JP4742899B2 - Exhaust gas purification filter - Google Patents

Description

  The present invention relates to an exhaust gas purification filter that purifies exhaust gas by burning PM (Particulate Matter) contained in exhaust gas such as a diesel engine.

  PM contained in exhaust gas from a diesel engine or the like has a particle size of approximately 1 μm or less, tends to float in the atmosphere, and is easily taken into the human body during breathing. Further, PM contains a carcinogenic substance, and strict regulations are imposed on the emission of PM from a diesel engine.

  As a method for removing PM, there is a method in which PM is collected by an exhaust gas purification filter made of heat-resistant ceramics, the filter is heated by a heater or the like, PM is burned, and is converted into gas and released. Further, by supporting an exhaust gas purification catalyst containing a metal oxide or the like on the exhaust gas purification filter, combustion can be performed at a temperature lower than the normal PM combustion temperature.

As an exhaust gas purification catalyst, a catalyst containing a metal oxide such as Cu or V is known to have high activity. For example, Patent Document 1 discloses an exhaust gas purification catalyst of a metal oxide containing Cu or V. Patent Document 2 discloses an exhaust gas purification catalyst in which a metal salt such as an alkali halide is added to an oxide such as V or Mo. Patent Document 3 discloses an exhaust gas purification catalyst in which an alkali metal oxide and a noble metal are added to an oxide such as Cu, Mn, and Mo, and an exhaust gas purification filter carrying the same.
JP 58-143840 A JP 58-174236 A Japanese Examined Patent Publication No. 4-42063

  However, the conventional exhaust gas purification filter carrying the exhaust gas purification catalyst has the following problems.

  The exhaust gas purification filter carrying the exhaust gas purification catalyst described in Patent Document 1 has difficulty in sufficiently burning PM at the exhaust gas temperature.

  Since the exhaust gas purification filter carrying the exhaust gas purification catalyst described in Patent Documents 2 and 3 has low heat resistance of the alkali metal salt, there is a possibility that the performance may be deteriorated by long-term use.

  A conventional exhaust gas purification filter carrying an exhaust gas purification catalyst may not be able to fully exhibit catalytic activity when the oxygen concentration in the exhaust gas is low or when the oxygen concentration is locally reduced by combustion of PM or the like.

  The present invention solves the above-described conventional problems, and provides an exhaust gas purification filter that has excellent heat resistance and can burn and remove PM at about the exhaust gas temperature even when the oxygen concentration in the exhaust gas is low. With the goal.

In order to achieve the above object, an exhaust gas purification filter of the present invention is a sulfate and / or Be, Mg composed of a metal oxide and a metal of any one of Li, Na, K, Rb, and Cs. , Ca, Sr, Ba, a sulfate composed of a group 2 metal, and a promoter having an oxygen storage ability, supported on a heat-resistant three-dimensional structure, and having an oxygen storage ability Is characterized by being cerium oxide supported on titanium oxide .

  With this configuration, it is possible to provide an exhaust gas purification filter that has excellent heat resistance and can burn and remove PM at about the exhaust gas temperature even when the oxygen concentration in the exhaust gas is low.

  According to the present invention, it is possible to provide an exhaust gas purification filter having excellent heat resistance and capable of burning and removing PM at about the exhaust gas temperature even when the oxygen concentration in the exhaust gas is low.

The invention according to claim 1 of the present invention is a sulfate and / or Be, Mg, Ca, Sr composed of a metal oxide and a metal of any one of Li, Na, K, Rb, and Cs. , A sulfate composed of any one of the two metals of Ba and a promoter having an oxygen storage ability are supported on a heat-resistant three-dimensional structure, and the promoter having the ability to store oxygen is titanium oxide. An exhaust gas purification filter, characterized in that the exhaust gas purification filter is cerium oxide supported on the surface.

  The coexistence of the metal oxide and the sulfate improves the catalytic activity of the metal oxide, and the catalyst has excellent heat resistance. Therefore, the exhaust gas purification filter carrying these can exhibit excellent PM purification ability and heat resistance.

  Further, the co-catalyst having oxygen storage ability coexists with the metal oxide and the sulfate, so that oxygen can be supplied when the oxygen concentration in the exhaust gas is low, and PM combustion can be assisted.

The case where the oxygen concentration in the exhaust gas is low indicates a case where the volume concentration of oxygen in the exhaust gas (hereinafter referred to as oxygen concentration) is 10% or less. Further, by using cerium oxide, oxygen can be effectively supplied when the oxygen concentration in the exhaust gas is low, and therefore combustion of PM can be assisted. Moreover, it is thought that deterioration by the heat | fever of a catalyst is suppressed by carrying | supporting a catalyst further to the cerium oxide carry | supported by titanium oxide. Further, by further supporting the catalyst on cerium oxide supported on titanium oxide, the contact area between the catalyst and PM can be increased. Therefore, it is thought that PM can be burned efficiently. Further, since titanium oxide has low reactivity with the catalyst component, the catalyst is hardly deteriorated. Therefore, the catalytic activity can be sufficiently exhibited.

  According to a second aspect of the present invention, the metal oxide is any one of V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sn, and Pb. The exhaust gas purifying filter according to claim 1, comprising a metal.

  Thereby, the exhaust gas purification filter can exhibit excellent PM purification ability.

  The invention according to claim 3 of the present invention is the exhaust gas purification filter according to claim 1 or 2, wherein the metal oxide is an oxide of V, Mn, Cu and / or a composite oxide. It is.

  Thereby, the exhaust gas purification filter can exhibit excellent PM purification ability.

  The invention according to claim 4 of the present invention is the exhaust gas purifying filter according to any one of claims 1 to 3, wherein the sulfate is cesium sulfate.

  Thereby, the exhaust gas purification filter can exhibit excellent PM purification ability and heat resistance.

The invention described in claim 5 of the present invention, the three-dimensional structure, cordierite, silicon carbide, characterized in that it is a honeycomb made of any metal, according to any one of claims 1 to 4 This is an exhaust gas purification filter.

  Thereby, the exhaust gas purification filter which is excellent in heat resistance and can collect PM at a high collection rate can be easily obtained.

Examples of the present invention will be described below.
( Reference Example 1)
To 3 L of pure water, 44.7 g of vanadium oxide sulfate, 0.171 g of manganese acetate tetrahydrate, 34.3 g of copper sulfate pentahydrate, 64.6 g of cesium sulfate, 137 g of cerium nitrate hexahydrate, Was dissolved to prepare an aqueous solution containing a catalyst component.

  Next, a cordierite wall-through honeycomb having a diameter of 5.66 inches, a height of 6 inches, and a cell density of 200 cells / square inch (hereinafter referred to as a honeycomb) is impregnated in the prepared aqueous solution for 5 minutes and then pulled up. The excess aqueous solution was removed by shaking. Next, the honeycomb was immersed in liquid nitrogen to freeze the attached aqueous solution, and then dried using a vacuum freeze-drying apparatus. Next, the honeycomb was fired at 900 ° C. for 5 hours in an air atmosphere by using an electric furnace to manufacture an exhaust gas purification filter carrying an exhaust gas purification catalyst.

  As a result, an exhaust gas purification filter carrying V, Mn, Cu oxides and composite oxides, cesium sulfate, and cerium oxide was easily obtained.

  The coexistence of oxides and composite oxides of V, Mn, and Cu and cesium sulfate improves the catalytic activity of the oxides and composite oxides, and the catalyst has excellent heat resistance. Therefore, the exhaust gas purification filter carrying these can exhibit excellent PM purification ability and heat resistance.

  In addition, cerium oxide coexists with oxides and composite oxides of V, Mn, Cu, and cesium sulfate, so that oxygen is supplied when the oxygen concentration in the exhaust gas is low, thereby helping combustion of PM. Can do.

  Moreover, by freeze-drying, movement of the catalyst component is suppressed during the drying process, and the catalyst can be uniformly supported on the honeycomb. Therefore, an exhaust gas purification filter having excellent PM purification ability and heat resistance can be obtained.

In Reference Example 1, V, Mn, and Cu were used as metals contained in the metal oxide, but other than these, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Zn, Ga, Sn, and Pb Any metal may be used.

Further, in Reference Example 1, cesium sulfate was used as the sulfate, but in addition to this, sulfate and / or Be, Mg, Ca, which is composed of a metal belonging to any one group of Li, Na, K, and Rb. A sulfate composed of a metal belonging to Group 2 of either Sr or Ba may be used.

In Reference Example 1, cerium oxide was used as a cocatalyst having oxygen storage capacity. However, for example, a solid solution of cerium oxide and lanthanum oxide may be used as the rare earth element oxide.

In Reference Example 1, a cordierite wall-through honeycomb is used as the three-dimensional structure, but a honeycomb made of metal such as silicon carbide or stainless steel may also be used.

In Reference Example 1, the honeycomb was immersed in liquid nitrogen during freeze-drying, but other cooling methods may be used as long as the aqueous solution containing the catalyst component adhering to the honeycomb can be quickly frozen.
(Example 1 )
42 g of polycarboxylic acid type polymer surfactant was dissolved in 4 L of pure water, and then 186 g of titanium oxide powder carrying cerium oxide was added with stirring to prepare a suspension. In the powder of titanium oxide supporting cerium oxide, cerium oxide is contained in an amount of 10 mol% of titanium oxide.

Next, a honeycomb having the same specifications as that used in Reference Example 1 was impregnated in the prepared suspension for 10 minutes, pulled up, and then air blown to remove excess liquid. Next, the honeycomb was dried at 300 ° C. using an electric furnace. After repeating the steps from impregnation into the suspension to drying four times, the honeycomb was fired at 600 ° C. for 5 hours in an air atmosphere using an electric furnace.

  Next, 790 g of vanadium oxide sulfate, 3 g of manganese acetate tetrahydrate, 600 g of copper sulfate pentahydrate, and 1140 g of cesium sulfate were dissolved in 3 L of pure water to prepare an aqueous solution containing a catalyst component.

  Next, the fired honeycomb was impregnated with the prepared aqueous solution for 5 minutes, pulled up, and then shaken to remove excess aqueous solution. Next, the honeycomb was immersed in liquid nitrogen to freeze the attached aqueous solution, and then dried using a vacuum freeze-drying apparatus. Next, the honeycomb was fired at 700 ° C. for 5 hours in an air atmosphere by using an electric furnace to manufacture an exhaust gas purification filter carrying an exhaust gas purification catalyst.

  The titanium oxide supporting cerium oxide supported on the honeycomb was 6.9% of the weight of the honeycomb. Further, the catalyst supported on the honeycomb was 18% of the weight of the honeycomb.

  As a result, an exhaust gas purification filter in which titanium oxide supporting cerium oxide was previously supported, and oxides and composite oxides of V, Mn, Cu, and cesium sulfate were supported thereon.

  The coexistence of oxides and composite oxides of V, Mn, and Cu and cesium sulfate improves the catalytic activity of the oxides and composite oxides, and the catalyst has excellent heat resistance. Therefore, the exhaust gas purification filter carrying these can exhibit excellent PM purification ability and heat resistance.

  In addition, cerium oxide coexists with oxides and composite oxides of V, Mn, Cu, and cesium sulfate, so that oxygen is supplied when the oxygen concentration in the exhaust gas is low, thereby helping combustion of PM. Can do.

  In addition, titanium oxide supporting cerium oxide is supported in advance, and oxides and composite oxides of V, Mn, Cu, and cesium sulfate are supported thereon, thereby suppressing deterioration of the catalyst due to heat. be able to. At the same time, the contact area between the catalyst and PM increases, and PM can be burned efficiently. At the same time, oxides and composite oxides and cesium sulfate are supported on the surface more easily and come into contact with PM, and therefore PM can be burned efficiently.

  Further, since titanium oxide has low reactivity with the catalyst component, the catalyst is hardly deteriorated. Therefore, the catalytic activity can be sufficiently exhibited.

  Further, since cerium is supported as cerium oxide before supporting the catalyst component, the firing temperature after supporting the catalyst component may be lower. Therefore, deterioration of the catalyst is suppressed, and the catalytic activity can be sufficiently exhibited.

  Moreover, by freeze-drying, movement of the catalyst component is suppressed during the drying process, and the catalyst can be uniformly supported on the honeycomb. Therefore, an exhaust gas purification filter having excellent PM purification ability and heat resistance can be obtained.

In Example 1 , V, Mn, and Cu were used as the metals contained in the metal oxide. However, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Zn, Ga, Sn, and Pb were also used. Any metal may be used.

Further, in Example 1 , cesium sulfate was used as a sulfate, but in addition, a sulfate composed of a metal of any one of Li, Na, K, and Rb and / or Be, Mg, Ca, A sulfate composed of a metal belonging to Group 2 of either Sr or Ba may be used.

Further, in Example 1 , titanium oxide supporting cerium oxide was used as a cocatalyst having oxygen storage capacity, but other rare earth element oxides supported on inorganic oxides include, for example, cerium oxide and lanthanum oxide. Alternatively, a titanium oxide supporting a solid solution of cerium oxide, a solid solution of cerium oxide and zirconium oxide, or the like may be used.

In Example 1 , a cordierite wall-through honeycomb is used as the three-dimensional structure, but a honeycomb made of metal such as silicon carbide or stainless steel may also be used.

In Example 1 , the honeycomb was immersed in liquid nitrogen during freeze-drying, but other cooling methods may be used as long as the aqueous solution containing the catalyst component adhering to the honeycomb can be quickly frozen.
(Evaluation example 1)
Using the exhaust gas purification filter of Example 1 , the following exhaust gas test was conducted.

  The exhaust gas test conducted will be described with reference to FIG.

  A diesel engine 1 having a displacement of 3431 cc was used, a switching valve 2 was provided on the exhaust line from the diesel engine 1, a bypass line 3 and a main line 4 were installed, and an exhaust gas purification filter 5 was installed on the main line 4 side.

  While exhausting to the bypass line 3, the diesel engine 1 was operated for 1 hour at 1500 rpm and a torque of 21 kg. After the exhaust became stable, exhaust gas was introduced into the main line 4 where the exhaust gas purification filter 5 was installed by the switching valve 2. The engine speed was maintained at 1500 rpm, and the exhaust gas temperature was increased from 250 ° C. to 490 ° C. in increments of 30 ° C. by changing the load on the diesel engine 1. Each exhaust gas temperature was maintained for 20 minutes, and the pressure sensor 6 was used to measure the differential pressure across the exhaust gas purification filter 5. Further, the oxygen concentration of the exhaust gas flowing into the exhaust gas purification filter 5 was measured using the oxygen sensor 7.

  As the PM is collected by the exhaust gas purification filter 5, the differential pressure across the exhaust gas purification filter 5 increases, but as the exhaust gas temperature rises, the catalytic activity increases, and the collected PM burns. By doing so, the differential pressure before and after the exhaust gas purification filter 5 becomes small. From the acquired differential pressure profile, the differential pressure change rate per unit time at each temperature is obtained, and the temperature when the differential pressure change rate becomes zero is defined as BPT (Balance Point of Temperature), and the lower the BPT is, the lower the BPT is. The PM purification ability of the exhaust gas purification filter is assumed to be excellent. The results are shown in FIG.

  The estimated BPT was 328 ° C., and it was confirmed that the exhaust gas purification filter of Example 2 had an excellent PM purification capacity.

  Moreover, the oxygen concentration of the exhaust gas flowing into the exhaust gas purification filter 5 is shown in FIG.

  The oxygen concentration decreased with increasing exhaust gas temperature, and was below 10% at 430 ° C. Further, it is presumed that the oxygen concentration was further reduced locally during PM combustion. However, the differential pressure change rate was maintained at 0 or less at an exhaust gas temperature of 328 ° C. or higher. Therefore, it was confirmed that the exhaust gas purification filter of Example 2 could burn and remove PM at about the exhaust gas temperature even when the oxygen concentration in the exhaust gas was low.

  The exhaust gas purification filter of the present invention is useful because it has excellent heat resistance and can burn and remove PM at about the exhaust gas temperature even when the oxygen concentration in the exhaust gas is low. Exhaust gas purification is applicable not only to automobiles but also to construction machines, generators, forklifts, cultivators, ships, etc. and can be applied.

The figure which shows the outline | summary of the exhaust gas test of the evaluation example 1 of this invention The figure which shows the result of the exhaust gas test of the evaluation example 1 of this invention The figure which shows the oxygen concentration in the exhaust gas test of the evaluation example 1 of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Diesel engine 2 Switching valve 3 Bypass line 4 This line 5 Exhaust gas purification filter 6 Pressure sensor 7 Oxygen sensor

Claims (5)

It is composed of a metal oxide and a sulfate composed of a group 1 metal of Li, Na, K, Rb, or Cs and / or a group 2 metal of any of Be, Mg, Ca, Sr, or Ba. And a promoter having an oxygen storage capacity is supported on a heat-resistant three-dimensional structure, and the promoter having an oxygen storage capacity is cerium oxide supported on titanium oxide. Exhaust gas purification filter. The metal oxide contains any metal selected from V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sn, and Pb. The exhaust gas purification filter according to 1. The exhaust gas purification filter according to claim 1 or 2, wherein the metal oxide is an oxide of V, Mn, Cu and / or a composite oxide. The exhaust gas purification filter according to any one of claims 1 to 3, wherein the sulfate is cesium sulfate. The exhaust gas purification filter according to any one of claims 1 to 4 , wherein the three-dimensional structure is a honeycomb made of any one of cordierite, silicon carbide, and metal.

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