KR100801880B1 - Catalyst for purifying waste gas of automobile - Google Patents
Catalyst for purifying waste gas of automobile Download PDFInfo
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- KR100801880B1 KR100801880B1 KR1020060069941A KR20060069941A KR100801880B1 KR 100801880 B1 KR100801880 B1 KR 100801880B1 KR 1020060069941 A KR1020060069941 A KR 1020060069941A KR 20060069941 A KR20060069941 A KR 20060069941A KR 100801880 B1 KR100801880 B1 KR 100801880B1
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- catalyst
- automobile
- gasoline
- alumina
- surface area
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- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 239000002912 waste gas Substances 0.000 title 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
본 발명은 가솔린 자동차용 촉매에 관한 것으로, 담체로서 비표면적 150~170㎡/g의 γ알루미나를 사용하고, 하부 층(Bottom layer)에는 Pd를 코팅하고 상부 층( Top layer)에는 Pd/Rh를 코팅한 것을 특징으로 한다. The present invention relates to a catalyst for a gasoline automobile, using a gamma alumina having a specific surface area of 150 to 170 m 2 / g, coating Pd on the bottom layer and Pd / Rh on the top layer. It is characterized by the coating.
자동차, 가솔린, 촉매 Car, gasoline, catalyst
Description
도 1은 본 발명의 가솔린 자동차용 촉매 제조에 사용된 Pd-수용액을 γ-Al2O3에 흡착시켜 PM 분산도를 측정한 결과를 나타낸 사진. 1 is a photograph showing the results obtained by measuring the PM dispersion by adsorbing Pd-aqueous solution used in the preparation of the catalyst for gasoline automobiles of the present invention to γ-Al 2 O 3 .
본 발명은 가솔린 자동차용 촉매에 관한 것으로, 구체적으로 CO 및 HC의 정화효율을 개선시킨 가솔린 자동차의 배기가스 정화용 촉매에 관한 것이다. The present invention relates to a catalyst for a gasoline vehicle, and more particularly, to a catalyst for purifying exhaust gas of a gasoline vehicle having improved purification efficiency of CO and HC.
종래 자동차 배기가스 정화용 산화촉매의 담체로 사용되는 알루미나는 비표면적이 그다지 넓지 않아 Pd 등의 귀금속을 흡착하는 효율이 그다지 좋지 않았고 특히 열적 안정성이 떨어지는 문제점이 있었다. Alumina, which is used as a carrier for the oxidation catalyst for automobile exhaust gas purification, has a problem in that the specific surface area is not so large that the efficiency of adsorbing precious metals such as Pd is not very good, and thermal stability is particularly poor.
또한, 일반적으로 삼원촉매의 경우에서 Pt/Rh보다 Pd가 내열성은 강하지만 피독에 영향을 많이 받는다. 종래 자동차 배기가스 정화용 산화촉매는 하부 층(bottom layer)에는 Pd를 코팅하고 상부 층( Top layer)에는 Rh를 코팅하였으나, 이 경우 CO 및 HC의 정화효율이 충분하지 못한 단점이 있었다. In general, Pd is more resistant to poisoning than Pt / Rh in the case of a three-way catalyst. Conventionally, the oxidation catalyst for automobile exhaust gas purification coated Pd on the bottom layer and Rh on the top layer, but in this case, the purification efficiency of CO and HC was not sufficient.
따라서, 본 발명의 목적은 열안정성이 좋으며 CO 및 HC의 정화효율이 우수한 가솔린 자동차용 촉매를 제공하는 것이다. Accordingly, an object of the present invention is to provide a catalyst for gasoline automobiles having good thermal stability and excellent purification efficiency of CO and HC.
상기 본 발명의 목적은 담체로서 비표면적 150-170㎡/g의 γ알루미나를 사용하고, 하부 층(Bottom layer)에는 Pd를 코팅하고 상부 층( Top layer)에는 Pd/Rh를 코팅한 것을 특징으로 하는 가솔린 자동차용 촉매에 의해 달성된다. An object of the present invention is characterized by using γ-alumina having a specific surface area of 150-170 m 2 / g as a carrier, coating Pd on the bottom layer and Pd / Rh on the top layer. Is achieved by a catalyst for a gasoline automobile.
종래의 가솔린 자동차용 촉매의 담체는 통상, 순수 알루미나로써 사용 전(Fresh) 상태의 비표면적이 140㎡/g, 1015℃에서 4시간 에이징한 후(Aged)상태의 비표면적이 85㎡/g이다. 본 발명의 제조공정에서는 종래의 알루미나 대신 비표면적이 넓고 고온에서도 안정한 알루미나를 사용하였다. 본 발명에 사용한 알루미나는 비표면적 150-170㎡/g의 γ알루미나이고, 1015℃ X 4시간 에이징 후(Aged)상태의 비표면적이 120㎡/g 이상이다. Conventional carriers for gasoline automobile catalysts are usually pure alumina, and the specific surface area of the fresh state is 140 m 2 / g and the specific surface area of the aged state after aging at 1015 ° C. for 4 hours (85 m 2 / g). . In the manufacturing process of the present invention, alumina, which has a large specific surface area and is stable at high temperatures, is used instead of the conventional alumina. The alumina used in the present invention is gamma alumina having a specific surface area of 150 to 170 m 2 / g, and has a specific surface area of at least 120 m 2 / g after aging at 1015 ° C for 4 hours.
종래의 가솔린 자동차용 촉매는 하부 층(Bottom layer)에는 Pd를 코팅하고 상부 층(Top layer)에는 Rh를 코팅하였으나, 본 발명의 제조 공정에서는 하부 층(Bottom layer)은 종래 기술과 동일하게 Pd를 코팅하였으나, 상부 층(Top layer)영역에 Pd/Rh를 사용하였다. 상부 층 영역에서의 Pd가 환원제를 산화시키기는 하지만 현재 사용되고 있는 가솔린 자동차용 촉매의 NOx 정화율이 100%에 가깝기 때 문에 Top washcoat에 1~5wt%의 Pd을 사용 Rh와 같이 흡착시키므로써 CO 및 HC의 정화효율을 개선하였다. Conventional gasoline automotive catalysts coated Pd on the bottom layer and Rh on the top layer, but in the manufacturing process of the present invention, the bottom layer is the same as the prior art. Although coated, Pd / Rh was used for the top layer region. Although Pd in the upper layer zone oxidizes the reducing agent, the NOx purification rate of the gasoline automobile catalysts currently used is close to 100%, so that 1 to 5 wt% of Pd is adsorbed to the top washcoat with Rh. And the purification efficiency of HC was improved.
이하 실시예를 사용하여 본 발명을 보다 상세하게 설명한다The present invention is explained in more detail using the following examples.
실시예 1 Example 1
하기 표 1의 조성으로 가솔린 자동차용 촉매를 제조하였다. 제조방법은 다음과 같다. To prepare a catalyst for a gasoline vehicle in the composition of Table 1 below. The manufacturing method is as follows.
표 1Table 1
1. 하부 층(Bottom layer) 제조1. Bottom layer fabrication
탈이온수에 BaO를 투입하였다. 다시 탈이온수를 투입하고 알루미나-2를 투입하였다. Ceria-2를 투입한 다음, Ceria-1을 투입하고 한시간 혼합 후 Pd을 투입하였다. 최종 pH를 6.0~7.0으로 조정하고 분쇄 후 입자 크기를 3.0~4.0㎛ 조정하였다. Pd을 γ-Al2O3에 흡착시켜 PM 분산도를 측정한 결과를 도 1에 게시하였다. 흡착 및 분산이 잘 이루어진 것을 알 수 있었다(5nm이하).BaO was added to deionized water. Deionized water was added again and alumina-2 was added. After adding Ceria-2, Ceria-1 was added and Pd was added after mixing for one hour. The final pH was adjusted to 6.0-7.0 and the particle size was adjusted to 3.0-4.0 μm after grinding. Pd was adsorbed to the γ-Al 2 O 3 were published the results of the measurement of the PM polydispersity in Fig. It was found that adsorption and dispersion were well performed (less than 5 nm).
2. 상부 층(Top layer) 제조. 2. Top layer manufacturing.
탈이온수를 투입한 다음, 알루미나-2를 투입하였다. Pd를 투입하고 15분간 혼합하였다. Rh을 투입한 다음에 알루미나-3을 투입하고 Ceria-1을 투입한 후 15분간 혼합하였다. 최종 pH를 6~7로 조정하고 분쇄후 입자 크기를 3.0~4.0um 조정하였다. Deionized water was added, followed by alumina-2. Pd was added and mixed for 15 minutes. After Rh was added, alumina-3 was added, Ceria-1 was added, and mixed for 15 minutes. Final pH was adjusted to 6-7 and particle size was adjusted 3.0-4.0um after grinding.
3. 코팅3. Coating
코오디라이트로 이루어진 벌집모양의 지지체에 코팅 후 80℃~120℃에서 수분을 제거하고 500℃에서 4시간 하소하여 촉매를 제작하였다.After coating on a honeycomb-shaped support made of cordierite, water was removed at 80 ° C. to 120 ° C. and calcined at 500 ° C. for 4 hours to prepare a catalyst.
비교예 1 Comparative Example 1
하기 표 2의 조성으로 가솔린 자동차용 촉매를 제조하였다. 제조방법은 종래의 일반적인 가솔린 촉매의 제조방법을 사용하였다. To prepare a catalyst for a gasoline vehicle in the composition of Table 2. As a manufacturing method, a conventional method of preparing a gasoline catalyst was used.
표 2TABLE 2
시험예 1 가솔린 자동차용 촉매의 정화율 시험Test Example 1 Purification Rate Test of Catalysts for Gasoline Vehicles
상기 실시예 1 및 비교예 1에서 제조된 촉매를 사용하여 아래와 같은 모델가스 테스트 조건에서 촉매 성능평가를 실시하였다. 그 결과를 하기 표 3에 게시하였다. Using the catalyst prepared in Example 1 and Comparative Example 1 was carried out catalyst performance evaluation under the model gas test conditions as follows. The results are published in Table 3 below.
공연비(λ) : 1.00 ± 0.03Air-fuel ratio (λ): 1.00 ± 0.03
주파수(Hz) : 1.0Frequency (Hz): 1.0
공간속도(Hr-1) : 60,000Space Speed (Hr -1 ): 60,000
승온속도(℃/min) : 30 Temperature increase rate (℃ / min): 30
시료규격(mm) : φ25.4 X L56.0Sample size (mm): φ25.4 X L56.0
표 3 TABLE 3
상기 실시에 및 비교예의 촉매의 성능시험 결과에서 알 수 있는 바와 같이, 본 발명에 의해 제조한 촉매를 1015℃ X 4시간 에이징 한 후 정화율을 활성으로 평가하였을 경우 fuel rich영역에서의 정화율이 10-20%이상 높아지고, LOT온도가 5-35℃이상 저감되는 촉매를 얻을 수 있었다.As can be seen from the performance test results of the catalysts of the Examples and Comparative Examples, the purification rate in the fuel rich region is increased when the catalyst prepared according to the present invention is aged at 1015 ° C. for 4 hours and the purification rate is evaluated as active. A catalyst with a higher 10-20% and a lower LOT temperature of 5-35 ° C or more was obtained.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101241421B1 (en) * | 2010-12-14 | 2013-03-11 | 오덱(주) | Palladium basedautomotive catalyst with asymmetric structure and manufacturing method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6019036A (en) | 1983-07-12 | 1985-01-31 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| KR950010783B1 (en) * | 1990-06-20 | 1995-09-23 | 가부시끼가이샤 닛뽕쇼꾸바이 | Use of a specific catalyst for purifying exhaust gases from disel engines |
| KR960037116A (en) * | 1995-04-28 | 1996-11-19 | 와다 요시히로 | Catalyst for purification of exhaust gas |
| JPH10328566A (en) | 1997-04-02 | 1998-12-15 | Toyota Motor Corp | Catalyst for purifying waste gas |
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- 2006-07-25 KR KR1020060069941A patent/KR100801880B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6019036A (en) | 1983-07-12 | 1985-01-31 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| KR950010783B1 (en) * | 1990-06-20 | 1995-09-23 | 가부시끼가이샤 닛뽕쇼꾸바이 | Use of a specific catalyst for purifying exhaust gases from disel engines |
| KR960037116A (en) * | 1995-04-28 | 1996-11-19 | 와다 요시히로 | Catalyst for purification of exhaust gas |
| JPH10328566A (en) | 1997-04-02 | 1998-12-15 | Toyota Motor Corp | Catalyst for purifying waste gas |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101241421B1 (en) * | 2010-12-14 | 2013-03-11 | 오덱(주) | Palladium basedautomotive catalyst with asymmetric structure and manufacturing method thereof |
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