KR100212911B1 - Purification device of diesel engine emission exhaust gas - Google Patents

Abstract

The present invention relates to an exhaust gas purification device for a diesel engine, and in particular, to heat the combustion network by an electric heater in a primary combustion chamber for post-treatment of exhaust gas of a diesel engine, to burn soot and unburned hydrocarbon, and to apply a second catalyst to the honey. It passes through the comb to remove NOx, oxidizes unburned hydrocarbons, particulate matter and carbon monoxide so that it can be used continuously without precipitation and periodic cleaning of particles, and has a high conversion rate for hydrocarbons, particulate matter, NOx and carbon monoxide at low temperature. , Metal-supported refractory inorganic oxides and rare earth oxides formed by supporting platinum group metals and additives such as Ni, lanthanum-based metals and other active metals in alumina, zeolites and yttria, and Ni in CeO ₂ and La ₂ O ₃ ; After supporting the active material containing at least one element selected from Cu, V, Cr, Co, dried and calcined The present invention relates to an exhaust gas purifier for a diesel engine, which uses an aqueous slurry to form an aqueous slurry, coats a honeycomb having a monolith structure, and calcinates the coating carrier.

Description

Exhaust Gas Purification System for Diesel Engine

The present invention relates to an exhaust gas purifying apparatus for a diesel engine, and in particular, unburned hydrocarbons and particulate matter are burned by a heating wire of an electric heater and a combustion network heated by the heating wire in a primary combustion chamber, and the metal oxide is coated in a honeycomb. To remove NOx by applying a catalyst to remove NOx at the inlet, and to oxidize secondary at the outlet by applying an oxidation catalyst to oxidize carbon monoxide to carbon dioxide or to remove NOx removal catalyst and catalyst The present invention relates to a diesel engine exhaust gas purifying apparatus which is uniformly distributed and used.

Conventionally, the method of reburning the filtered particulate matter using only a filter medium with a heating wire, a burner, etc. was used. This method is to apply the pressure sensor before and after the filter medium, and when it reaches a certain pressure or more, it is heated by a burner or the like and air is supplied to the blower to burn off particulate matter deposited on the filter medium. However, this method increases the temperature rapidly due to burning unburned hydrocarbons or particulate matter at one time, which shortens the life of the filter medium. In addition, while regenerating the filter medium, the exhaust gas from the diesel engine must be filtered or bypassed with the second filter medium, which is inefficient, and has a disadvantage in that a device cost such as a sensor is high.

In addition, in the past, a ceramic filter (honeycomb) was coated with a catalyst containing a noble metal to oxidize hydrocarbons and carbon monoxide and reduce NOx.In the catalyst, a precious metal having a limited amount is used effectively, such as activated alumina. Efforts have been made to support noble metals with high dispersion on high surface area refractory inorganic oxides.

However, catalysts with high dispersion of noble metals have high initial activity, but when they are subjected to severe conditions such as high temperature oxidation atmosphere in the process of burning and regenerating particulate matter trapped in ceramic filter materials, Reaction with noble metals and promoters tends to occur, which leads to problems in the durability of the activity.

Therefore, in order to form a coating layer containing alumina and zirconia as a carrier for supporting physical properties such as specific surface area of the zirconia catalyst, a method of supporting precious metals is proposed in Japanese Patent Application Laid-Open Nos. 57-29215 and 57-153737.

However, in these methods, deactivation occurs due to the above-mentioned causes because most of the precious metals are highly dispersed in alumina. In addition, zirconia (US Pat. No. 4,231,389) or alpha alumina (US Pat. No. 4,420,407) has been proposed in the art as a carrier material that does not interact with precious metals in high temperature oxidation atmosphere.

The technical problem to be achieved by the present invention is to provide an exhaust gas purifying apparatus for diesel engines that has excellent durability even under extreme conditions and has a high purification ability at low temperatures against harmful components.

Technical problem of the present invention is a metal-supported refractory inorganic oxide and a rare earth oxide formed by supporting platinum group metals and additives such as Ni, lanthanum-based metals and other active metals in alumina, zeolite and yttria, and Ni in CeO ₂ and La ₂ O ₃ . It is achieved by coating a honeycomb having a monolith structure with a composition impregnated with at least one element selected from Fe, Cu, V, Cr, and Co, and firing the coating carrier in an exhaust gas purifier for a diesel engine. do.

1 is a schematic view showing an exhaust gas purification apparatus for a diesel engine of the present invention.

2 is a perspective view showing the electric heater and the combustion network of the present invention.

* Explanation of symbols for main parts of the drawings

10: primary combustion chamber 11: hot wire

12: support 20: secondary catalytic oxidation treatment unit

21: honeycomb 30: combustion network

의 낮은 온도에서 입자상물질과 탄화수소를 산화시켜 주는 2차 촉매산화처리부(20)로 구성된다.Exhaust gas purification apparatus for a diesel engine of the present invention is connected to the engine side as shown in Figures 1 to 2, the primary combustion chamber 10 for burning particulate matter and hydrocarbons that are difficult to oxidize, and the metal oxide Coated honeycomb 21 is installed and 200 to 450

It consists of a secondary catalytic oxidation unit 20 for oxidizing particulate matter and hydrocarbons at a low temperature.

The primary combustion chamber 10 is alternately provided with a heating wire 11, which is supported by the support 12 to form a concentric circle, and a dense combustion network 30, and the combustion network 30 generates heat by the heating wire 11. As a result, particulate matter and hydrocarbons that pass through the combustion network 30 are combusted.

∼450

의 낮은 온도의 2차 촉매산화처리부(20)인 금속산화물이 피복된 허니콤(21)내에서 미연소 입자상물질과 탄화수소를 완전히 산화시켜줄 수 있게 될 뿐만 아니라 허니콤(21)에 입자상물질 침전 및 주기적인 청소없이 연속적으로 사용이 가능하게 되는 것이다.That is, the particulate matter and hydrocarbons in the diesel engine exhaust gas that is difficult to oxidize are combusted while passing through the combustion network 30 in the primary combustion chamber 10, thereby providing 200

-450

In the low temperature secondary catalytic oxidation unit 20, the metal oxide-coated honeycomb 21 can completely oxidize unburned particulate matter and hydrocarbons, as well as depositing particulate matter in the honeycomb 21. It can be used continuously without periodic cleaning.

As the power source of the heating wire 11, a storage battery used for starting a diesel engine is used. The heating wire 11 uses nichrome wire, cantal wire, metal composite heating wire as it is or uses ceramic coating, and the combustion network 30 is 30 One or more stainless steels of ˜800 mesh are used in connection, but more preferably, a wire mesh having a size of 100 to 400 mesh is generated by the heating wire 11. The support 12 uses a ceramic or mica plate.

In the secondary catalytic oxidation unit 20 of the present invention, the active ingredients used for metal oxide coating include finely divided aluminum oxides, zeolites, yttria and platinum group metals and additives Ni and Li, which are attached to a mixture thereof. A catalyst composition containing at least one element selected from Na, K, Cs, Rb, and Fr is applied to the honeycomb 21, and Ni is included in CeO ₂ and La ₂ O ₃ , and Fe, Cu, V, Cr After impregnating at least one element selected from, Co, the composition is applied to the honeycomb 21 and used.

Platinum group compounds and additives include platinum (A), palladium (B), nickel (C) and one element (D) selected from Li, Na, K, Cs, Rb, and Fr, and platinum, palladium, nickel, and (D The composition ratio of the substance is (A) :( B) = 1: 1.5 to 1.5: 1, (C) / ((A) + (B)) = 0.005 to 0.20, (C) :( D) = 0.5: It has a ratio of 1 to 1: 0.1 and these metals are supported on refractory inorganic compounds and rare earth oxides.

If the platinum group metal exceeds this ratio or is used only as an element of platinum or palladium, or if the materials of (C) and (D) are not used in proportion, the oxidation conversion rate of particulate matter, HC (hydrocarbon) and CO will decrease and Pt and It is hard to get synergistic effect between Pd. If the range exceeds 0.10, there is a disadvantage that the oxidation conversion rate does not last long. If the conversion rate is less than 0.005, the oxidation conversion rate is low and it is difficult to obtain a synergistic effect between Pt and Pd.

로 0.1중량

보다 작을 경우 원하는 활성을 얻기 힘들고 3중량

보다 높을 경우 금속 입자끼리의 입자성장이 촉진되어 활성 저하의 원인이 된다.Platinum group metal oxides and additives are supported on refractory inorganic compounds and rare earth oxides.

0.1 weight

Less than 3 weight

When higher, the grain growth between metal particles is promoted, which causes a decrease in activity.

As refractory inorganic oxides and rare earth oxides, zeolites and yttria are used, and a mixture of zeolites and yttria with alumina is finely divided with a weight ratio of alumina and other oxides from 99: 1 to 50:50. It is characterized by including. As the platinum and palladium source used for the platinum group metal used in the present invention, chloroplatinic acid, dinitrodiamine platinum, platinum sulfide complex salts, platinum tetramine chloride, palladium chloride, palladium nitrate and the like are preferable.

Nickel used as an additive is nickel chloride or nickel nitrate.

이어도 가능하지만 바람직하게는 1~50중량

를 사용함으로서 충분한 발명의 효과가 발휘될 수 있다.The zeolite used in the present invention has a Si / Al ratio of 1 to 500, and the amount of yttria used is 0.5 to 95 weight of the refractory inorganic oxide composition.

It is possible, but preferably 1 to 50 weight

The effect of sufficient invention can be exhibited by using

이상에서 6시간이상 건조시킨 후 300∼650

에서 소성시킨다.The platinum group metal, the additive, and the lanthanum-based promoter obtained in this way were supported on rare earth oxides or refractory inorganic oxides.

After drying for more than 6 hours above 300 ~ 650

Fire at

에서 바람직하게는 250∼600

의 온도에서 1∼10시간, 바람직하게는 1∼4시간동안 행해진다.The calcined platinum group metal, the additive-supported rare earth oxide, and the refractory inorganic oxide are made into aqueous sludge using a boil mill, etc., wash coated on a honeycomb carrier having an integral structure, and then dried and calcined as necessary to form a finished catalyst. Firing is 110 ~ 650

Preferably from 250 to 600

At a temperature of 1 to 10 hours, preferably 1 to 4 hours.

Among the zeolites, LaY-Zeolite, NaY-Zeolite, ZSM-5, HY-Zeolite, CoY-Zeolite, NaX-Zeolite, HX-Zeolite, etc. are used.The zeolite maintains strong acidity so as to crack hydrocarbons and particulate matter. In addition to using P and P and Ni as an additive, it contains at least one element selected from Li, Na, K, Cs, Rb, and Fr.Alumina acts as a carrier but adheres well to honeycomb during wash coating. It is also used for the purpose.

In addition, to reduce nitrogen oxides and promote oxidation of hydrocarbons and carbon monoxide, CeO ₂ and La ₂ O ₃ contain Ni, and contain at least one element selected from Cu, Fe, V, Cr, and Co. The content is CeO ₂ and La. for each selected element as Ce, La molar ratio between the ₂ O ₃ 0.2: to be impregnated is 1: 1 to 1.

Impregnate one or more metals containing Ni in these two oxides by using a ratio of CeO ₂ and La ₂ O ₃ 1: 5 to 5: 1 rather than supporting the metal in either CeO ₂ or La ₂ O ₃ This shows good performance in removing nitrogen oxides.

를 사용함으로써 충분한 발명효과가 발휘된다.These compounds are 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the metal-supported refractory inorganic oxide and rare earth oxide.

Sufficient invention effect is exhibited by using.

The honeycomb having a monolithic structure used in the present invention may be made of corderite, mullite, mordenite, spinel, α-alumina, β-alumina, zirconia, titania, titanium phosphate, aluminum titanate, ferrite, aluminosilicate and magnesium silicate. Carriers made of materials and the like are preferable, and cordieritie is particularly preferable for diesel internal combustion engines.

The active oil and fat is a diesel engine exhaust gas purifying catalyst and apparatus, characterized in that it is present at a concentration of 30 to 400 g / dm ³ (catalyst volume) suitably 70 to 250 g / dm ³ (catalyst volume).

The products obtained in this way can be used in diesel vehicles, ships, locomotives, industrial internal combustion engines, etc., and in particular, it can be used in aircraft as it does not take back pressure.

The present invention will be described in more detail with reference to the following Examples, which are not to be construed as limiting the present invention.

로 되는 조건에서 100시간 촉매정화재를 에이징하였다. SV=약 15만 hr^-1에서 TPM(총입사상물질), HC(탄화수소), VOF(휘발성 organic fraction), CO, NOx를 조사하였으며 신품시와 에이징 후 50

전환율을 조사하여 낮은 온도에서의 정화능과 전환율 지속성능을 측정하였다.Examples 1 to 17 The comparative examples 1 to 19 were examined for the diesel engine exhaust gas purifying catalyst and the purification performance after the engine endurance running of the apparatus. The endurance engine used commercially available four-cylinder diesel engine, 2476cc, compression ratio 21: 1, maximum torque / engine speed = 20.0kgm / 2000rpm, maximum output / engine speed = 85ps / 4200rpm. 450 at normal temperature

The catalytic purifier was aged for 100 hours under the following conditions. TPM (total particulate matter), HC (hydrocarbon), volatile organic fraction (VOF), CO and NOx were investigated at SV = 150,000 hr ^-1 .

The conversion was investigated to determine the purification and conversion sustainability at low temperatures.

Table 1 shows the components of the honeycomb catalyzed, and Table 2 shows the performance of the diesel exhaust gas purification catalyst and the device.

Example 1

에서 12시간동안 건조 후 600

에서 2시간동안 소성시켜 산화촉매용 분체를 얻었다. 산화세륨분체 3g과 산화란타늄 분체 3g에 Ni 0.4g과 Fe 0.4g을 담지시켜 120

에서 12시간동안 건조 후 600

에서 2시간동안 소성시켜 NOx 제거용 분체를 얻었으며, 보올밀에 의하여 20시간동안 습식분쇄 함으로써 각각의 수성슬러리를 조제하였다. 단면적 1평방인치당 약 400개의 가스유통셀을 갖는 외경 144mm 길이 150mm의 코오데라이트제 모노리스 담체를 입구부는 NOx제거용 슬러리에, 출구부는 산화촉매용 상기 슬러리에 침지하고 취출하여 셀 내의 과잉슬러리를 압축공기에 의하여 블로잉하고, 그후 120

에서 12시간 건조하고 다시 600

에서 2시간 소성하여 촉매 처리된 허니콤을 얻었으며 1차 연소실(10)에 제1도 및 제2도에 도시된 바와 같이 열선(11) 및 연소망(30)과 설치하여 사용되는 디젤엔진용 배출가스 정화장치이다.Chloride containing 10 g of titania with a specific surface area of 70 m ² / g, an average particle diameter of 0.5 μm, 10 g of NaY-zeolite with a specific surface area of 550 m ² / g, and 160 g of γ-Al ₂ O ₃ with a specific surface area of 210 m ² / g. Immerse in aqueous platinum chloride solution containing aqueous palladium and 1.5 g of platinum and aqueous sodium hydroxide solution containing 0.1 g of nickel chloride and 0.2 g of nickel, 120 g

After drying for 12 hours at 600

The mixture was calcined for 2 hours to obtain a powder for oxidation catalyst. 3 g of cerium oxide powder and 3 g of lanthanum oxide powder were loaded with 0.4 g of Ni and 0.4 g of Fe.

After drying for 12 hours at 600

It was calcined at for 2 hours to obtain a powder for removing NOx, and each aqueous slurry was prepared by wet milling for 20 hours with a bowl mill. An outer diameter of 144 mm long 150 mm corderite monolith carrier having about 400 gas flow cells per square inch of cross-sectional area is immersed in the slurry for NOx removal, and the outlet is immersed in the slurry for oxidation catalyst and taken out to compress excess slurry in the cell. Blown by air, then 120

12 hours in dry and back to 600

The honeycomb was calcined for 2 hours at, to obtain a catalyst-treated honeycomb, and used in the primary combustion chamber 10 as installed in the first combustion chamber 10 with the heating wire 11 and the combustion network 30. Emission gas purification device.

Example 2

Except for the component (D) in Table 1, K is 0.1g, the exhaust gas purification device for a diesel engine similar to Example 1.

Example 3

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that (D) component of Table 1 is 0.1 g of Li.

Example 4

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that (D) component of Table 1 is 0.1 g of Cs.

Example 5

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that (D) component of Table 1 is 0.1 g of Fr.

Example 6

Exhaust gas purification device for a diesel engine similar to Example 1 except that component (D) in Table 1 is 0.1 g of Rb.

Example 7

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that component (E) of Table 1 was 10 g of HX zeolite.

Example 8

Except for the component (E) in Table 1, 10 g of NaY zeolite (Si / AL = 5), the exhaust gas purifier for a diesel engine is the same as that of Example 1.

Example 9

Except for the component (E) of Table 1, 10 g of NaX zeolite, the exhaust gas purifying apparatus for the diesel engine was the same as that of Example 1.

Example 10

Except for the component (E) in Table 1, 10 g of HZSM-5 (Si / Al = 80), the exhaust gas purifier for a diesel engine is the same as that of Example 1.

Example 11

Except for the component (E) in Table 1, 10 g of NaZSM-5 (Si / Al = 80), the exhaust gas purifier for a diesel engine is the same as that of Example 1.

Example 12

Except for the component (E) in Table 1, 10g of LaY zeolite (Si / Al = 5), the exhaust gas purifying apparatus for the diesel engine was the same as that of Example 1.

Example 13

Except that the component (E) of Table 1 is 10 g of yttria, it is the exhaust gas purification device for a diesel engine similar to Example 1.

Example 14

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that (J) component of Table 1 is 0.4g of Cu.

Example 15

Exhaust gas purifying apparatus is the same as that of Example 1 except that (J) component of Table 1 is 0.4 g of Co.

Example 16

Exhaust gas purification device for a diesel engine similar to Example 1 except that (J) component of Table 1 is 0.4 g of Cr.

Example 17

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that (J) component of Table 1 is V 0.4g.

Comparative Example 1

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that nothing is added as component (D) of Table 1.

Comparative Example 2

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that nothing is added as component (C) in Table 1.

Comparative Example 3

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that nothing is added to the components (C) and (D) in Table 1, respectively.

[Comparative Example 4]

Except for using Pd 3g as the component (A) of Table 1, and nothing is added to the components (B), (C), and (D), respectively, the exhaust gas purifier for a diesel engine is the same as that of the first embodiment.

[Comparative Example 5]

Except for using Pt 3g as component (B) of Table 1, and nothing is added to each of the components (A), (C) and (D), the exhaust gas purifier for a diesel engine is the same as that of Example 1.

Comparative Example 6

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that nothing is added as component (E) of Table 1.

Comparative Example 7

Except for the same diesel engine as in Example 1, except that Pd 5g as component (A), Pt 5g as component (B), Ni 2g as component (C) and Na 1g as component (D) are used. It is a gas purifier.

Comparative Example 8

Except for using Pd 0.05g as component (A) of Table 1 and Pt 0.05g as component (B), the exhaust gas purification apparatus for a diesel engine is the same as that of Example 1.

Comparative Example 9

Except for using 1.5 g of Pd as component (A) of Table 1 and 0.5 g of Pt as component (B), the same diesel engine exhaust gas purifier as Example 1 was used.

Comparative Example 10

Except for using 1.0 g of Ni as component (C) in Table 1, the exhaust gas purification apparatus for a diesel engine is the same as that of Example 1.

Comparative Example 11

Except for using 0.001g of Ni as the component (C) of Table 1 and 0.001g of Na as the component (D), the exhaust gas purification apparatus for a diesel engine is the same as that of Example 1.

Comparative Example 12

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that nothing is added to the components (A), (B), (C) and (D) of Table 1, respectively.

Comparative Example 13

Exhaust gas purification device for a diesel engine similar to Example 1 except that nothing is added to the components (G), (H), (I) and (J) in Table 1, respectively.

Comparative Example 14

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that nothing is added as component (H) of Table 1.

Comparative Example 15

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that nothing is added as component (G) of Table 1.

[Comparative Example 16]

Exhaust gas purification apparatus for a diesel engine similar to Example 1 except that nothing is added as component (I) of Table 1.

[Comparative Example 17]

Exhaust gas purification device for a diesel engine similar to Example 1 except that nothing is added as component (J) in Table 1.

[Comparative Example 18]

Except for using 0.01 g of Ni as component (I) of Table 1 and 0.01 g of Fe as component (J), the exhaust gas purifier for a diesel engine is the same as that of Example 1.

Comparative Example 19

Except for using Ni 7g as the component (I) of Table 1, and Fe 7g as the component (J), the exhaust gas purification apparatus for a diesel engine is the same as that of Example 1.

The present invention includes a metal-supported refractory inorganic oxide and a rare earth oxide formed by supporting platinum group metals and additives such as Ni, lanthanum-based metals and other active metals in alumina, zeolites and yttria, and Ni in CeO ₂ and La ₂ O ₃ , and Fe A honeycomb having a monolith structure is coated with a composition impregnated with at least one element selected from among Cu, V, Cr, and Co, and the calcined carrier is used in an exhaust gas purifier for a diesel engine even under extreme conditions. It has excellent durability and high purification ability at low temperature against harmful ingredients.

Claims (8)

The primary combustion chamber 10, which burns particulate matter and hydrocarbons, which are difficult to oxidize by being connected to the engine side, and the honeycomb 21 coated with metal oxide, are provided with 200 to 450.

In the second catalytic oxidation unit 20 for oxidizing particulate matter and hydrocarbons at a low temperature of the honeycomb 21, the honeycomb 21 is composed of alumina, nickel, lanthanum-based metals and other active metals. Metal-supported refractory inorganic oxides and rare earth oxides formed by supporting zeolites and yttria, and active oils containing Ni in CeO ₂ and La ₂ O ₃ and one or more elements selected from Fe, Cu, V, Cr, and Co. After supporting water, drying and calcining to form an aqueous slurry with a bowl mill to coat the honeycomb having a monolithic structure and calcining the coating carrier, the exhaust gas purification apparatus for a diesel engine. The method of claim 1, wherein the platinum group compound and the additive is composed of platinum (A), palladium (B), nickel (C) and one element (D) selected from Li, Na, K, Cs, Rb, and Fr. The composition ratio of palladium, nickel and (D) material is (A) :( B) = 1: 1.5-1.5: 1, (C) / ((A) + (B)) = 0.005-0.20, (C): (D) = 0.5: 1 to 1: 0.1 and the platinum group metal oxides and additives are 0.1 to 3 weights of the refractory inorganic compound and the rare earth oxide.

Exhaust gas purification apparatus for a diesel engine, characterized in that supported. The catalyst for removing nitrogen oxides of claim 1, wherein CeO ₂ and La ₂ O ₃ contain Ni, and at least one element selected from Cu, Fe, V, Cr, and Co, CeO ₂ and La ₂ O ₃ The ratio of is maintained at 1: 5 to 5: 1, and impregnated with a molar ratio between CeO ₂ and La ₂ O ₃ of the selected element and Ce and La to be 0.2: 1 to 1: 1, respectively. 0.1 to 20 wt% based on refractory inorganic oxides and rare earth oxides

It is preferably 0.5 to 10 weight

Emission gas purification device for a diesel engine, characterized in that the use. According to claim 1, wherein the refractory inorganic oxides and rare earth oxides are zeolites and yttria, and the mixture of alumina and the zeolites together with the alumina is fine in a state in which the weight ratio of alumina and other oxides is 99: 1 to 50:50. Exhaust gas purification device for a diesel engine, characterized in that it comprises as a divided maintenance. The zeolite has a Si / Al ratio of 1 to 500, and the use amount of yttria is 0.5 to 95 weight of the refractory inorganic oxide composition.

Preferably it is 1-50 weight

Emission gas purification device for a diesel engine, characterized in that using the. The method according to claim 1, wherein the metal oxide and the additive are supported on a rare earth oxide or a refractory inorganic oxide to form 110

After drying for more than 6 hours above 110 ~ 650

Calcined for 1 to 10 hours, the calcined metal, the additive-supported rare earth oxide, and the refractory inorganic oxide were made into aqueous sludge using a bowl mill, wash coated on a honeycomb carrier having an integral structure, and then dried and calcined to complete the catalyst. Emission gas purification device for a diesel engine, characterized in that the supporting honeycomb making. 2. The exhaust gas purification of claim 1, wherein the active oil and fat is present in a concentration of 30 to 400 g / dm ³ (catalyst volume), suitably 70 to 250 g / dm ³ (catalyst volume). Device. The honeycomb carrier according to claim 1, wherein the honeycomb carrier is made of corderite, mordenite, mullite, α-alumina, γ-alumina, aluminosilicate, spinel, magnesium silicate, and is preferably corderite. Emission gas purification device for diesel engine.

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