JPH11226402A - Catalyst for purification of exhaust gas and purifying method of exhaust gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for purification of exhaust gas and a purifying method of exhaust gas by which NOx purification performance can be improved even in a low temp. region at a low HC/NOx ratio where a conventional catalyst can not show enough purification performance, and the deterioration of the catalyst can be suppressed even under high temp. hydrothermal conductions. SOLUTION: This catalyst for purification of exhaust gas consists of a first catalyst layer containing a component of one or more kinds selected from platinum Pt, palladium Pd and rhodium Rh and a component of one or more kinds selected from among alkali metals, alkaline earth metals and rare earth metals, a second catalyst layer containing alumina and/or silica, and a third catalyst layer containing a zoelite continuing copper Cu and/or cobalt Co component, and β-zeolite and/or Y-zeolite. The second catalyst layer is formed on the first catalyst layer, and the third catalyst layer is formed on the second layer. Preferably, the catalyst for purification of exhaust gas is used for an internal composition engine whose exhaust gas contains >=14.7 airfuel ratio, >=5% oxygen concn. and <=10 HC/NOx ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying catalyst and an exhaust gas purifying method, and more particularly to an exhaust gas purifying catalyst for purifying nitrogen oxides (NO _x ) in exhaust gas containing excess oxygen with high efficiency. And a method for purifying exhaust gas.

[0002]

2. Description of the Related Art A three-way catalyst is generally widely used as a catalyst for purifying an exhaust gas containing an oxidation component and a reduction component substantially equal to each other, such as a conventional automobile engine exhaust gas. These are platinum (Pt), palladium (P
d), noble metal components such as rhodium (Rh) and ceria (C
e) a catalyst composed mainly of supported activated alumina various metal components of the components or the like, to purify a harmful components hydrocarbons (HC) such in the exhaust gas, carbon monoxide (CO) and NO _x Can be.

On the other hand, in recent years, from the viewpoint of improving fuel efficiency and reducing carbon dioxide emissions, a lean burn engine that can be operated even at an air-fuel ratio higher than the stoichiometric air-fuel ratio has attracted attention. The exhaust gas of such an engine (hereinafter, referred to as "lean exhaust gas") has a higher oxygen content than the exhaust gas of a conventional engine operating near the stoichiometric air-fuel ratio (hereinafter, referred to as "stoichiometric exhaust gas"). rate is high, the purification of the NO _x becomes insufficient in the conventional three-way catalyst. Therefore, new catalyst that can purify the NO _x in lean exhaust gas with high efficiency is desired.

[0004] Various metallic components Y type, L-type, mordenite, zeolite-supported zeolite-based catalyst such as MFI zeolite, the presence of HC classes in a lean exhaust gas, the ability to relatively efficiently purify NO _x have. Such metal components include copper (Cu), cobalt (Co), silver (Ag), nickel (Ni), and iron (Fe).
And noble metal components such as platinum (Pt) have also been found to be effective.
u- zeolitic catalysts, to indicate a relatively good _the NO _x purification performance even at a high flow rate gas conditions, for application to the exhaust gas purification of small mobile sources and stationary private power generation engine such as an automobile Expectations are over.

However, a zeolite-based metal component is supported.
The catalyst has the following problems. In other words, conventional zeorai
Catalyst is NO_xTemperature range that can relatively efficiently purify
The surrounding area is narrow, especially the relatively low temperature range of 150 ° C to 300 ° C.
NO in the area_xPurification capacity cannot be obtained, and exhaust gas
Under relatively low levels of HCs, especially under NO _xAnd H
C reacts and NO_xNecessary to convert nitrogen into nitrogen
Classification and NO_xRatio to the amount (HC / NO_xRatio) is 5-6 or less
Under the conditions below, NO_xPurification capacity has dropped sharply
I will. On the other hand, high temperature (600 ° C or higher)
Under conditions (hydrothermal conditions), catalyst degradation is extremely large
Because of a fundamental problem, lean burn
Has not yet been put into practical use as an exhaust gas purification catalyst
Is the current situation.

Accordingly, in order to improve the NO _x purification ability in the low temperature region, for example, by providing a noble metal catalyst layer below the Cu-zeolite catalyst layer, the reaction heat of the noble metal catalyst layer is utilized. It has been proposed to operate the upper Cu-zeolite catalyst from a low temperature (Japanese Patent Application Laid-Open Nos. 1-127044 and 5-68888).

However, in this case, the heat of the oxidation reaction in the lower noble metal catalyst layer causes a large deterioration of the catalyst, and the strong oxidation activity of the noble metal catalyst layer causes the preferential oxidation and consumption of HC by the noble metal catalyst layer. , A decrease in the NO _x purification rate is caused. This effect is caused by the coexistence of a noble metal component in the Cu-zeolite-based catalyst layer (JP-A-1-31074,
In Japanese Patent Application Laid-Open No. 5-168939, this is particularly large.

When a Pt-based catalyst is used, 20
Although NO _x can be converted even in a relatively low temperature range of ₀ to 250 ° C., not only conversion to N ₂ but also generation of N ₂ O cannot be ignored, and it is difficult to use because of adverse effects on the environment. It is in.

Accordingly, in the conventional catalyst such as Cu- zeolite-based catalyst and Pt-based catalysts, in the low exhaust gas conditions HC / NO _x ratio, NO _x purifying performance becomes insufficient, and therefore, the reducing agent HC A purification method has also been proposed in which alcohols, alcohols, and the like are secondarily supplied to the catalyst inlet.

However, in this case, it is necessary to mount a reducing agent tank on the vehicle or to directly use fuel as the reducing agent. A problem arises in that the fuel efficiency of the engine is sacrificed.

[0011]

The purpose of the invention [0006] claims 1-9 wherein also NO _x in the low temperature range and the low HC / NO _x ratio in the conventional catalyst could not exhibit sufficient purification performance An object of the present invention is to provide an exhaust gas purifying catalyst capable of improving purification performance and suppressing catalyst deterioration even under high-temperature hydrothermal conditions.

The purpose of the description of claim 10 is to provide
NO of the catalyst for purification of exhaust gas of Ming _xEspecially effective
To provide a method for purifying an exhaust gas purifying catalyst that can be effectively used
In

[0013]

According to a first aspect of the present invention, there is provided an exhaust gas purifying catalyst comprising one or more components selected from the group consisting of platinum (Pt), palladium (Pd) and rhodium (Rh); A first catalyst layer containing one or more components selected from the group consisting of metals, alkaline earth metals and rare earth metals, a second catalyst layer containing alumina and / or silica, and copper (Cu) and / or A third catalyst layer containing a zeolite containing a cobalt (Co) component and a β zeolite and / or a Y-type zeolite, wherein a second catalyst layer is formed on the first catalyst layer, and a third catalyst layer is formed on the second catalyst layer. The third catalyst layer is located.

According to a second aspect of the present invention, there is provided the exhaust gas purifying catalyst according to the first aspect, wherein the alkali metal, the alkaline earth metal and the rare earth metal contained in the first catalyst layer are magnesium (Mg). , Calcium (Ca),
Potassium (K), barium (Ba), lanthanum (L
a), strontium (Sr), cesium (Cs), and cerium (Ce).

According to a third aspect of the present invention, there is provided the exhaust gas purifying catalyst according to the first or second aspect.
The content of at least one component selected from the group consisting of an alkali metal, an alkaline earth metal and a rare earth metal contained in the catalyst layer is more than 0.1 mol and 0.6 mol per 1 L of the exhaust gas purifying catalyst. It is characterized by the following range.

The exhaust gas purifying catalyst according to a fourth aspect of the present invention is the exhaust gas purifying catalyst according to any one of the first to third aspects, wherein the β / zeolite in the third catalyst layer has a silica / alumina ratio of 20 to 20. 150, characterized in that the silica / alumina ratio of the Y-type zeolite is from 4 to 50.

According to a fifth aspect of the present invention, there is provided the exhaust gas purifying catalyst according to the fourth aspect, wherein the amount of β zeolite and / or Y type zeolite in the third catalyst layer is reduced. It is characterized by weighing 10 to 150 g per liter.

According to a sixth aspect of the present invention, there is provided the exhaust gas purifying catalyst according to any one of the first to fifth aspects, wherein the zeolite containing Cu and / or Co component in the third catalyst layer is used. With a silica / alumina ratio of 20 to 80
It is a FI zeolite and / or a β zeolite.

According to a seventh aspect of the present invention, there is provided the exhaust gas purifying catalyst according to the sixth aspect, wherein the amount of Cu and / or Co in the third catalyst layer is per liter of the exhaust gas purifying catalyst. It is characterized by being in the range of 0.05 to 0.5 mol.

[0020] The exhaust gas purifying catalyst according to claim 8 is the exhaust gas purifying catalyst according to claim 7, wherein the amount of the zeolite containing Cu and / or Co component in the third catalyst layer is reduced. 120g-300g per liter of catalyst
It is characterized by being.

According to a ninth aspect of the present invention, there is provided the exhaust gas purifying catalyst according to any one of the first to eighth aspects, wherein the amount of alumina and / or silica in the second layer is the same as the exhaust gas purifying catalyst. 20 g to 100 g per liter of the catalyst.

According to a tenth aspect of the present invention, there is provided an exhaust gas purifying method according to any one of the first to ninth aspects, wherein the exhaust gas purifying catalyst has an air-fuel ratio (A / F) of 14.7 or more, at a concentration of 5% or more, and the ratio of the amount of hydrocarbon and nitrogen oxide amount necessary to convert the nitrogen oxides and hydrocarbons react with nitrogen oxides into nitrogen (= HC / NO _x ratio) of 10 or less It is characterized in that it is used for an internal combustion engine.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The exhaust gas purifying catalyst of the present invention
The first catalyst layer, which has a layer structure and is the lowermost layer, is composed of Pt, P
one or more components selected from the group consisting of d and Rh;
At least one component selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals.

The one or more noble metal components selected from the group consisting of Pt, Pd and Rh are, for example, Pt, Rh, P
Various combinations such as only d, Rh, and Pd are possible. By containing the precious metal component according to the first catalyst layer, giving oxidizing power, by removing the excess reducing gas component in a lean atmosphere, it is possible to promote the absorption of NO _x activity.

The content of the noble metal, but of absorption of NO _x performance and three-way catalyst performance is not particularly limited as long enough to obtain,
If the amount is less than 0.1 g, sufficient ternary performance cannot be obtained, and
g of the exhaust gas purifying catalyst of the present invention.
0 g is preferred.

The first catalyst layer contains an alkali metal, an alkaline earth metal and a rare earth metal component in an amount of more than 0.1 mol per 1 L of the exhaust gas purifying catalyst of the present invention.
It is preferable to contain it in the range of mol or less. Potassium, lithium and sodium are preferred as alkali metals, especially sodium, barium, strontium, calcium and magnesium as alkaline earth metals, and Y, La, Cs, Ce, Pr, Nd, Pm, as rare earth metals.
It is preferable that Sm particularly use Cs and Ce.

The amount is determined according to the exhaust gas purifying catalyst 1 of the present invention.
If it is 0.1 mol or less per L, the NO _x absorption becomes insufficient, and if it exceeds 0.6 mol, the effect of the noble metal is negated, so that it is more than 0.1 mol and 0.6 mol or less. preferable.

The first catalyst of the present invention is preferably used in a honeycomb form. As the honeycomb material, cordierite-based materials are generally widely used, but are not limited thereto, and a honeycomb carrier made of a metal material is also effective, and the catalyst powder itself is formed into a honeycomb shape. You can also. Cars have a honeycomb-shaped catalyst, which increases the contact area between the catalyst and exhaust gas and reduces pressure loss, causing vibrations and processing a large amount of exhaust gas in a limited space. This is extremely advantageous when used as an automobile catalyst which is required to be used.

The first catalyst layer oxidizes NO _x by coexisting a noble metal component and at least one component selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, It has the function of converting to more reactive NO _x species, and promotes the low-temperature activity of the NO _x reducing material of the third catalyst layer described later.

The exhaust gas purifying catalyst of the present invention is characterized in that the first
On the catalyst layer, a second catalyst layer containing alumina and / or silica as an isolation layer is provided. Such alumina and / or silica do not contain any precious metal components. By including such alumina and / or silica in the catalyst, the thermal stability of the active component in the first and third catalyst layers can be improved, and high durability can be realized.

That is, when the noble metal-containing catalyst layer as the first catalyst layer and the NO _x reducing material layer as the third catalyst layer come into direct contact, a reaction between the active components occurs, which is not always preferable in terms of catalyst deterioration. Therefore, the second catalyst layer has a function as an isolation layer.

The amount is determined according to the exhaust gas purifying catalyst 1 of the present invention.
20 to 100 g per L is preferable because it plays a role of the separating layer and does not prevent the exhaust gas from diffusing into the first catalyst layer.

The exhaust gas purifying catalyst of the present invention further comprises a third catalyst layer comprising a zeolite containing a Cu and / or Co component and a β zeolite and / or a Y-type zeolite on the second catalyst layer. Having.

The zeolite containing Cu and / or Co component includes MFI type zeolite, Y type zeolite,
Mordenite, ferrierite, β-zeolite and the like can be used, but MFI-zeolite and β-zeolite are particularly preferred in terms of high heat resistance and high NO _x purification performance.

The silica / alumina ratio of the zeolite containing the Cu and / or Co component is preferably from 20 to 80. If the silica / alumina ratio is smaller than this range, the zeolite skeleton becomes unstable and is supported by ion exchange. In addition, the amount of the components (Cu and / or Co) becomes excessive, the dispersibility is reduced, the activity per active point is rapidly reduced, and aggregation between the active sites is likely to occur. On the other hand, if the silica / alumina ratio is larger than this range, the number of active sites is too small to obtain sufficient activity.

[0036] Cu and / or Co component to be supported has a function as active sites showing the _the NO _x purification function in a lean exhaust gas, the amount is 0.05 per catalyst catalyst 1L for purifying exhaust gases It is preferably contained in the range of 0.5 mol. This is because sintering due to heat is less likely to occur within this range.

The zeolite supporting Cu and / or Co has a function as a NO _x reducing agent, and from the viewpoint of its use conditions, 120 to 300 per liter of exhaust gas purifying catalyst.
g is preferred.

Furthermore, the fact that the third catalyst layer uniformly mixes the NO _x reducing material and β zeolite and / or Y-type zeolite as the HC trapping material is advantageous in that a large amount of HC exists in the NO _x reducing site. Is preferred. Such β-zeolite and / or Y-type zeolites, metal components are not supported, the amount, it is 10~150g catalyst per 1L for purifying exhaust gases of the amount of HC adsorbed amount and _the NO _x purification agent It is preferable from the viewpoint of balance.

The silica / alumina ratio of the β zeolite is preferably from 20 to 150, and the silica / alumina ratio of the Y-type zeolite is preferably from 4 to 50 from the viewpoint of heat resistance and the amount of acid sites.

If the silica / alumina ratio is smaller than this range, the zeolite skeleton becomes unstable. Conversely, if the silica / alumina ratio is larger than this range, the ability to retain HCs is weakened, and the NO _{x of} the third catalyst layer is reduced. HCs cannot be stored until the temperature at which the reducing material starts operating. As the Y-type zeolite, particularly, USY-type zeolite is preferably used because the hydrothermal resistance is improved.

The total coating amount of the third catalyst layer is preferably 120 to 300 g per liter of the exhaust gas purifying catalyst.
If the coating amount of the third catalyst layer is less than this range, the activity under high SV becomes insufficient, and if it is more than this range, diffusion of the reactive molecules to the first and second layers is hindered, An adverse effect such as an increase in pressure loss occurs.

[0042] Such third layer, the exhaust gas is the HC classes efficiently trapped when in the low temperature region, by supplying HC class if _the NO _x reduction material is a temperature range to operate to promote the reduction of the NO _x . In particular, the way to push mixing uniformly and trap material and _the NO _x reduction material HC classes, the HC classes in _the NO _x reduction, it is possible to more efficiently use.

The β zeolite and / or Y-type zeolite in the first catalyst layer and the third catalyst layer are capable of oxidizing NO _x and adsorbing HCs of the third catalyst layer which has deteriorated under high-temperature hydrothermal conditions. In order to compensate for the quality effect, it is possible to suppress catalyst deterioration due to high-temperature hydrothermal conditions as the whole catalyst.

The exhaust gas purifying catalyst of the present invention comprises the above three layers, and the combination of the three layers comprises a NO _x reducing material and an HC
The third catalyst layer containing an adsorbent on the outermost surface, a first catalyst layer containing the precious metal component is disposed in the lowest layer, the second layer that isolates the _the NO _x reduction material layer and the precious metal catalyst layer arranged therebetween. With such an arrangement of the catalyst layer, the HC adsorbent becomes NO _x
The HC is efficiently supplied by being present in the same layer as the reducing agent, and the catalyst is warmed from a low temperature in the first layer, so that the third
The temperature at which the layer is activated is lower.

The various zeolites used in the present invention are stabilized by increasing the crystallinity by hydrothermal treatment, resynthesis, etc., and a catalyst having high heat resistance and durability can be obtained. Is preferred.

The metal raw material compound for catalyst preparation used in the present invention includes inorganic acid salts such as nitrates and carbonates, ammonium salts, organic acid salts, halides, oxides, sodium salts, and the like.
Although an ammine complex compound or the like can be used in combination, it is particularly preferable to use a water-soluble salt from the viewpoint of improving the catalyst performance. The method of supporting the noble metal is not limited to a special method, and various methods such as a known evaporation and drying method, a precipitation method, an impregnation method, and an ion exchange method can be used as long as no significant uneven distribution of components is involved. In particular, the ion-exchange method is preferably used for loading on zeolite from the viewpoint of ensuring metal dispersibility.

In the case of the ion exchange method or the impregnation method, since the metal raw material is often used in a solution, the pH can be adjusted by adding an acid or a base to the solution. pH
By adjusting the value, the state of supporting the metal can be further controlled, and the heat resistance can be ensured.

The thus obtained catalyst used in the present invention is pulverized into a slurry, coated on a catalyst carrier, and calcined at a temperature of 400 to 900 ° C. to obtain the exhaust gas purifying catalyst of the present invention. Obtainable.

Since the exhaust gas purifying catalyst of the present invention has a multilayer structure, it is preferably used in a honeycomb shape. In this case, the catalyst carrier can be appropriately selected from known catalyst carriers. Examples thereof include a honeycomb carrier and a metal carrier having a monolith structure made of a refractory material. These carriers are coated with the zeolite-based catalyst of the present invention and used. The shape of the catalyst carrier is not particularly limited, but is usually preferably used in a honeycomb shape. As the honeycomb material, cordierite-based materials such as ceramics are generally used in many cases. It is also possible to use a honeycomb made of a metal material, and further, the catalyst powder itself may be formed into a honeycomb shape. By making the shape of the catalyst into a honeycomb shape, the contact area between the catalyst and the exhaust gas is increased and the pressure loss is suppressed, so it is required to process a large amount of exhaust gas in a vibrating and limited space. It is suitable for use as an automotive catalyst or the like.

The use conditions of the exhaust gas purifying catalyst of the present invention are not particularly limited. However, in order to exhibit high-efficiency purifying performance, the exhaust gas purifying catalyst is preferably used under lean conditions where the air-fuel ratio (A / F) is 14.7 or more. The exhaust gas purifying catalyst of the present invention is installed in an exhaust system of an internal combustion engine operated at a temperature of 5% or more, and nitrogen oxides and hydrocarbons react to convert nitrogen oxides to nitrogen. It is preferable that an exhaust gas having a ratio of the amount of hydrocarbon and the amount of nitrogen oxide (= HC / NO _x ratio) of 10 or less be passed and contacted. This is because if the oxygen concentration is low and the amount of hydrocarbons is too large, coking on the catalyst surface is likely to occur, and catalyst deterioration is promoted. Can withstand long-term use and maintain high purification performance.

[0051]

[Example 1]

(1) Formation of First Catalyst Layer After adding activated alumina powder to an aqueous solution of dinitrodiammine platinum and stirring well, the mixture was dried at 120 ° C. for 8 hours in a drier and then calcined at 500 ° C. for 2 hours in a stream of air. Pt
Was obtained, whereby about 1.0% by weight of Pt-activated alumina powder was obtained. A nitric acid-alumina sol and water were added to the catalyst powder in a magnetic ball mill pot, mixed and pulverized for about 20 minutes to obtain a slurry of Pt-activated alumina. The addition amount of alumina sol was 5% by weight. The thus obtained slurry was applied to 1.0 L of cordierite-based honeycomb carrier having about 400 channels per square inch cross section, dried with hot air at 150 ° C., and fired at 500 ° C. for 1 hour. Thus, a honeycomb catalyst having a coating amount of about 35 g / L was obtained.

The honeycomb catalyst was immersed in a mixed aqueous solution containing calcium acetate, barium acetate and lanthanum nitrate, dried at 120 ° C., and then calcined at 500 ° C. for 1 hour to convert Ca, Ba and La into 1 L of the honeycomb catalyst. Thus, a honeycomb catalyst A1 coated with a first catalyst layer containing 0.1 mol, 0.15 mol, and 0.1 mol, respectively, was obtained.

(2) Formation of the second catalyst layer Alumina sol and water were added to the activated alumina powder containing γ-alumina as a main component in a magnetic ball mill pot, and the mixture was added for about 20 minutes.
The mixture was mixed and crushed for minutes to obtain a slurry. At this time, the addition amount of the alumina sol was 5% by weight as Al ₂ O ₃ . The slurry obtained in this manner is applied to the honeycomb catalyst A1 obtained in the above (1), dried at 150 ° C. with hot air, baked at 500 ° C. for 1 hour, and coated at about 55 g / L.
The honeycomb catalyst A2 having the second catalyst layer was obtained.

(3) Formation of Third Catalyst Layer SiO ₂ / Al ₂ O was mixed in a 0.17 mol / L copper nitrate / cobalt nitrate mixed aqueous solution (Cu: Co = 8.2).
₃ molar ratio was added to powder of about 35 NH ₄ type MFI zeolite well stirred, followed by separation of the solid-liquid by filtration. By repeating the above-mentioned stirring / filtration operation three times, an MFI zeolite catalyst cake carrying Cu and Co on ion exchange was obtained. This catalyst cake is placed in a dryer for 12 hours.
By drying at 0 ° C. for 24 hours or more, and then baking at 600 ° C. for 4 hours in an air atmosphere using an electric furnace, Cu-Co carrying 3.9% by weight of Cu and 0.8% by weight of Co
-An MFI zeolite catalyst powder was obtained.

The catalyst powder and H-type β zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of about 25 were mixed with alumina sol and water at a ratio of 2: 1 and pulverized in a magnetic ball mill pot for 20 minutes to obtain a slurry. And This slurry was coated on the above honeycomb catalyst A2, and dried at 120 ° C.
For 8 hours, and then calcined at 450 ° C. for 1 hour in an air stream to obtain an exhaust gas purifying catalyst 1 of the present invention. The coating amount of the third catalyst layer was about 300 g / L.

[Example 2] The MFI zeolite powder in the third catalyst layer was mixed with N ₂ having a SiO ₂ / Al ₂ O ₃ molar ratio of about 42.
It was replaced by H ₄ type β-zeolite in the same manner as in Example 1 to obtain an exhaust gas purifying catalyst 2 of the present invention.

Example 3 The H-type β zeolite powder in the third catalyst layer was mixed with N ₂ having a SiO ₂ / Al ₂ O ₃ molar ratio of about 30.
It was replaced by H _4-inch Y-type zeolite in the same manner as in Example 1 to obtain an exhaust gas purifying catalyst 3 of the present invention.

Example 4 Pt (1.0%) in the first catalyst layer
Wt%) to Pd-Rh (1.2 wt%-0.2 wt%)
In the same manner as in Example 1 except that the catalyst was changed to, the exhaust gas purifying catalyst 4 of the present invention was obtained.

Example 5 1.0 mol of Ca, 0.15 mol of Ba and 0.1 mol of La in the first catalyst layer were replaced with 0.1 mol of Mg.
Exhaust gas purifying catalyst 5 of the present invention was obtained in the same manner as in Example 1 except that the amount was changed to 01 mol, 0.1 mol of Ba, and 0.01 mol of K.

Example 6 1.0 mol of Ca, 0.15 mol of Ba and 0.1 mol of La in the first catalyst layer were replaced with 0.1 mol of Ba.
2 mol, Sr 0.05 mol, Cs 0.04 mol, Ce
An exhaust gas purifying catalyst 6 of the present invention was obtained in the same manner as in Example 1 except that the amount was changed to 0.29 mol.

Example 7 Cu-Co- in the third catalyst layer
Exhaust gas purification catalyst 7 of the present invention was obtained in the same manner as in Example 1 except that the mixing ratio of the MFI catalyst powder and the H-type β zeolite was changed to 5: 1.

Example 8 The coating amount of the third catalyst layer was 15
0 g / L instead of Cu-Co-MFI catalyst powder and H-type β
Exhaust gas purification catalyst 8 of the present invention was obtained in the same manner as in Example 1 except that the mixing ratio of zeolite was changed to 5: 1.

Example 9 The coating amount of the second catalyst layer was 25
Exhaust gas purification catalyst 9 of the present invention was obtained in the same manner as in Example 1 except that g / L was used.

Example 10 The coating amount of the second catalyst layer was 9
Except that the amount was changed to 6 g / L, an exhaust gas purifying catalyst 10 of the present invention was obtained in the same manner as in Example 1.

Example 11 The present invention was carried out in the same manner as in Example 1 except that the MFI zeolite in the third catalyst layer was replaced with an H-type MFI zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of about 24. The exhaust gas purifying catalyst 11 was obtained.

Example 12 The present invention was carried out in the same manner as in Example 1 except that the MFI zeolite in the third catalyst layer was replaced with an H-type MFI zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of about 76. The exhaust gas purifying catalyst 12 was obtained.

Example 13 An exhaust gas purifying catalyst 13 of the present invention was obtained in the same manner as in Example 1 except that the activated alumina powder in the second catalyst layer was changed to silica powder.

Comparative Example 1 An exhaust gas purifying catalyst (1) was prepared in the same manner as in Example 1 except that the third catalyst layer was directly coated on the first catalyst layer without providing the second catalyst layer. Obtained.

Comparative Example 2 An exhaust gas purifying catalyst (2) was obtained in the same manner as in Example 1 except that H-type β zeolite was not mixed in the third catalyst layer.

Comparative Example 3 0.01 mol of Mg, 0.
1 mol, 0.01 mol of K, 0.03 mol of Mg, Ba
Example 5 except for changing to 0.04 mol and K0.01 mol
In the same manner as in the above, an exhaust gas purifying catalyst (3) was obtained.

[Comparative Example 4] Ba 0.2 mol, Sr 0.0
5 mol, Cs 0.04 mol, Ce 0.29 mol
0.3 mol, Sr 0.02 mol, Cs 0.3 mol, Ce
An exhaust gas purifying catalyst (4) was obtained in the same manner as in Example 6, except that the amount was changed to 0.01 mol.

Comparative Example 5 The coating amount of the third catalyst layer was 10
An exhaust gas purifying catalyst (5) was obtained in the same manner as in Example 8, except that the amount was changed to 0 g / L.

Comparative Example 6 The coating amount of the third catalyst layer was 32
An exhaust gas purifying catalyst (6) was obtained in the same manner as in Example 8, except that the amount was changed to 0 g / L.

[Comparative Example 7] The coating amount of the second catalyst layer was 17
Except that g / L was used, an exhaust gas purifying catalyst (7) was obtained in the same manner as in Example 1.

Comparative Example 8 The coating amount of the second catalyst layer was 11
An exhaust gas purifying catalyst (8) was obtained in the same manner as in Example 1 except that the amount was changed to 5 g / L.

[Comparative Example 9] The MFI zeolite in the third catalyst layer was converted to H-type M having a SiO ₂ / Al ₂ O ₃ molar ratio of about 17
Exhaust gas purification catalyst (9) was obtained in the same manner as in Example 1 except that FI zeolite was used instead.

Comparative Example 10 Exhaust gas was obtained in the same manner as in Example 1 except that the MFI zeolite in the third catalyst layer was replaced with an H-type MFI zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of about 82. A purification catalyst (10) was obtained.

Comparative Example 11 Exhaust gas purifying catalyst (except that the molar ratio of SiO ₂ / Al ₂ O ₃ of H-type zeolite in the third catalyst layer was changed to about 15) 1
1) was obtained.

[Comparative Example 12] NH ₄ type Y in the third catalyst layer
The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite is about 1.
Except for using Example 5, an exhaust gas purifying catalyst (12) was obtained in the same manner as in Example 3.

The compositions of the exhaust gas purifying catalysts obtained in Examples 1 to 13 and Comparative Examples 1 to 12 are shown in Tables 1 to 3.

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

Test Example The catalytic performance of the exhaust gas purifying catalysts obtained in Examples 1 to 13 and Comparative Examples 1 to 12 was evaluated by the following method.

Catalyst Performance Test Example 1 Each exhaust gas purifying catalyst was incorporated into the exhaust system of an engine dynamo apparatus equipped with a 4-cylinder 2.5 L diesel engine, and subjected to a rapid endurance treatment at 630 ° C. × 30 hours.
Next, the exhaust gas purifying catalyst after the endurance treatment is incorporated into an exhaust system of an engine dynamo device equipped with a 4-cylinder 2.5L diesel engine, and the catalyst inlet temperature is raised to 100 ° C to 500 ° C. The NO _x conversion performance at the time was measured. The rate of temperature rise from 100 ° C. to 500 ° C. was about 30 ° C./min, the average HC / NO _x ratio in the exhaust gas was 2.8, and the gas space velocity was 45000 h ⁻¹ .

The above engine dynamo apparatus can change the HC / NO _x ratio in the exhaust gas by injecting light oil from a nozzle provided between the engine manifold and the catalyst.

The NO _x conversion performance was determined by _{measuring the} concentration of NO _{x at the} inlet of the catalyst and the concentration of NO _{x at the} outlet of the catalyst MEXA-60 manufactured by HORIBA.
It was measured by 00SH and determined by the following equation.

[0088]

(Equation 1)

Table 4 shows the obtained catalyst activity evaluations.

[0090]

[Table 4]

[0091] Catalyst examples are clearly higher _the NO _x purification rate than the catalyst of Comparative Example, which is due to the catalytic performance difference, those embodiments, efficiently trapping the HC such a low temperature range and the HC at temperature rising process in order to utilize with high efficiency, believed to exhibit superior _the NO _x purification efficiency.

When the amount of alkali metal, alkaline earth metal and rare earth metal carried and the silica / alumina ratio of the zeolite are out of the range of the present invention, the first layer and the third
It can be seen that the above function of the layer is reduced, and particularly, the silica / alumina ratio of the third layer zeolite has a large effect on the catalytic performance. Further, it is clear that the coating amounts of the second layer and the third layer also have a large effect on the catalytic performance.

[0093] In the catalytic performance test Example 2 Test Example 1, using the catalyst of Example 2, the light-off - Light On repeated 10 times, the HC / NO _x ratio of the engine exhaust gas 2.0 to 15. 0 each light-off after performed varied from - NO _x average conversion versus HC / NO _x ratio in the light-on test (100 to 5
The temperature rise / fall test at 00 ° C. was repeated 10 times with each HC / NO, and at that time, the respective NO _x conversion rates were obtained, and the average NO _x conversion rate) was obtained. Each NO _x conversion was determined by the above equation (1).

FIG. 1 shows the results. FIG. 1 shows that the horizontal axis is H
The C / NO _x ratio is shown, and the average conversion rate of NO _x is shown on the vertical axis. In the catalyst of the present invention, when the HC / NO _x ratio is 10 or more, the NO _x conversion rate sharply decreases, and rather a moderate H
It can be seen that a sufficiently high NO _x conversion can be obtained with the amount of carbon.

Test Example 3 of Catalyst Performance In Test Example 1, the catalyst of Example 2 was used, and light-off / light-on was repeated 10 times, and the oxygen concentration in the engine exhaust gas composition was changed in the range of 2% to 10%. each light-off after performed by - was determined NO _x average conversion versus oxygen concentration in the light-on test. The NO _x conversion was determined by the above equation (repeated 10 times at each oxygen concentration, and conducted a temperature rise / fall test).

FIG. 2 shows the results. 2, the oxygen concentration on the horizontal axis indicates the average conversion of the NO _x on the vertical axis. Light-off oxygen concentration is 5% or less - when repeated light-on test, well understood that the NO _x conversion performance can not be sufficiently obtained. Therefore, the exhaust gas purifying catalyst of the present invention exhibits high performance under the condition of an oxygen concentration of 5% or more and a relatively large amount of oxygen.

[0097]

The exhaust gas purifying catalyst according to any one of claims 1 to 9 includes a low temperature range of 150 ° C. or lower and has a low HC / NO _x ratio condition.
In particular, since the purification of NO _x can be performed with high efficiency, it is possible to provide an automobile with low environmental pollution and excellent economic efficiency (fuel efficiency).

Further, the exhaust gas purifying method according to the tenth aspect exhibits the NO _x purifying action of the exhaust gas purifying catalyst of the present invention particularly efficiently even in a low temperature range and a low HC / NO _x ratio condition. Can be done.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing an example of the NO.
FIG. 3 is a diagram illustrating an example of a relationship between an _x purification rate and an HC / NO _x ratio in exhaust gas.

FIG. 2 is a graph showing NO in the exhaust gas purifying catalyst of the present invention.
FIG. 3 is a diagram illustrating an example of a relationship between an _x purification rate and an O ₂ concentration in exhaust gas.

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁶ identifications FI B01J 29/072 B01J 37/02 301L 29/46 F01N 3/28 301P 37/02 301 B01D 53/36 104A F01N 3/28 301 B01J 23/56 301A

Claims (10)

[Claims] At least one component selected from the group consisting of platinum (Pt), palladium (Pd) and rhodium (Rh) and one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals. A first catalyst layer containing one or more components, a second catalyst layer containing alumina and / or silica, a zeolite containing a copper (Cu) and / or cobalt (Co) component, and a β zeolite and / or A third catalyst layer containing a Y-type zeolite, wherein the second catalyst layer is located on the first catalyst layer, and the third catalyst layer is located on the second catalyst layer. catalyst. 2. An alkali metal, an alkaline earth metal and a rare earth metal contained in the first catalyst layer are magnesium (M
g), calcium (Ca), potassium (K), barium (Ba), lanthanum (La), strontium (S
The exhaust gas purifying catalyst according to claim 1, wherein r) is cesium (Cs) or cerium (Ce). 3. The content of at least one component selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals contained in the first catalyst layer is 0.1 mol per liter of exhaust gas purifying catalyst. 3. The exhaust gas purifying catalyst according to claim 1, wherein the range is more than 0.6 mol and less. 4. The silica / alumina ratio of the β zeolite in the third catalyst layer is 20 to 150, and the silica / alumina ratio of the Y zeolite is 4 to 50 in the third catalyst layer. The exhaust gas purifying catalyst according to the above item. 5. The exhaust gas purifying catalyst according to claim 4, wherein the amount of β zeolite and / or Y type zeolite in the third catalyst layer is 10 to 150 g per liter of exhaust gas purifying catalyst. . 6. The zeolite containing Cu and / or Co component in the third catalyst layer has a silica / alumina ratio of 20 to 20.
The exhaust gas purifying catalyst according to any one of claims 1 to 5, wherein the catalyst is 80 MFI zeolite and / or β zeolite. 7. The amount of the Cu and / or Co component in the third catalyst layer is 0.05 to 0.1 / L per 1 L of the exhaust gas purifying catalyst.
7. The exhaust gas purifying catalyst according to claim 6, wherein the amount is within a range of 5 mol. 8. The amount of the zeolite containing Cu and / or Co component in the third catalyst layer is 1 L of the exhaust gas purifying catalyst.
The exhaust gas purifying catalyst according to claim 7, wherein the weight is 120 g to 300 g per unit. 9. The exhaust gas purifying apparatus according to claim 1, wherein the amount of alumina and / or silica in the second layer is 20 g to 100 g per liter of the exhaust gas purifying catalyst. catalyst. 10. The exhaust gas purifying catalyst according to any one of claims 1 to 9, wherein the exhaust gas has an air-fuel ratio (A / F) of 1.
4.7 or more, the oxygen concentration is 5% or more, and the ratio of the amount of hydrocarbons to the amount of nitrogen oxides necessary for the nitrogen oxides and hydrocarbons to react and convert the nitrogen oxides to nitrogen (= HC / NO) _x
An exhaust gas purification method characterized by being used for an internal combustion engine having a ratio of 10 or less.