상기 제1코팅층은 산화산화알루미늄, 산화스트론듐, 산화세륨 및 팔라듐을 포함하는 것으로 한다.According to a preferred feature of the invention, the first coating layer is to comprise aluminum oxide, strontium oxide, cerium oxide and palladium.
본 발명의 더 바람직한 특징에 따르면, 상기 제1코팅층은 산화산화알루미늄 70 내지 71 중량부, 산화스트론듐 4 내지 4.5 중량부, 산화세륨 24 내지 25 중량부 및 팔라듐 0.5 내지 1 중량부를 포함하는 것으로 한다.According to a more preferred feature of the invention, the first coating layer is to include 70 to 71 parts by weight of aluminum oxide, 4 to 4.5 parts by weight of strontium oxide, 24 to 25 parts by weight of cerium oxide and 0.5 to 1 parts by weight of palladium do.
본 발명의 더욱 바람직한 특징에 따르면, 상기 제2코팅층은 산화산화알루미늄, 산화스트론듐, 산화세륨 및 팔라듐을 포함하는 것으로 한다.According to a more preferred feature of the invention, the second coating layer is to comprise aluminum oxide, strontium oxide, cerium oxide and palladium.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 제2코팅층은 산화산화알루미늄 54 내지 55 중량부, 산화스트론듐 10 내지 11 중량부, 산화세륨 32 내지 33 중량부 및 팔라듐 2 내지 2.5 중량부를 포함하는 것으로 한다.
According to a further preferred feature of the invention, the second coating layer comprises 54 to 55 parts by weight of aluminum oxide, 10 to 11 parts by weight of strontium oxide, 32 to 33 parts by weight of cerium oxide and 2 to 2.5 parts by weight of palladium Shall be.
또한, 본 발명의 목적은 담체의 외표면에 제1코팅액을 도포하는 제1코팅단계, 상기 제1코팅액 도포된 담체의 외표면에 제2코팅액을 도포하는 제2코팅단계, 상기 제2코팅액이 도포된 담체를 80 내지 120℃의 온도로 가열하여 수분을 제거하는 건조단계 및 상기 건조단계를 거친 담체를 500 내지 600℃의 온도로 가열하는 소성단계를 포함하는 것을 특징으로 하는 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매의 제조방법을 제공함에 의해서도 달성될 수 있다.In addition, an object of the present invention is a first coating step of applying a first coating liquid to the outer surface of the carrier, a second coating step of applying a second coating liquid to the outer surface of the carrier coated with the first coating liquid, the second coating liquid is Palladium having an asymmetric structure, characterized in that it comprises a drying step of heating the applied carrier to a temperature of 80 to 120 ℃ to remove moisture and a firing step of heating the carrier after the drying step to a temperature of 500 to 600 ℃ It can also be achieved by providing a method for producing a catalyst for a system gasoline automobile.
본 발명의 바람직한 특징에 따르면, 상기 제1코팅액은 탈이온수 100 중량부, 산화산화알루미늄 70 내지 71 중량부, 산화스트론듐 4 내지 4.5 중량부, 산화세륨 24 내지 25 중량부 및 팔라듐 0.5 내지 1 중량부를 혼합하여 혼합물을 제조하는 혼합물제조단계, 상기 혼합물의 pH를 6.0 내지 7.0으로 조절하는 산도조절단계 및 산도가 조절된 혼합물을 3.0 내지 4.5㎛의 입자크기로 분쇄하는 밀링단계로 제조되는 것으로 한다.According to a preferred feature of the invention, the first coating liquid is 100 parts by weight of deionized water, 70 to 71 parts by weight of aluminum oxide, 4 to 4.5 parts by weight of strontium oxide, 24 to 25 parts by weight of cerium oxide and 0.5 to 1 of palladium A mixture preparation step of preparing a mixture by mixing parts by weight, an acidity adjusting step of adjusting the pH of the mixture to 6.0 to 7.0, and a milling step of grinding the adjusted acidic mixture into a particle size of 3.0 to 4.5 μm. .
본 발명의 더 바람직한 특징에 따르면, 상기 제2코팅액은 탈이온수 100 중량부, 산화산화알루미늄 54 내지 55 중량부, 산화스트론듐 10 내지 11 중량부, 산화세륨 32 내지 33 중량부 및 팔라듐 2 내지 2.5 중량부를 혼합하여 혼합물을 제조하는 혼합물제조단계, 상기 혼합물의 pH를 6.0 내지 7.0으로 조절하는 산도조절단계 및 산도가 조절된 혼합물을 3.0 내지 4.5㎛의 입자크기로 분쇄하는 밀링단계로 제조되는 것으로 한다.
According to a more preferred feature of the invention, the second coating liquid is deionized water 100 parts by weight, aluminum oxide 54 to 55 parts by weight, strontium oxide 10 to 11 parts by weight, cerium oxide 32 to 33 parts by weight and palladium 2 to It is prepared by the mixture preparation step of preparing a mixture by mixing 2.5 parts by weight, the acidity control step of adjusting the pH of the mixture to 6.0 to 7.0 and the milling step of grinding the mixture of the adjusted acidity to a particle size of 3.0 to 4.5㎛ do.
본 발명에 따른 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매 및 그 제조방법은 코팅성분의 함량이 서로 다른 두개의 코팅층을 담채 표면에 비대칭으로 형성하여 초기 열중량의 감소로 인해 정화효율이 향상된 촉매를 제공하는 탁월한 효과를 나타낸다.The catalyst for palladium-based gasoline automobile having an asymmetric structure according to the present invention and a method for manufacturing the same are formed asymmetrically on the surface of two coating layers having different coating components, thereby improving catalyst efficiency due to a reduction in initial thermogravimetric weight. Excellent effect provided.
또한, 두개의 코팅층에 함유되는 팔라듐의 함유량을 달리하여 초기 일산화탄소 및 탄화수소의 반응성이 향상된 촉매를 제공하는 탁월한 효과를 나타낸다.
In addition, by varying the content of palladium contained in the two coating layers has an excellent effect of providing a catalyst with improved initial reactivity of carbon monoxide and hydrocarbons.
도 1은 본 발명에 따른 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매의 제조과정을 나타낸 순서도이다.1 is a flow chart illustrating a process for preparing a catalyst for a palladium-based gasoline vehicle having an asymmetric structure according to the present invention.
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.
Hereinafter, preferred embodiments of the present invention and physical properties of the respective components will be described in detail with reference to the accompanying drawings. However, the present invention is not limited thereto, And this does not mean that the technical idea and scope of the present invention are limited.
본 발명에 따른 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매는 담체, 전술한 담체의 외표면에 형성되는 제1코팅층 및 전술한 제1코팅층의 외표면에 형성되는 제2코팅층을 포함하여 이루어진다.
The catalyst for a palladium-based gasoline automobile having an asymmetric structure according to the present invention comprises a carrier, a first coating layer formed on the outer surface of the carrier described above, and a second coating layer formed on the outer surface of the first coating layer described above.
전술한 담체는 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매의 기재가 되는 것으로, 구 또는 허니컴 구조가 적용될 수 있으며, 재료는 특별히 한정되지 않지만 철, 산화산화알루미늄 및 마그네슘이 주성분인 근청석(Cordierite)으로 이루어지는 것이 바람직하다.
The carrier described above is a substrate of a catalyst for a palladium-based gasoline automobile having an asymmetric structure, and a spherical or honeycomb structure can be applied, and the material is not particularly limited, but cordierite mainly composed of iron, aluminum oxide, and magnesium It is preferable that it consists of.
전술한 제1코팅층은 전술한 담체의 외표면에 형성되는데, 산화알루미늄, 산화스트론듐, 산화세륨 및 팔라듐으로 이루어지며, 더욱 바람직하게는 산화알루미늄 70 내지 71 중량부, 산화스트론듐 4 내지 4.5 중량부, 산화세륨 24 내지 25 중량부 및 팔라듐 0.5 내지 1 중량부로 이루어진다.
The first coating layer described above is formed on the outer surface of the carrier, and is composed of aluminum oxide, strontium oxide, cerium oxide and palladium, more preferably 70 to 71 parts by weight of aluminum oxide, 4 to strontium oxide 4.5 parts by weight, 24 to 25 parts by weight of cerium oxide and 0.5 to 1 parts by weight of palladium.
전술한 제2코팅층은 전술한 제1코팅층의 외표면에 형성되는데, 산화알루미늄, 산화스트론듐, 산화세륨 및 팔라듐으로 이루어지며, 더욱 바람직하게는 산화알루미늄 54 내지 55 중량부, 산화스트론듐 10 내지 11 중량부, 산화세륨 32 내지 33 중량부 및 팔라듐 2 내지 2.5 중량부로 이루어진다.
The above-described second coating layer is formed on the outer surface of the above-described first coating layer, and is composed of aluminum oxide, strontium oxide, cerium oxide and palladium, more preferably 54 to 55 parts by weight of aluminum oxide, strontium oxide 10 to 11 parts by weight, 32 to 33 parts by weight of cerium oxide and 2 to 2.5 parts by weight of palladium.
전술한 제1코팅층 및 전술한 제2코팅층은 담체에 각각 성분의 함량차이로 인해 초기 열중량의 감소로 인해 정화효율이 향상된 촉매를 제공하는 탁월한 효과를 나타내며, 두개의 코팅층에 함유되는 팔라듐의 함유량의 차이로 인해 초기 일산화탄소 및 탄화수소의 반응성이 향상된 촉매를 제공하는 탁월한 효과를 나타낸다.
The first coating layer and the second coating layer described above have an excellent effect of providing a catalyst having improved purification efficiency due to a reduction in initial thermogravimetry due to a difference in content of components in the carrier, and the content of palladium contained in the two coating layers. Due to this difference, it shows an excellent effect of providing a catalyst with improved initial reactivity of carbon monoxide and hydrocarbons.
또한, 본 발명에 따른 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매의 제조방법은 담체의 외표면에 제1코팅액을 도포하는 제1코팅단계(S101), 전술한 제1코팅액 이 도포된 담체의 외표면에 제2코팅액을 도포하는 제2코팅단계(S103), 전술한 제2코팅액이 도포된 담체를 80 내지 120℃의 온도로 가열하여 수분을 제거하는 건조단계(S105) 및 전술한 건조단계(S105)를 거친 담체를 500 내지 600℃의 온도로 가열하는 소성단계(S109)를 포함한다.
In addition, the method for producing a catalyst for a palladium-based gasoline vehicle having an asymmetric structure according to the present invention is the first coating step (S101) for applying a first coating liquid to the outer surface of the carrier, the outside of the carrier coated with the first coating liquid described above The second coating step (S103) for applying a second coating liquid to the surface, the drying step (S105) and the drying step (S105) and the above-mentioned drying step by heating the carrier to which the above-described second coating liquid is applied to a temperature of 80 to 120 ℃ It includes a firing step (S109) for heating the carrier passed through S105 to a temperature of 500 to 600 ℃.
전술한 제1코팅단계(S101)는 담체의 외표면에 제1코팅액을 도포하는 단계로, 전술한 제1코팅액은 탈이온수 100 중량부, 산화알루미늄 70 내지 71 중량부, 산화스트론듐 4 내지 4.5 중량부, 산화세륨 24 내지 25 중량부 및 팔라듐 0.5 내지 1 중량부를 혼합하여 혼합물을 제조하는 혼합물제조단계, 전술한 혼합물의 pH를 6.0 내지 7.0으로 조절하는 산도조절단계 및 산도가 조절된 혼합물을 3.0 내지 4.5㎛의 입자크기로 분쇄하는 밀링단계를 통해 제조된다.The first coating step (S101) is a step of applying a first coating liquid to the outer surface of the carrier, the first coating liquid is 100 parts by weight of deionized water, 70 to 71 parts by weight of aluminum oxide, 4 to strontium oxide 4.5 parts by weight, 24 to 25 parts by weight of cerium oxide and 0.5 to 1 part by weight of palladium to prepare a mixture to prepare a mixture, the acidity adjusting step of adjusting the pH of the above mixture to 6.0 to 7.0 and the acidity-adjusted mixture It is prepared through a milling step of grinding to a particle size of 3.0 to 4.5㎛.
전술한 혼합물 제조단계는 탈이온수, 산화알루미늄, 산화스트론듐 및 산화세륨을 30분간 혼합하고, 혼합이 완료되면 팔라듐을 투입하여, 최종 pH를 6.0 내지 7.0으로 조절한다.In the above-described mixture preparation step, deionized water, aluminum oxide, strontium oxide and cerium oxide are mixed for 30 minutes, and when the mixing is completed, palladium is added to adjust the final pH to 6.0 to 7.0.
pH의 조정이 완료되면 전술한 밀링머신을 이용하여 입자크기가 3.0 내지 4.5㎛로 균일화 되게 분쇄한다.
When the adjustment of the pH is completed, using the milling machine described above is ground to uniform particle size to 3.0 to 4.5㎛.
전술한 제2코팅단계(S103)는 전술한 제1코팅액이 도포된 담체의 외표면에 제2코팅액을 도포하는 단계로, 전술한 제2코팅액은 탈이온수 100 중량부, 산화알루미늄 54 내지 55 중량부, 산화스트론듐 10 내지 11 중량부, 산화세륨 32 내지 33 중량부 및 팔라듐 2 내지 2.5 중량부를 혼합하여 혼합물을 제조하는 혼합물제조단계, 전술한 혼합물의 pH를 6.0 내지 7.0으로 조절하는 산도조절단계 및 산도가 조절된 혼합물을 3.0 내지 4.5㎛의 입자크기로 분쇄하는 밀링단계를 통해 제조된다.The above-described second coating step (S103) is a step of applying a second coating liquid to the outer surface of the carrier to which the first coating liquid described above, the second coating liquid is 100 parts by weight of deionized water, 54 to 55 weight of aluminum oxide Part, a mixture preparation step of preparing a mixture by mixing 10 to 11 parts by weight of strontium oxide, 32 to 33 parts by weight of cerium oxide and 2 to 2.5 parts by weight of palladium, and adjusting the pH of the aforementioned mixture to 6.0 to 7.0. Step and acidity is adjusted through a milling step of grinding the mixture to a particle size of 3.0 to 4.5㎛.
전술한 혼합물 제조단계는 탈이온수, 산화알루미늄, 산화스트론듐 및 산화세륨을 30분간 혼합하고, 혼합이 완료되면 팔라듐을 투입하여, 최종 pH를 6.0 내지 7.0으로 조절한다.In the above-described mixture preparation step, deionized water, aluminum oxide, strontium oxide and cerium oxide are mixed for 30 minutes, and when the mixing is completed, palladium is added to adjust the final pH to 6.0 to 7.0.
pH의 조정이 완료되면 전술한 밀링머신을 이용하여 입자크기가 3.0 내지 4.5㎛로 균일화 되게 분쇄한다.When the adjustment of the pH is completed, using the milling machine described above is ground to uniform particle size to 3.0 to 4.5㎛.
전술한 제1코팅단계(S101) 및 제2코팅단계(S103)를 통해 형성된 코팅층의 두께는 160 내지 180㎛인 것이 바람직하다.
The thickness of the coating layer formed through the first coating step S101 and the second coating step S103 is preferably 160 to 180 μm.
전술한 건조단계(S105)는 전술한 제2코팅액이 도포된 담체를 80 내지 120℃의 온도로 가열하여 수분을 제거하는 단계로, 전술한 제2코팅액이 도포된 담체를 80 내지 120℃의 온도로 가열하면, 전술한 제1코팅층 및 제2코팅층에 함유되어 있던 탈이온수가 증발하면서 제1코팅층 밑 제2코팅층을 건조된다.
The above-mentioned drying step (S105) is a step of removing moisture by heating the carrier coated with the above-described second coating liquid to a temperature of 80 to 120 ° C., and the temperature of the carrier coated with the above-mentioned second coating liquid at a temperature of 80 to 120 ° C. When heated to, the second coating layer under the first coating layer is dried while the deionized water contained in the first coating layer and the second coating layer is evaporated.
전술한 소성단계(S107)는 전술한 건조단계(S105)를 거친 담체를 500 내지 600℃의 온도로 가열하여 소성하는 단계로, 500 내지 600℃의 온도에서 4 내지 5시간 동안 소성과정을 거치면, 전술한 제1코팅층 및 제2코팅층에 함유되어 있던 불순물이 제거되고, 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매가 제조된다.
The above-described firing step (S107) is a step of baking by heating the carrier having passed the above-mentioned drying step (S105) to a temperature of 500 to 600 ℃, if the firing process for 4 to 5 hours at a temperature of 500 to 600 ℃, Impurities contained in the first coating layer and the second coating layer described above are removed, and a catalyst for a palladium-based gasoline automobile having an asymmetric structure is produced.
이하에서는, 본 발명에 따른 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매의 제조방법으로 제조된 촉매의 물성을 실시예를 들어 설명한다.Hereinafter, the physical properties of the catalyst prepared by the method for preparing a catalyst for a palladium-based gasoline automobile having an asymmetric structure according to the present invention will be described with reference to Examples.
(단, 실시예에 사용되는 제1코팅액 및 제2코팅액은 아래의 과정을 통해 제조된 것이 사용된다.(However, the first coating liquid and the second coating liquid to be used in the examples are prepared by the following process.
제1코팅액 : 탈이온수 100 중량부, 산화산화알루미늄 70. 31 중량부, 산화스트론듐 4.14 중량부, 산화세륨 24.81 중량부 및 팔라듐 0.74중량부를 혼합하여 혼합물을 제조하고, 혼합물의 pH를 6.0 내지 7.0으로 조절하고, 산도가 조절된 혼합물을 3.5㎛의 입자크기로 분쇄하여 제조된다.First coating solution: 100 parts by weight of deionized water, 70.31 parts by weight of aluminum oxide, 4.14 parts by weight of strontium oxide, 24.81 parts by weight of cerium oxide and 0.74 parts by weight of palladium to prepare a mixture, the pH of the mixture is 6.0 to The mixture is adjusted to 7.0, and the acidity-adjusted mixture is prepared by grinding to a particle size of 3.5 mu m.
제2코팅액 : 탈이온수 100 중량부, 산화산화알루미늄 54. 29 중량부, 산화스트론듐 10.86 중량부, 산화세륨 32.57 중량부 및 팔라듐 2.28중량부를 혼합하여 혼합물을 제조하고, 혼합물의 pH를 6.0 내지 7.0으로 조절하고, 산도가 조절된 혼합물을 3.5㎛의 입자크기로 분쇄하여 제조된다.)
Second coating liquid: 100 parts by weight of deionized water, 54.29 parts by weight of aluminum oxide, 10.86 parts by weight of strontium oxide, 32.57 parts by weight of cerium oxide and 2.28 parts by weight of palladium to prepare a mixture, the pH of the mixture is 6.0 to Adjusted to 7.0, and the acidity-adjusted mixture is prepared by grinding to a particle size of 3.5 μm.)
<실시예 1>≪ Example 1 >
근청석으로 이루어지고 허니컴 구조로 형성된 담체의 표면에 제1코팅액을 도포하고, 제1코팅액이 도포된 담체의 외표면에 제2코팅액을 도포하고, 제2코팅액이 도포된 담체를 100℃의 온도로 가열하여 수분을 제거하고, 수분이 제거된 담체를 550℃의 온도로 가열하여 소성하여 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매를 제조하였다.
A first coating liquid is applied to the surface of the carrier made of cordierite and formed of a honeycomb structure, a second coating liquid is applied to the outer surface of the carrier on which the first coating liquid is applied, and the carrier coated with the second coating liquid is heated at a temperature of 100 ° C. Heat was removed to remove water, and the carrier was removed by heating to a temperature of 550 ℃ to prepare a catalyst for palladium-based gasoline vehicle having an asymmetric structure.
<비교예 1>≪ Comparative Example 1 &
근청석으로 이루어지고 허니컴 구조로 형성된 담체의 표면에 산화산화알루미늄 60.12 중량부, 산화바륨 9.49 중량부, 산화세륨 28.48 중량부, 팔라듐 1.90 중량부를 혼합하여 이루어진 코팅액을 도포하고, 1000℃에서 20시간 동안 소성하여 팔라듐계 가솔린 자동차용 촉매를 제조하였다.
A coating liquid consisting of 60.12 parts by weight of aluminum oxide, 9.49 parts by weight of barium oxide, 28.48 parts by weight of cerium oxide, and 1.90 parts by weight of palladium was applied to the surface of the carrier formed of cordierite and formed of a honeycomb structure. Firing was performed to prepare a catalyst for a palladium-based gasoline vehicle.
전술한 실시예 1 및 비교예 1을 통해 제조된 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매와 팔라듐계 가솔린 자동차용 촉매의 FRESH상태와 AGING상태의 비표면적을 비표면적 측정기(Specific Surface Area Analyzer)로 측정하여 아래 표 1에 나타내었다.The specific surface areas of the FRESH and AGING states of the palladium-based gasoline automobile catalyst and the palladium-based gasoline automobile catalyst having the asymmetric structure prepared through the above-described Example 1 and Comparative Example 1 were measured using a specific surface area analyzer. The measurement is shown in Table 1 below.
(단, Aging 조건은 Oven을 이용하여 1000℃의 온도에서 20시간동안 진행하였다.)
(However, Aging conditions were performed for 20 hours at a temperature of 1000 ℃ using Oven.)
<표 1>TABLE 1
위에 표 1에 나타낸 것처럼 본 발명에 의해 제조된 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매는 종래에 사용되던 가솔린 자동차용 촉매에 비해 FRESH상태와 AGING상태에서 비표면적이 모두 향상되는 것을 알 수 있다.
As shown in Table 1 above, the catalyst for a palladium-based gasoline automobile having an asymmetric structure prepared by the present invention can be seen that the specific surface area is improved in both the FRESH state and AGING state compared to the catalyst for gasoline automobiles used in the prior art.
전술한 실시예 1 및 비교예 1을 통해 제조된 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매와 팔라듐계 가솔린 자동차용 촉매의 활성능력(Conversion)과 LOT(Light-Off Temperature)를 측정하여 아래 표 2 및 표 3에 나타내었다.Palladium-based gasoline automobile catalyst and palladium-based gasoline automobile catalyst having an asymmetric structure prepared through the above-described Example 1 and Comparative Example 1 by measuring the conversion (Light) and LOT (Light-Off Temperature) And in Table 3.
{단, 활성능력 및 LOT는 활성능력 및 LOT 측정기인 HINZECAT-1004를 이용하여 측정하였으며, LOT는 초기 정화시점에서 50%에 도달되는 온도 LOT를 평가하여 나타내었고, ANALYZER는 HC, CO, NOx, O2 및 CO2이며, 촉매의 성능 평가조건은 모의 활성 가스벤치(Synthetic Gas Bench)를 이용하였고, 모의 활성 가스벤치의 조건은 다음과 같다. 주파수(Hz) : 1.0, 공간속도(Hr-1) : 100,000, 승온속도(℃/min) : 30, 시료 Size : (D)25.4 × 56, Aging Condition : 1100℃ × 10 시간(Oven Aging)}
{However, the activity capacity and LOT were measured using HINZECAT-1004, which is the activity capacity and LOT measuring instrument, and LOT was expressed by evaluating the temperature LOT reaching 50% at the time of initial purification, and ANALYZER is HC, CO, NOx, O 2 and CO 2 , the performance evaluation conditions of the catalyst was used a simulated gas bench (Synthetic Gas Bench), the conditions of the simulated active gas bench are as follows. Frequency (Hz): 1.0, Space Speed (Hr-1): 100,000, Heating Rate (℃ / min): 30, Sample Size: (D) 25.4 × 56, Aging Condition: 1100 ℃ × 10 Hours (Oven Aging)}
<표 2><Table 2>
위에 표 2에 나타낸 것처럼 활성능력으로 정화율을 평가하게 되면 본 발명의 의해 제조된 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매는 종래에 사용되던 가솔린 자동차용 촉매에 비해 정화효율이 월등하게 향상되는 것을 알 수 있다.
As shown in Table 2 above, when evaluating the purification rate by the activity capacity, the catalyst for a palladium-based gasoline automobile having an asymmetric structure manufactured by the present invention shows that the purification efficiency is significantly improved compared to the catalyst for gasoline automobiles used in the prior art. Able to know.
<표 3><Table 3>
위에 표 3에 나타낸 것처럼 LOT를 측정한 결과 초기 정화시점 50%에 도달되는 온도가 18 내지 26℃ 정도 저감되는 것을 알 수 있다.
As shown in Table 3 above, as a result of measuring LOT, it can be seen that the temperature reaching the initial purification point of 50% is reduced by about 18 to 26 ° C.
S101 ; 제1코팅단계
S103 ; 제2코팅단계
S105 ; 건조단계
S107 ; 소성단계S101; The first coating step
S103; The second coating step
S105; Drying step
S107; Firing stage
Claims (8)
상기 담체의 외표면에 형성되는 제1코팅층; 및
상기 제1코팅층의 외표면에 형성되는 제2코팅층;을 포함하며,
상기 제1코팅층은 팔라듐 0.5 내지 1 중량부가 함유되며,
상기 제2코팅층은 산화알루미늄 54 내지 55 중량부, 산화스트론듐 10 내지 11 중량부, 산화세륨 32 내지 33 중량부 및 팔라듐 2 내지 2.5 중량부를 포함하는 것을 특징으로 하는 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매.
carrier;
A first coating layer formed on an outer surface of the carrier; And
And a second coating layer formed on an outer surface of the first coating layer.
The first coating layer contains 0.5 to 1 parts by weight of palladium,
The second coating layer is palladium-based gasoline having an asymmetric structure, characterized in that it comprises 54 to 55 parts by weight of aluminum oxide, 10 to 11 parts by weight of strontium oxide, 32 to 33 parts by weight of cerium oxide and 2 to 2.5 parts by weight of palladium. Automotive catalysts.
상기 제1코팅층은 산화알루미늄, 산화스트론듐, 산화세륨 및 팔라듐을 포함하는 것을 특징으로 하는 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매.
The method according to claim 1,
The first coating layer is palladium-based gasoline automotive catalyst having an asymmetric structure, characterized in that it comprises aluminum oxide, strontium oxide, cerium oxide and palladium.
상기 제1코팅층은 산화알루미늄 70 내지 71 중량부, 산화스트론듐 4 내지 4.5 중량부, 산화세륨 24 내지 25 중량부 및 팔라듐 0.5 내지 1 중량부를 포함하는 것을 특징으로 하는 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매.
The method according to claim 1,
The first coating layer is a palladium gasoline having an asymmetric structure, characterized in that it comprises 70 to 71 parts by weight of aluminum oxide, 4 to 4.5 parts by weight of strontium oxide, 24 to 25 parts by weight of cerium oxide and 0.5 to 1 parts by weight of palladium. Automotive catalysts.
상기 제1코팅액이 도포된 담체의 외표면에 제2코팅액을 도포하는 제2코팅단계;
상기 제2코팅액이 도포된 담체를 80 내지 120℃의 온도로 가열하여 수분을 제거하는 건조단계; 및
상기 건조단계를 거친 담체를 500 내지 600℃의 온도로 가열하는 소성단계;를 포함하며,
상기 제1코팅액은 팔라듐 0.5 내지 1 중량부가 함유되고,
상기 제2코팅액은 탈이온수 100 중량부, 산화알루미늄 54 내지 55 중량부, 산화스트론듐 10 내지 11 중량부, 산화세륨 32 내지 33 중량부 및 팔라듐 2 내지 2.5 중량부를 혼합하여 혼합물을 제조하는 혼합물제조단계;
상기 혼합물의 pH를 6.0 내지 7.0으로 조절하는 산도조절단계; 및
산도가 조절된 혼합물을 3.0 내지 4.5㎛의 입자크기로 분쇄하는 밀링단계;로 제조되는 것을 특징으로 하는 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매의 제조방법.
A first coating step of applying a first coating liquid to an outer surface of the carrier;
A second coating step of applying a second coating liquid to an outer surface of the carrier to which the first coating liquid is applied;
A drying step of removing moisture by heating the carrier coated with the second coating solution to a temperature of 80 to 120 ° C .; And
It includes; firing step of heating the carrier after the drying step to a temperature of 500 to 600 ℃;
The first coating liquid contains 0.5 to 1 parts by weight of palladium,
The second coating solution is a mixture to prepare a mixture by mixing 100 parts by weight of deionized water, 54 to 55 parts by weight of aluminum oxide, 10 to 11 parts by weight of strontium oxide, 32 to 33 parts by weight of cerium oxide and 2 to 2.5 parts by weight of palladium. Manufacturing step;
PH adjustment step of adjusting the pH of the mixture to 6.0 to 7.0; And
Milling step of grinding the mixture is adjusted to a particle size of 3.0 to 4.5㎛ acidity; Method of producing a catalyst for a palladium-based gasoline vehicle having an asymmetric structure characterized in that it is prepared by.
상기 제1코팅액은 탈이온수 100 중량부, 산화알루미늄 70 내지 71 중량부, 산화스트론듐 4 내지 4.5 중량부, 산화세륨 24 내지 25 중량부 및 팔라듐 0.5 내지 1 중량부를 혼합하여 혼합물을 제조하는 혼합물제조단계;
상기 혼합물의 pH를 6.0 내지 7.0으로 조절하는 산도조절단계; 및
산도가 조절된 혼합물을 3.0 내지 4.5㎛의 입자크기로 분쇄하는 밀링단계;로 제조되는 것을 특징으로 하는 비대칭 구조를 갖는 팔라듐계 가솔린 자동차용 촉매의 제조방법.The method of claim 6,
The first coating solution is a mixture to prepare a mixture by mixing 100 parts by weight of deionized water, 70 to 71 parts by weight of aluminum oxide, 4 to 4.5 parts by weight of strontium oxide, 24 to 25 parts by weight of cerium oxide and 0.5 to 1 parts by weight of palladium. Manufacturing step;
PH adjustment step of adjusting the pH of the mixture to 6.0 to 7.0; And
Milling step of grinding the mixture is adjusted to a particle size of 3.0 to 4.5㎛ acidity; Method of producing a catalyst for a palladium-based gasoline vehicle having an asymmetric structure characterized in that it is prepared by.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100801880B1 (en) * | 2006-07-25 | 2008-02-12 | 오덱(주) | Catalyst for purifying waste gas of automobile |
| KR20090128418A (en) * | 2007-03-19 | 2009-12-15 | 우미코레 아게 운트 코 카게 | Two-layer three-way catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100801880B1 (en) * | 2006-07-25 | 2008-02-12 | 오덱(주) | Catalyst for purifying waste gas of automobile |
| KR20090128418A (en) * | 2007-03-19 | 2009-12-15 | 우미코레 아게 운트 코 카게 | Two-layer three-way catalyst |
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