JP4678596B2 - Exhaust purification device and exhaust purification system - Google Patents

Description

  The present invention relates to an exhaust purification device for purifying particulate matter containing soot discharged from an internal combustion engine such as a diesel engine, and more particularly, exhaust purification capable of purifying soot contained in particulate matter in exhaust gas from a low temperature range. The present invention relates to an apparatus and an exhaust purification system.

  As for gasoline engines, harmful components in the exhaust are steadily reduced due to strict regulations on exhaust and technological advances that can cope with it. However, for diesel engines, the toxic components are discharged as particulates (particulate matter: sulfur fine particles such as soot composed of carbon fine particles, sulfate, soluble organic components (SOF), etc., hereinafter referred to as PM)) Therefore, many technical problems for exhaust purification remain.

  Known exhaust gas purification devices for diesel engines that have been developed so far include, for example, a trap type exhaust gas purification device (wall flow) and an open type exhaust gas purification device (straight flow). Among these, as a trap type exhaust purification device, a ceramic plug-type honeycomb body (diesel PM filter (hereinafter referred to as DPF)) is known. This DPF is formed by alternately sealing both ends of the openings of the cells of the ceramic honeycomb structure, for example, in a checkered pattern, adjacent to the inflow side cells clogged on the exhaust downstream side and the inflow side cells. It consists of an outflow side cell clogged upstream of the exhaust, and a filter partition that separates the inflow and outflow cells, and suppresses exhaust by filtering the exhaust through the pores of the filter partition and collecting PM. To do.

  However, in the DPF, pressure loss (hereinafter referred to as pressure loss) increases due to the accumulation of PM. Therefore, it is necessary to periodically remove and regenerate PM accumulated by some means. Therefore, conventionally, when pressure loss increases, so-called forced regeneration is performed in which PM is spontaneously combusted and DPF is regenerated by flowing high-temperature exhaust that causes PM to oxidize spontaneously or by heating with a heater. Has been done. However, in this case, since PM burns spontaneously, the temperature control of the DPF becomes impossible, the temperature rises excessively, and the DPF may be melted or damaged due to thermal stress.

Therefore, in recent years, an exhaust purification device in which an oxidation catalyst is disposed on the upstream side of the DPF has been used. For example, Japanese Laid-Open Patent Publication No. 01-318715 (Patent Document 1) discloses an exhaust purification device in which an oxidation catalyst is disposed on the upstream side of a DPF, and Japanese Patent Laid-Open No. 2002-502927 (Patent Document 2) and Special Table 2004-451191. Japanese Patent Publication (Patent Document 3) discloses an exhaust purification device using both an oxidation catalyst and a NO _x selective reduction catalyst using NH ₃ . According to these purification apparatuses, it is possible to oxidize and remove PM collected in the DPF by NO ₂ generated from NO by the oxidation catalyst.

The technologies described in Patent Document 2 and Patent Document 3 are both technologies that generate NO ₂ upstream of the DPF and purify PM by the oxidizing power of NO ₂ . Therefore, a catalyst using a noble metal is required to oxidize NO, and there is a problem in terms of cost. And engine conditions are not necessarily advantageous for the generation of NO ₂ . Moreover, in order to reduce forced regeneration as much as possible, it is necessary to actively generate NO ₂ . In this case, it is difficult to control the NO ₂ concentration. Further, even if NO ₂ control is actually performed, it is not always possible to completely purify PM. Furthermore, it becomes necessary to suppress the emission of NO _x.

  Therefore, the use of Ce can be considered. The temperature at which only soot is oxidized is about 600 ° C., but it is known that the oxidation temperature is significantly lowered when the contact between the ceria powder and the soot is increased. As a technique using Ce, for example, SAE2002-01-0436 (Non-Patent Document 1) discloses a method of adding Ce to fuel, and describes that soot can be burned at about 350 ° C. . Moreover, as such an additive, what was described in Japanese translations of PCT publication No. 11-501609 (patent document 4) is also known.

However, in the method of adding Ce to the fuel, the added Ce is accumulated in the filter as CeO ₂ , but does not promote the oxidation of the soot deposited on the filter, and in fact, forced regeneration must be frequently performed. Arise. Thus, when the fuel to which Ce is added burns in the combustion chamber, contact with the soot produced at the same time is ensured to some extent, so that some effects can be seen, but the performance of CeO ₂ can be fully exploited. The current situation is not possible.

  In JP 2002-227688 A (Patent Document 5) or JP 2002-213229 A (Patent Document 6), exhaust of a rich atmosphere is allowed to flow until the temperature of the deposited PM rises to a natural combustion temperature. It describes the control of flowing exhaust gas in a lean atmosphere after reaching that temperature. Although this technique burns the reducing component by flowing exhaust gas in a rich atmosphere and quickly raises the temperature using the generated heat, there is a problem that fuel consumption deteriorates. Further, PM cannot be oxidized while the atmosphere is rich. Furthermore, since the lean atmosphere is set after the temperature rise, there is a case where PM spontaneously burns in the same manner as the forced regeneration described above, the temperature cannot be controlled, the temperature rises excessively, and the base material is melted. Problems arise.

On the other hand, from the viewpoint of achieving both PM purification and NO _x , HC, and CO purification, it is mainly a challenge to achieve both NO _x purification. As a technology for purifying NO _x under a lean atmosphere, a technology for selectively reducing NO _x with NH ₃ , a NO _x absorption / release material is used to absorb NO _x in a lean atmosphere, and NO _x is released in a rich atmosphere. Techniques for reduction are known. Examples of techniques for selectively reducing NO _x with NH ₃ and simultaneously purifying PM include Patent Document 2 and Patent Document 3 described above. In order to purify NO _x in addition to PM, it is necessary to control the addition of urea or NH ₃ , so that NO ₂ is generated almost continuously and soot is continuously oxidized to reduce forced regeneration as much as possible. If it does so, it will be very complicated control including engine control.

Furthermore, as known techniques for using Ag added to ceria for PM purification, JP-A-10-151348 (Patent Document 7), JP-A-2004-042021 (Patent Document 8), and the like are known. Among these, in Patent Document 7 by the present applicants, the addition of La, Y, Pr, and Zr to ceria promotes the movement of oxygen in the cerium oxide. It is disclosed that it is further promoted. Further, it is disclosed that the combustion temperature of PM can be further lowered by further supporting Ag as a catalyst component, and the contribution to the activation of oxygen is disclosed as the reason for the reduction of the PM oxidation temperature by the combination of ceria and Ag. Has been. Further, as the ceria in this case, ceria having a high specific surface area of 50 to 300 m ² / g is desirable, and the supported amount of Ag is 1 to 50% by weight (in mol% with respect to Ce and Ag, Ag: 1.6 mol% to (Corresponding to 61.64 mol%) is also preferred.

On the other hand, Patent Document 8 discloses that a catalyst composition having ceria stabilized with Ag and / or Co promotes soot oxidation during regeneration of DPF, and the molar ratio of Ag to ceria is 4: 1. ˜1: 4 (corresponding to 20% by mole to 80% by mole in terms of mol% with respect to Ce and Ag), preferably 3: 1 to 1: 3 (in terms of mol% with respect to Ce and Ag, Ag: 33 mol% to 67 mol%) Equivalent). Among them, Ag: 75 mol% has the maximum activity in the TGA evaluation by loose-contact. This indicates that this catalyst composition generates active oxygen species in the gas phase. Further, according to this catalyst production method, a cellulose material (Whatman filter paper # 540) is impregnated with a nitrate precursor, dried at room temperature overnight, and then burned at 600 ° C. for 2 hours to obtain about 70 can produce a composition having a high specific surface area of concentrated porosity and 14~150m ² / g to about ~200Å, Ag: in the case of 75 mol% composition is described to be a specific surface area of ^{10 m} 2 / g Yes.

  There are mainly two evaluation methods in Patent Document 8, one is a method of measuring the decomposition rate by TGA in a 10% oxygen atmosphere, etc., in which the diesel soot and the catalyst composition are loosely contacted with a spatula, and the other is by DPF. This is a method of performing a pressure loss balance test.

In the TGA evaluation of the catalyst having a composition of Ag: 75 mol%, as shown in Table 14 of Patent Document 8, the oxidation rate at 323 ° C. even under the best catalyst composition of NO ₂ : 1010 ppm and O ₂ : 10%. Is 0.117 hr ⁻¹ . That is, even under the condition that a strong oxidant of NO ₂ is sufficiently present, the ratio of soot oxidized in one hour is only 11.7%. On the other hand, in the pressure loss balance test of FIG. 3 in the same document, it is supposed that PM can be substantially oxidized in the vicinity of 325 ° C. in CPF-15 which is an Ag—Ce system. Thus, the results of both tests contradict each other, and in the actual pressure loss balance test, there is a possibility that the soot component slips out due to oxidation of SOF or the like.
Japanese Patent Laid-Open No. 01-318715 Japanese translation of PCT publication No. 2002-502927 Japanese translation of PCT publication No. 2004-511691 Japanese National Patent Publication No. 11-501609 JP 2002-227688 A JP 2002-213229 A JP-A-10-151348 JP 2004-042021 A SAE2002-01-0436

The present invention has been made in view of the above circumstances, and the soot from the low temperature range can continuously oxidized, it is easy to control for PM oxidation, also simultaneously purified harmful components such as NO _x together It is an object of the present invention to provide an exhaust purification device and an exhaust purification system that can be used.

The feature of the exhaust emission control device of the present invention that solves the above problems is
A base material capable of collecting particulate matter discharged from an internal combustion engine;
Present on the included in the substrate or the base material, an acidic compound adsorption means for adsorbing acidic compounds,
An acidic compound desorbing means for an acidic compound adsorbed on the acidic compound adsorption means desorb,
Tona is, and,
The acidic compound adsorption means is obtained by baking the precipitate after obtaining a precipitate in the presence of a base from a solution containing Ce and Ag, and the ratio of Ag to the total amount of Ce and Ag is 35-60. A composition containing ceria that is mol%, or ceria obtained by impregnating ceria into a solution containing Ag and calcining, and the ratio of Ag to the total amount of Ce and Ag is 10 to 40 mol% A composition comprising
It is in.

Further, the feature of the exhaust purification system of the present invention is that
An exhaust emission control device of the present invention;
Detecting means for detecting a physical quantity related to at least one selected from the temperature of the base material, the amount of soot in the exhaust gas flowing into the base material, and the amount of soot deposited on the base material;
Control means for controlling the driving of the acidic compound detachment means based on the detection value of the detection means;
It is in having.

According to the exhaust gas purification apparatus and the exhaust gas purification system of the present invention, soot can be continuously oxidized from a low temperature range at low cost by positively desorbing acidic compounds. Therefore, when the filter device is used as the base material, the filter device can be continuously regenerated, so that forced regeneration is unnecessary or the number of times can be greatly reduced. Furthermore, problems such as melting damage of the filter device can be avoided, and an increase in pressure loss can also be suppressed. In addition to the soot, it is possible to simultaneously purify HC, CO, SOF, and NO _x by further disposing a NO _x purification material, an oxidation catalyst, and the like.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

As described in the background art, it is known that when the contact between the ceria powder and the soot is increased, the oxidation temperature is remarkably lowered. When 625 ppm of the Ce compound is added to the fuel, the temperature continuously exceeds 350 ° C. It can be reproduced (Non-Patent Document 1). In the filter, the added Ce should be oxidized and accumulated at the ash level as CeO ₂ , but just like the case of applying CeO ₂ to the filter, it alone oxidizes the deposited soot. It is not possible.

Therefore, the present inventors have intensively studied by recalling that active oxygen typified by oxygen of CeO ₂ is efficiently used for soot oxidation. Then, it was not sufficient to simply bring soot and CeO ₂ into physical contact with each other, and attention was paid to the fact that soot oxidation performance was dramatically improved by chemically interacting. As a result, in the oxidation process of soot, it was considered that the carbon atom network on the surface of the soot was cut by oxygen atoms, or bonds between carbon atoms and oxygen atoms were formed, and CO and CO ₂ were gradually formed. Then, the carbon and oxygen atoms on the surface of the soot are extracted as CO or CO ₂ , and the CO and CO ₂ are actively released out of the system, soot oxidation is promoted and supplied from CeO ₂ or the like. The present inventors have found that soot can be continuously oxidized from a low temperature region by effectively using the active oxygen produced.

  That is, the exhaust emission control device of the present invention includes a base material capable of collecting particulate matter discharged from an internal combustion engine, an acidic compound adsorption unit, and an acidic compound desorption unit. As the substrate, a honeycomb substrate having a straight flow structure used for a conventional catalyst, or a honeycomb filter or a foam filter used as a DPF can be used. As the material, cordierite, SiC, SiN, metal or the like is used.

The acidic compound refers CO produced by the oxidation of soot, CO _2, and CO discharged from the internal combustion engine, CO ₂ and NO _x and the like. In general terms, CO is not included in the acidic compound, but when oxidized to CO _2, it becomes an acidic compound, and in this specification, the acidic compound includes CO.

The acidic compound adsorbing means contained in or existing on the base material is temporary CO, CO ₂ produced by soot oxidation and CO, CO ₂ and NO _x exhausted from the internal combustion engine. Refers to a substance that easily adsorbs acidic compounds adsorbed by acidic compound desorption means described later, alkaline metals such as lithium, sodium and potassium, alkaline earth metals such as barium, calcium and magnesium, Alternatively, a composition containing a basic oxide such as ceria or zirconia is desirable. Among these, those having oxygen absorption / release capability such as complex oxides containing ceria and ceria-zirconia solid solutions are desirable, complex oxides containing ceria are more desirable, and complex oxides containing ceria and alumina are particularly desirable. This is because soot oxidation is promoted by the released active oxygen, and itself absorbs oxygen in the lean atmosphere to restore the oxygen releasing ability. Depending on the amount or temperature of oxygen in the atmosphere, the soot may be efficiently oxidized and purified even if the acidic compound adsorbing means does not have the ability to absorb and release oxygen.

  The oxygen absorbing / releasing capability is preferably higher in surface oxygen capability than in bulk capability. For example, when the acidic compound detachment agent is a reducing component, it is possible to suppress consumption of the acidic compound detachment agent by the supplied oxygen by using a material having a high oxygen releasing ability as surface oxygen. it can. For example, the ceria-zirconia solid solution has a high oxygen storage / release capacity as a bulk, but in the present invention, it is preferable to use ceria which is inferior in the oxygen storage / release capacity as a bulk.

  Furthermore, by using an acidic compound adsorption means, it is possible to prevent thermal runaway when a large amount of particulate matter unexpectedly accumulates on the substrate and spontaneous oxidation starts. This is because by receiving the heat of spontaneous oxidation, a large amount of the acidic compound adsorbed on the acidic compound adsorbing means is desorbed, and the supply of oxygen to the particulate matter can be blocked.

  If the base material itself is configured to contain a basic oxide, the base material can also serve as the acidic compound adsorption means, but in general, the acidic compound adsorption means is supported on the inner peripheral surface of the exhaust passage of the base material. Used. In order to do this, a basic oxide that serves as an acidic compound adsorption means may be coated on the inner peripheral surface of the exhaust passage, or a basic oxide that serves as an acidic compound adsorption means may be coated on a pre-formed coating layer. You may carry. The material of the coating layer is not particularly limited, such as alumina, magnesia, ceria, zirconia, titania, silica, and may be a basic oxide that serves as an acidic compound adsorption means as described above, or an acidic oxide. May be. This is because if the coat layer is formed of an acidic oxide, the acidic compound generated by the soot oxidation is preferentially adsorbed by the acidic compound adsorbing means without being adsorbed by the coat layer.

The amount of the acidic compound adsorbing means is not particularly limited, but is preferably 10 g or more per 1 L of the base material volume capable of collecting the particulate matter. If the amount of the acidic compound adsorption means is less than this, the amount of adsorption of acidic compounds such as CO and CO ₂ will be insufficient, and it will be difficult to promote the soot oxidation. Moreover, it is preferable that the quantity of an acidic compound adsorption | suction means shall be 200 g or less per 1 L of volumes of a base material. This is because if it exceeds this, the pressure loss tends to increase, which affects the operation of the internal combustion engine.

  The acidic oxide is generated by the oxidation of soot and discharged from the internal combustion engine. In the present invention, since the acidic compound adsorbing means is arranged together with the base material capable of collecting particulate matter containing soot, it can be preferentially adsorbed when an acidic compound is produced by soot oxidation. .

The acidic compound desorbing means means means for desorbing the acidic compound adsorbed on the acidic compound adsorbing means, and examples thereof include a heating means for heating the reaction system and an acidic compound desorbing agent. As a heating means, there are a method of heating with an electric heater, and a method of increasing the exhaust temperature by performing post injection. However, since a large amount of CO ₂ or HC is generated in the method of post injection, a method using an acidic compound desorbing agent or a method using an electric heater is desirable. The heating temperature by the heating means varies depending on the material of the acidic compound adsorption means. For example, when ceria is used as the acidic compound adsorption means, the adsorbed acidic compound can be desorbed by heating to 300 ° C. or higher. Further, even if the conditions in which soot is frequently generated continue, it can be desorbed by heating up to 350 ° C., so there is no problem with the engine. Furthermore, it is advantageous compared to the method of adding Ce to the fuel.

An acidic compound can be used as the acidic compound detaching agent. In this case, the acidic compound used as the acidic compound desorbing agent will be adsorbed by the acidic compound adsorbing means, so that the acidic compound can be desorbed by using another acidic compound desorbing agent. It is preferable that the acidic compound produced by soot oxidation is easily adsorbed. For example, when CO ₂ is adsorbed on the acidic compound adsorbing means, it is possible to desorb CO ₂ using NO _x that is an acidic compound, and the adsorbed NO _x is desorbed from the acidic compound. It can be eliminated by using NH ₃ or the like as an agent.

As the acidic compound desorbing agent, a gas containing a large amount of N ₂ can be used, but a gas such as H ₂ or NH ₃ is particularly preferable. These gases easily desorb the acidic compound adsorbed on the acidic compound adsorption means from the acidic compound adsorption means. Above all, when NH ₃ is used, the acidic compound can be eliminated particularly easily because it is basic. Although it is possible to desorb even by flowing a rich atmosphere exhaust gas containing a large amount of HC, since such exhaust gas contains a large amount of CO and CO ₂ , the action of the acidic compound adsorption means It is not preferable from the aspect.

For example in the case of using NH ₃ as the acidic compound release agent, to the NH ₃ may be added directly into the exhaust gas, it is also possible to use a NH ₃ source, such as urea. When urea is used, it may be added to the exhaust gas as an aqueous solution or a sublimation gas. Further, NH ₃ may be generated from the exhaust using a three-way catalyst or the like. H ₂ can also be generated from the exhaust by a steam reforming reaction, a CO shift reaction, or the like.

The timing of desorbing the acidic compound adsorbed on the acidic compound adsorbing means may be performed continuously or before the adsorption amount of the acidic compound adsorbing means is saturated. Further, when NH ₃ is used as the acidic compound desorbing agent and a NO _x selective reduction catalyst is used as the NO _x purification material, control for NO _x purification may be performed. Furthermore, when supplying an acidic compound desorbing agent, it is preferable to perform adsorption and desorption continuously because the acidic compound can be desorbed simultaneously with the contact of the acidic compound desorbing agent. This can be done by supplying the acidic compound desorbing agent continuously or intermittently into the exhaust and bringing it into contact with the acidic compound adsorption means. Even in this case, the acidic compound produced by the surface oxidation of the soot does not react with the acidic compound desorbing agent, but is first adsorbed to the acidic compound adsorbing means, and almost simultaneously from the acidic compound adsorbing means by the acidic compound desorbing agent. Detach. Therefore, the soot can be continuously oxidized and purified.

  The acidic compound desorption means can be always driven, but it should be driven flexibly according to the temperature of the substrate, the amount of soot flowing into the substrate, the amount of soot deposited on the substrate, etc. Is desirable. Therefore, the exhaust purification system of the present invention relates to the exhaust purification system of the present invention and at least one selected from the temperature of the base material, the amount of soot in the exhaust gas flowing into the base material, and the amount of soot deposited on the base material. Detection means for detecting the physical quantity, and control means for controlling the driving of the acidic compound detachment means based on the detection value of the detection means.

  The detection means is means for detecting a physical quantity related to at least one selected from the temperature of the base material, the amount of soot in the exhaust gas flowing into the base material, and the amount of soot deposited on the base material. Examples of the physical quantity related to the temperature of the substrate include the temperature of the substrate itself and the temperature of exhaust gas. In order to detect the exhaust gas temperature, the exhaust gas temperature may be detected directly, or the exhaust gas temperature may be estimated from the operating state of the engine and the air temperature.

  In order to detect the amount of soot in the exhaust, it can be estimated from the operating state of the engine. Alternatively, it can be detected by measuring the transparency of the exhaust. The amount of deposited soot can be estimated by measuring the pressure difference between the exhaust gas on the inlet side and the outlet side of the substrate. Alternatively, it is possible to calculate from the load status of the engine.

  The control means controls the driving of the acidic compound detachment means based on the detection value of the detection means, and it is preferable to use a computer, but it can also be controlled mechanically.

The exhaust purification device and the exhaust purification system of the present invention preferably include soot oxidation promoting means for promoting soot oxidation. As this soot oxidation promoting means, means for supplying an oxidant such as NO ₂ and ozone to the exhaust, means for oxidizing NO in the exhaust to NO ₂ and supplying it to the exhaust, such as an oxidation catalyst, or ceria, Fe ₂ O ₃ Examples thereof include oxygen storage / release materials such as zirconia. In these means, it is not always necessary to completely oxidize soot, and it is possible to partially oxidize soot. For example, since NO ₂ and ozone can oxidize the surface of soot at a low temperature, soot oxidation can be further promoted when used in combination with the present invention.

  If an oxygen storage / release material such as ceria is used as the acidic compound adsorption means, the acidic compound adsorption means also serves as the soot oxidation promotion means. Moreover, the thing which added yttrium to zirconia improves the oxygen absorption / release action by stabilizing the crystal structure. Similarly, a material obtained by adding Ag, Fe, Co, Y, Pr, Nd, Sm, Eu, Gd, Tb or the like to ceria is also useful as a soot oxidation promoting means. As such an acidic compound adsorbing means that also serves as a soot oxidation promoting means, one in which at least one of Ag, Fe, Pr, and Co is added to ceria is more preferable, and one in which Ag is added to ceria is particularly preferable. Further, it is more preferable that Al is contained in such ceria (preferably high specific surface area ceria).

  As a preparation method of the acidic compound adsorption means using such a composition containing ceria, the following preparation method (i) or preparation method (ii) is preferable.

Preparation method (i) <Precipitation method>
Precipitation was carried out in the presence of a base (eg, ammonia) from a solution containing Ce and other raw metal (eg, nitrate solution), and the resulting precipitate was calcined to add other metals to ceria. An acidic compound adsorption means is obtained. In addition, it is preferable to perform an aging treatment when generating the precipitate, since dissolution / reprecipitation is promoted by heating heat and growth of precipitated particles occurs. Such aging treatment is performed at room temperature or higher, preferably 100 to 200 ° C, more preferably 100 to 150 ° C. When the aging temperature is less than 100 ° C., the effect of promoting aging is small, and the time required for aging tends to be long. On the other hand, when the aging temperature is higher than 200 ° C., the decomposition rate of the oxide precursor may increase, so that the firing temperature for obtaining an oxide tends to be unfavorable.

  When obtaining an acidic compound adsorption means in which Ag is added to ceria by such a preparation method (i), the ratio of Ag to the total amount of Ce and Ag (molar basis) is preferably 35 to 60%. When the Ag ratio is less than 35%, the soot oxidation ability tends to decrease. On the other hand, when the Ag ratio exceeds 60%, the soot oxidation ability decreases and a large amount of Ag tends to increase, resulting in an increase in cost. is there.

Preparation method (ii) <Support method>
By impregnating ceria with a solution containing a metal as another raw material (for example, a nitrate solution), evaporating to dryness, and further firing, an acidic compound adsorption means in which the other metal is supported on the ceria is obtained. In this case, the ceria, preferably used high specific surface area ceria 50 to 300 m ² / g, it is particularly preferable to use a high specific surface area ceria 100 to 300 m ² / g. When the specific surface area of ceria is less than 50 m ² / g, the soot oxidation ability tends to decrease, and when the specific surface area of ceria exceeds 300 m ² / g, it tends to be difficult to uniformly support other metals such as Ag. is there.

Further, it is more preferable that such ceria contains Al, and it is particularly preferable that Al is supported mainly at least near the surface of the ceria as Al ₂ O ₃ . Thus, when ceria contains Al, it is preferable that the ratio (molar basis) of Al in the total amount of Ce and Al is 10 ppm to 5%, and more preferably 15 ppm to 1%. If the Al content is less than the lower limit, the soot oxidation ability tends to be reduced. On the other hand, if the Al content exceeds the upper limit, other metals such as Ag tend not to be uniformly supported.

  The method for preparing ceria containing Al is not particularly limited. For example, the ceria containing Al can be obtained by impregnating ceria into an Al-containing solution (for example, aluminum nitrate solution), evaporating to dryness, and further firing. can get.

  When obtaining an acidic compound adsorbing means in which Ag is supported on ceria by such a preparation method (ii), the ratio (Mole basis) of Ag in the total amount of Ce and Ag is preferably 10 to 40%. More preferably more than% and less than 20 mol%. When the Ag ratio is less than 10%, the soot oxidation ability tends to decrease. On the other hand, when the Ag ratio exceeds 40%, the soot oxidation ability decreases and a large amount of Ag tends to be required, resulting in an increase in cost. is there.

  In the present invention, it is also preferable to further include contact promoting means for promoting contact between the acidic compound adsorbing means and soot. This contact promoting means is for physically capturing soot to increase the contact probability with the acidic compound adsorbing means. As described in SAE2002-01-0436, it is a means for adding Ce to the exhaust gas at an exhaust temperature. Examples include a molten salt that melts into a liquid phase, or means for alternately performing forward flow and reverse flow in the direction of exhaust gas flowing through the filter device as described in Japanese Patent Application No. 2004-030058. The contact promoting means preferably promotes contact between the soot oxidation promoting means and soot.

  The molten salt is at least one selected from silver carbonate, alkali metal carbonate, alkaline earth metal carbonate, rare earth carbonate, silver halide, alkali metal halide, and alkaline earth metal halide. And / or the thing containing the complex salt which multiple types chosen from these complexed can be used. The amount of the molten salt supported is preferably 1% by weight or more with respect to the solid support constituting the coat layer. If the loading amount is less than this, it becomes difficult to capture the soot. The amount of soot that is captured tends to increase as the loading amount increases. However, if it is supported by 120% by weight or more, the retention on the carrier is insufficient, and it may flow to the downstream and aggregate. It is desirable to do.

In addition, the exhaust purification device and the exhaust purification system of the present invention desirably include HC removal means for removing HC in the exhaust on the exhaust upstream side of the base material. Exhaust gas from which HC and SOF, which are more easily oxidized than soot, are removed in advance flows into the base material, so that the soot can be more easily oxidized and purified. As the HC removal means, an oxidation catalyst, a three-way catalyst, a method using a steam reforming reaction, or an HC adsorbent such as zeolite can be used. Further, if the steam reforming reaction is used, HC is removed and H ₂ is generated, so that this H ₂ can be used as an acidic compound desorbing agent. NH ₃ produced by the reaction between H ₂ and NO _x may be used as the acidic compound desorbing agent. Note that in the case of the oxidation catalyst, need not be particularly oxidation of NO to NO _2.

The exhaust purification device and the exhaust purification system of the present invention preferably also use at least one selected from a three-way catalyst, a NO _x selective reduction catalyst, and a NO _x storage reduction catalyst. This makes it possible to purify HC in addition to the soot, the SOF and NO _x simultaneously. This catalyst is desirably arranged on the exhaust downstream side of the substrate. In this way, it is possible to avoid such a problem that NH ₃ as the acidic compound desorbing agent is oxidized and discharged as NO _x . Further, HC, SOF and NO _x can be simultaneously purified, and an acidic compound desorbing agent can be used for NO _x reduction. And since it is consumed in the reduction of the NO _x can supply many acidic compounds release agent, surely eliminated acidic compounds adsorbed on the acidic compound adsorption means by supplying a large amount of acidic compound release agent And soot oxidation is promoted.

Examples of the NO _x selective reduction catalyst include a Cu-zeolite catalyst, an Fe-zeolite catalyst, and a V ₂ O ₅ / WO ₃ / TiO ₂ catalyst. In addition, as the NO _x storage reduction catalyst, a catalyst in which a noble metal and a NO _x storage material are supported on a support such as alumina can be used.

In addition, in the case of an exhaust emission control device in which NH ₃ is added upstream of the base material and a NO _x selective reduction catalyst is arranged downstream of the base material, exhaust gas is being exhausted between the base material and the NO _x selective reduction catalyst. It is also preferable to add a reducing agent. In this way, it is possible to prevent NH _{3 from} being oxidized to NO _x while performing soot oxidation, and NO _x can be reduced by the NO _x selective reduction catalyst. In this case, since it is necessary to supply the acidic compound desorbing agent or reducing agent to the exhaust system at a plurality of locations, it seems that complicated control is required at first glance, but the control upstream of the substrate is simple. Therefore, it is sufficient to consider mainly the control of the supply of the reducing agent.

Although such a structure seems to be described in Patent Document 3, it is quite misplaced. That is, Patent Document 3 does not show a technical idea for promoting soot oxidation by an acidic compound adsorption means and an acidic compound desorption means. Even in the case of a configuration in which a reducing agent having a configuration similar to that of the present invention is supplied to the upstream side of the DPF (FIGS. 14B and 14C of the same document), the opposite direction to the present invention is disclosed. . That is, as described in paragraph [0066] of the same document, when HC is used as the reducing agent, it can be supplied upstream of the DPF. However, when NH ₃ is used as the reducing agent, NH ₃ is oxidized. In order to prevent NO _x , it is described that it is desirable to supply the downstream side of the DPF as shown in FIG. 14A of the same document. Therefore, the technology that functions NH ₃ as an acidic compound desorption means in the DPF. There is no room to interpret that is disclosed.

  The concept of the operation of the exhaust emission control device of the present invention is shown in FIG. First, as shown in FIG. 1A, the acidic compound formed on the surface of the soot is extracted by the acidic compound adsorption means, and the oxidation of the soot is promoted.

  When soot oxidation is promoted and the acidic compound on the substrate increases as shown in FIG. 1B, the soot oxidation is suppressed. Therefore, an acidic compound detachment means is operated. Then, as shown in FIG. 1C, the acidic compound on the substrate is reduced, and the soot oxidation is promoted again.

  EXAMPLES Hereinafter, although an Example and a test example demonstrate this invention concretely, this invention is not limited to a following example. In this embodiment, the present invention is applied to an exhaust system of a diesel engine of an automobile.

Example 1
FIG. 2 shows the exhaust emission control device of this embodiment. In the exhaust flow path, DPF 1 is arranged in which both ends of the openings of the cells of the ceramic honeycomb structure are alternately plugged in a checkered pattern. In the DPF 1, as shown in FIG. 3, a coating layer 20 made of ceria containing one kind selected from Ag, Pr, and Fe is formed on the surface of the cell partition wall, and the coating layer 20 constitutes the acidic compound adsorption unit 2. . In the vicinity of the DPF 1, a heater 10 is disposed as an acidic compound detachment unit.

  As heating for so-called forced regeneration of the DPF 1, it is common to raise the temperature to 550 ° C. to 600 ° C. at which soot in the PM component spontaneously starts combustion, but by forming the coat layer 20 A temperature rise of 250 to 350 ° C is sufficient. Note that the exhaust temperature of the diesel engine may reach this temperature range without control such as post injection, but in this embodiment, this temperature range is always maintained in order to continuously purify the soot. The heater 10 is controlled.

The coat layer 20 was formed as follows. First, it was prepared _CeO 2 -Ag composition powder according to the test example 1-3 described below.

  This was slurried, introduced from one end face of DPF 1 and then sucked from the other end face to remove excess slurry, and baked at 250 ° C. to form coat layer 20. The formation amount of the coat layer 20 is preferably in the range of 10 g to 200 g per liter of DPF1.

(Test Example 1)
<Preparation by precipitation of _CeO 2 -Ag composition>
The Ag content (mol%) relative to the total amount of Ce and Ag is 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol. %, And a nitrate solution containing Ce and Ag was prepared to be 85 mol%. Note that cerium nitrate hexahydrate was used as the Ce material, and silver nitrate was used as the Ag material. Next, 25% aqueous ammonia containing NH ₃ amount necessary for precipitating the nitrates was prepared. Then, the nitrate solution was mixed while stirring the ammonia water (reverse coprecipitation), or the ammonia water was mixed while stirring the nitrate solution (coprecipitation). In either case, stirring was continued for 10 minutes, and then an aging treatment was performed at 150 ° C. for 2 hours. Then, the obtained precipitate was baked at 500 ° C. for 6 hours in the air to prepare a CeO ₂ —Ag composition made of ceria to which Ag was added.

In the present invention, a composition obtained by using mol% of Ag with respect to (Ce + Ag) in the nitrate solution preparation stage is expressed. For example, the composition obtained by preparing a nitrate solution so that Ag might be 60 mol% was expressed as “CeO ₂ -Ag60” (or “Ce-Ag60”). Moreover, the case where it prepared by the coprecipitation method was shown as "coprecipitation", and the case where it prepared by the reverse coprecipitation method was shown as "reverse coprecipitation".

<Preparation by supporting method of _CeO 2 -Ag composition>
First, a high specific surface area ceria was prepared as follows. That is, 21.06 g of diammonium cerium (V) nitrate was dissolved in 32.06 ml of ion-exchanged water to obtain a cerium salt solution. Next, 200 ml of ion-exchanged water was heated to reflux, and the cerium salt solution was dropped therein over 15 minutes. Thereafter, the obtained precipitate was filtered while being washed with ethanol, and calcined in the atmosphere at 500 ° C. for 5 hours to prepare a high specific surface area ceria. The specific surface area (BET method) of the obtained high specific surface area ceria was 150 m ² / g. The high specific surface area ceria thus obtained was designated as “high specific surface area CeO ₂ ”.

Next, a high specific surface area CeO ₂ containing Al was prepared as follows. That is, 100 g of the high specific surface area CeO ₂ was impregnated in an aluminum nitrate aqueous solution having a concentration of 0.05 mol / l, evaporated to dryness, and further baked at 500 ° C. for 5 hours in the atmosphere to contain Al. A high specific surface area CeO ₂ was prepared. The Al content (mol%) of the obtained high specific surface area ceria was 0.05 mol%. The high specific surface area CeO ₂ containing Al thus obtained was indicated as “Al-containing high specific surface area CeO ₂ ”.

Next, an Al-containing high specific surface area CeO ₂ supporting Ag was prepared as follows. That is, 10 g of the Al-containing high specific surface area CeO ₂ was impregnated in an aqueous silver nitrate solution having a concentration of 1.0 mol / l, evaporated to dryness, and further baked at 500 ° C. for 5 hours in the atmosphere, whereby Ce and Ag Al-containing high specific surface area CeO ₂ on which Ag was supported was prepared such that the Ag content (mol%) was 5 mol%, 10 mol%, 15 mol%, 20 mol%, and 30 mol% with respect to the total amount. The thus obtained Al-containing high specific surface area CeO ₂ having an Ag content (mol%) of 15 mol% was indicated as “Ag (15) / Al-containing high specific surface area CeO ₂ (85)”.

Further, Ag was supported in the same manner as described above except that the high specific surface area CeO ₂ was used instead of the Al-containing high specific surface area CeO ₂ , and the Ag content (mol%) relative to the total amount of Ce and Ag was 15 mol. % High specific surface area CeO ₂ on which Ag was supported was prepared. The high specific surface area CeO ₂ having the Ag content (mol%) of 15 mol% thus obtained was indicated as “Ag (15) / high specific surface area CeO ₂ (85)”.

Further, Ag was supported in the same manner as described above except that ceria having a specific surface area of 55 m ² / g synthesized by a precipitation method was used instead of the Al-containing high specific surface area CeO ₂ , and the Ag content relative to the total amount of Ce and Ag was increased. Ceria carrying Ag was prepared so that the content (mol%) was 10 mol%, 20 mol%, and 30 mol%. The ceria thus obtained with an Ag content (mol%) of 20 mol% was designated as “Ag (20) / CeO ₂ (80)”.

<Test>
CeO ₂ -Ag compositions of various compositions prepared by the above-described production method were used and mixed with soot (carbon composition 99.9% or more) using a mortar. The mixing ratio of the CeO ₂ -Ag composition and the soot was 2 g: 0.1 g by weight. The mixing was performed by using a stirrer “MMPS-M1” (manufactured by ASONE) and a magnetic mortar “MP-02” (manufactured by ASONE) for 3 minutes by electric mixing with a speed scale 3 to prepare a uniform mixture. .

Here, as in the evaluation in loose-contact in Patent Document 7, even if an oxidizing agent such as NO ₂ is present, soot is oxidized only at about 10% per hour at 323 ° C., soot oxidation evaluation method Is not appropriate. In this case, there is a possibility that the oxidation evaluation of SOF has been performed. In actual diesel exhaust, a certain degree of contact with the catalyst component is ensured to some extent in the exhausted PM, and the molten salt type catalyst described in JP-A No. 2002-210368 or Japanese Patent Application No. 2004-030058 is described. If means for alternately performing forward flow and reverse flow is used, the contact can be made closer. Therefore, in this test example, soot containing no SOF was used, and a CeO ₂ -Ag composition and a light-contact were made using a mortar, so that evaluation based on the reality of soot oxidation was performed.

Using the above various mixtures, only soot and only ceria, the CO ₂ generation intensity at the time of temperature rise was measured by the TG-mass method. As the thermogravimetric analyzer, “TG8120” (manufactured by Rigaku Corporation) was used. “GC-MS5972A” (manufactured by Hewlett Packard) was connected to the thermogravimetric analyzer, and the mass spectrum of gas components generated by the thermogravimetric analyzer was measured. Measurement conditions were as follows. In an O ₂ 10% / He balance atmosphere, the temperature was increased to 800 ° C. at a temperature increase rate of 20 K / min, and m / e = 44 component was measured as a CO ₂ component generated by soot oxidation. The results are shown in FIGS.

Further, using the same thermogravimetric analyzer, the temperature was maintained for 10 minutes at each measurement temperature in an O ₂ 10% / He balance atmosphere, and the soot oxidation rate was calculated from the weight M ₁ and the total soot weight M _{2 at} that time. The calculation method is to calculate the soot weight M ₂ based on the weight when the temperature is finally raised to 800 ° C. after the measurement of the first weight M ₁ , and from the measurement time t (here, 1/6 hour) according to the following formula: Calculated. The results are shown in FIG.

Soot oxidation rate = (M ₁ −M ₂ ) / {(M ₁ + M ₂ ) × t / 2}
<Evaluation>
4 and 5 show the results of the CeO ₂ -Ag composition prepared by the reverse coprecipitation method. The composition ratio of Ce and Ag (composition in the nitrate solution) is preferable when Ag is more than 35 mol% and less than 80 mol%, and is more preferable when Ag is more than 55 mol% and less than 65 mol%. The CeO ₂ -Ag composition obtained in this case has an Ag content of around 50 mol%, and therefore the composition ratio of Ce and Ag in the CeO ₂ -Ag composition is preferably closer to 1: 1 in terms of molar ratio.

6 and 7 show the results of _CeO 2 -Ag composition prepared by loading Ag on CeO _2. 6 has a specific surface area of results using a 166m ² / g Al-containing high specific surface area CeO _2, and FIG. 7 is a specific surface area prepared by the precipitation method was used CeO ₂ of ^55m 2 / g Is the result of the case. It can be seen that the composition ratio of Ce and Ag is preferable when Ag is 5 mol% or more, and more preferable when Ag is more than 10 mol% and less than 20 mol%. The specific surface area of CeO _2, if a high specific surface area of 50 to 300 m ² / g, it can be seen that the effect of soot oxidation promotion.

FIG. 8 shows a comparison between Ag (15) / Al-containing high specific surface area CeO ₂ (85) and Ag (15) / high specific surface area CeO ₂ (85). As is clear from the results shown in FIG. 8, it is confirmed that when Al is contained in the high specific surface area ceria, it has a soot oxidation peak on the lower temperature side and the soot oxidation ability is improved. It was.

  FIG. 9 shows the soot oxidation rate. It can be seen that the inclusion of Ag improves the oxidation rate in the low temperature region, which is consistent with the above order.

Table 1 shows the BET specific surface area of each CeO ₂ -Ag composition used. For the supported product, Ag and Ce are expressed in mol%. By referring to FIGS. 4 to 8, the soot oxidation promoting effect is recognized even at a specific surface area of about 10 m ² / g. It can also be seen that when Ag is added by loading, it is desirable that the specific surface area after loading is 50 m ² / g or more.

The 10 and 11, showing the pore size distribution of the _CeO 2 -Ag composition measured by a mercury porosimeter. FIG. 12 shows XRD measured by the θ-2θ method using Cu-Kα rays. Unlike the composition disclosed in Patent Document 8, each CeO ₂ -Ag composition has pores centered on 0.1 μm (1000 cm). In the compositions carrying the silver to the high specific surface area CeO _2, although the pores of the same 70~200Å Patent Document 8 also seen as shown in Figure 11, the pores of most is centered at 0.1μm .

CeO 2 _-Ag compositions of this test example is different from the composition disclosed in Patent Document 8. Patent Document 8 describes that it was produced by the method described in US Pat. No. 6,139,814, and US Pat. No. 6,139,814 describes that it shows a pore distribution centered on 100%. Therefore, none of them has a pore distribution centered on 0.1 μm as disclosed in this test example.

That is, in order to promote the soot oxidation in actual use, it is desirable to use a CeO ₂ -Ag composition having a pore distribution centered on 0.1 μm. Also the XRD, the peak of Ag to main peak 2 [Theta] = 38.1 ° with CeO ₂ to the main peak at 2 [Theta] = 28.5 ° was observed. Although the composition showing the same XRD pattern as in FIG. 12 does not necessarily have a low soot oxidation rate, it can be said that a composition advantageous for soot oxidation has XRD peaks of CeO ₂ and Ag. .

It was then evaluated for differences in manufacturing method of _CeO 2 -Ag composition. FIG. 13 shows the intensity of CO ₂ generation at the time of temperature rise, and FIG. 14 shows the soot oxidation rate. Since there is a difference between the coprecipitation method and the reverse coprecipitation method, the composition may differ depending on the formation of the ammonium salt. However, it is clear that by performing the aging treatment, the difference is reduced and the oxidation temperature of the soot is shifted to a low temperature range.

Note Each _CeO 2 -Ag composition was subjected to composition analysis by ICP emission spectrometry. The results are shown in Table 2.

Table 2 As can be seen from the results shown in, Ag is different from that which forms a water soluble ammonium salt, the ratio of Ce and Ag of CeO 2 _-Ag composition obtained has the ratio of nitrate solution Care must be taken as there are cases. When the content ratio (mol%) of Ag with respect to the total amount of Ce and Ag in the CeO ₂ -Ag composition is 40% or less, the composition in the nitrate solution is almost equal, but the content ratio of Ag is more than that. When it comes to the ratio, it becomes different from the composition in the nitrate solution. For example, when an aqueous nitrate solution is prepared so that the Ag content is 55 mol%, the Ag content in the CeO ₂ -Ag composition is 49.1 mol% (Ce: Ag = 50.9: 49.1). ) When the aqueous nitrate solution is prepared so that the Ag content is 60 mol%, the Ag content in the CeO ₂ -Ag composition is 50.2 mol%, and the Ag content is 80 mol%. When a nitrate aqueous solution is prepared, the content of Ag in the CeO ₂ -Ag composition is 53.8 mol%. For soot oxidation, it is preferable that Ag is close to 50 mol%, that is, Ce: Ag = 1: 1.

Also by performing the aging treatment, Ce: Ag = 1: it is easy to form a 1 of _CeO 2 -Ag composition. Although its action is unknown, it is considered that the ammonium salt of Ag is taken into the precipitate by aging treatment. Furthermore, when the aging treatment is not performed, Ag metal may be mixed in the CeO ₂ -Ag composition. However, by performing the aging treatment, the distribution of Ce and Ag becomes uniform, and the uniform black CeO _2. -Ag composition is obtained.

  Further, from the results shown in Table 2, for example, those prepared using a nitrate aqueous solution having an Ag content of 60 mol% are “with reverse coprecipitation / ripening”, Ag: 50.2 mol%, “with coprecipitation / ripening” Ag: 48.9 mol%, “No reverse coprecipitation / aging”, Ag: 33.8 mol%, “No coprecipitation / aging”, Ag: 36.1 mol%. From this, it is considered that a composition close to Ce: Ag = 1: 1 (molar ratio) preferable for soot oxidation could be formed by performing the aging treatment.

Next, an endurance test was performed in which each CeO ₂ -Ag composition was held at 800 ° C. for 5 hours at an O ₂ 10% / N ₂ balance, and then the CO ₂ generation strength and the soot oxidation rate were measured in the same manner as described above. did. The results are shown in FIGS. In view of durability at 800 ° C. or higher, it is understood that it is advantageous to use a CeO ₂ —Ag composition in which Ag is supported on CeO ₂ having a high specific surface area.

(Test Example 2)
A CeO ₂ —Pr composition and a CeO ₂ —Fe composition were prepared in the same manner as in Test Example 1 except that Pr and Fe nitrates were used instead of Ag and only the reverse coprecipitation method was used. In addition, praseodymium nitrate hexahydrate was used as the Pr raw material, and iron nitrate nonahydrate was used as the Fe raw material. Then, the CO ₂ generation intensity was measured in the same manner as in Test Example 1, and the results are shown in FIGS.

From FIG. 17 and FIG. 18, it is clear that the CeO ₂ —Pr composition and the CeO ₂ —Fe composition also show the same effect as the CeO ₂ —Ag composition.

Furthermore, XRD of each composition was measured by the θ-2θ method using Cu—Kα rays, and the main peak of ceria is shown in FIGS. 19 and 20. In the CeO ₂ —Pr composition, the peak is shifted to a lower angle side than CeO ₂ , and in the CeO ₂ —Fe composition, the peak is shifted to a higher angle side than CeO ₂ . That is, in the CeO ₂ —Pr composition and the CeO ₂ —Fe composition, by adding Fe having an atomic number smaller than Ce or Pr having a larger atomic number, the distance between Ce atoms changes, and lattice oxygen is added to soot oxidation. It is thought that it came to be used effectively.

Besides this, it is also preferable to use a CeO ₂ —Co composition. The composition ratio (molar ratio) of Ce and Co is set to Ce: Co = 50: 50 as a charging ratio, and a composition manufactured by a reverse coprecipitation method as in CeO ₂ -Ag is preferable. The composition according to ICP emission analysis in this case was 38 mol% Co. The reason why a composition different from the charging ratio is obtained is that Co forms an ammonium salt in the same manner as Ag. In XRD, a pattern of CeO ₂ and CO ₃ O ₄ was obtained.

(Test Example 3)
<Preparation of _CeO 2 -Ag composition>
In this test example, a CeO ₂ -Ag composition was prepared according to the preparation method disclosed in Patent Document 8. That is, 0.1M and 0.5M solutions were prepared so as to have a molar ratio of Ce: Ag = 25: 75 and impregnated into cellulose material (Whatman filter paper 540), and then the cellulose material was burned at 600 ° C. for 2 hours. Removed. In addition, it is described in US Pat. No. 6,139,814 cited in Patent Document 8 that a solution concentration of 0.1 M is preferable. In this test example, it cannot be said that it is disclosed in any of Patent Document 8 and US Pat. No. 6,139,814, and conversely, from column 24 of US Pat. The test was also conducted at a concentration of 0.5M, which is considered to be less preferable than 0.1M over 26 rows.

<Evaluation>
In the same manner as in Test Example 1, the CeO ₂ -Ag composition and soot were mixed in a mortar. However, each weight of _CeO 2 -Ag compositions and soot except CeO ₂ was 0.3g and 0.015g in this test example. Then, in the same manner as in Test Example 1, the CO ₂ generation intensity by the TG-mass method was compared and shown in FIG. The case where the solution concentration was 0.1M and 0.5M was described as “Ce-Ag75 filter 0.1M” and “Ce-Ag75 filter 0.5M”, respectively.

In FIG. 21, for comparison, a test was also performed on a composition obtained by firing CeO ₂ —Ag 60 (with reverse coprecipitation and aging) of Test Example 1 at 600 ° C. in the same manner as in this Test Example. As a result, the Ce-Ag75 filter 0.1M disclosed in Patent Document 8 was only slightly soot purification performance than CeO ₂ is improved. On the other hand, although it is not disclosed in Patent Document 8 and there is no suggestion that it is preferable to set to 0.5 M, when it is set to 0.5 M, it is 100 ° C. compared with 0.1 M. The above also had a soot oxidation peak at a low temperature and had a remarkable effect. However, towards the CeO 2 _-Ag compositions disclosed Test Example 1 was excellent in soot oxidation.

About the composition of this test example, the BET specific surface area measurement was performed. "Ce-Ag75 filter 0.1M" is 17.18m ² / g, "Ce-Ag75 filter 0.5M" was 11.59m ² / g. Patent Document 8 describes that the specific surface area of “Ce-Ag75 filter 0.1M” is 19 m ² / g, and since the value of those who have the same manufacturing method is close, “Ce-Ag75 of this test example” It can be said that “filter 0.1M” is the same substance as “Ag0.75Ce0.25” disclosed in Patent Document 8.

(Summary)
That is, the compositions used in this test example all promote the soot oxidation, and have the properties as an acidic compound adsorption means or the soot oxidation promotion means. It is preferable to use it in a purification device. In addition, the composition used in the test example may further use an alkali metal or an alkaline earth metal. By doing so, SO _x is absorbed by these metals, and SO _x poisoning of CeO ₂ and Ag can be suppressed.

(Example 2)
In this embodiment, as shown in FIG. 22, in addition to the exhaust purification device of Embodiment 1, the NH ₃ supply nozzle 3 is provided on the exhaust upstream side of the DPF 1 so that NH ₃ can be supplied into the exhaust flowing into the DPF 1. Has been.

While heating by the heater 10 up to 250 to 350 ° C., by constantly 50ppm supplying NH ₃ from NH ₃ supply nozzle 3, since the elimination of acidic compounds is further promoted, the oxidation of soot is further promoted .

(Example 3)
FIG. 23 shows the exhaust emission control device of this example. In the exhaust flow path, DPF 1 is arranged in which both ends of the openings of the cells of the ceramic honeycomb structure are alternately plugged in a checkered pattern. In the DPF 1, as shown in FIG. 24, a coat layer 20 containing ceria is formed on the surface of the cell partition wall, and the coat layer 20 constitutes the acidic compound adsorbing means 2.

An NH ₃ supply nozzle 3 is disposed on the exhaust upstream side of the DPF 1 so that NH ₃ can be supplied into the exhaust flowing into the DPF 1. A NO _x selective reduction catalyst 30 is disposed on the exhaust downstream side of the DPF. The NO _x selective reduction catalyst 30 is formed by forming a coating layer made of Fe-zeolite on a honeycomb substrate having a straight flow structure per 100 L of the substrate.

In the exhaust purification apparatus of the present embodiment, NH ₃ is supplied into the exhaust gas from the NH ₃ supply nozzle 3 in synchronization with the driving of the engine. The NH ₃ amount may be a necessary amount with respect to the NO _x selective reduction catalyst 30, but even when NH ₃ is not necessary for NO _x reduction, 5 ppm or more is always supplied. This is also desirable because NO _x and PM emissions are in a trade-off relationship.

In this exhaust gas purification device, when exhaust gas flows into the DPF 1, the surface of the soot comes into contact with the ceria of the coat layer 20 to oxidize the surface, and acidic compounds such as CO and CO ₂ are generated. Since this acidic compound is adsorbed and removed by ceria almost simultaneously with the generation, oxidation further proceeds on the surface of the soot, and a new acidic compound is generated and adsorbed on ceria.

And since the NH ₃ from the NH ₃ supply nozzle 3 is supplied into the exhaust, NH ₃ is in contact with the coating layer 20 to desorb the acid compound adsorbed to ceria ceria. As a result, the ability of ceria to adsorb acidic compounds is recovered, and soot oxidation proceeds smoothly.

Even if the excess NH ₃ fed, NH ₃ passing through the DPF1, since in _the NO _x selective reduction catalyst 30 is consumed in the reduction purification of NO _x, emissions NH ₃ does not occur. Further, even when NH ₃ is not required for NO _x reduction, NH ₃ is adsorbed on Fe-zeolite, and thus emission can be suppressed to a minimum.

That is, according to the exhaust gas purification apparatus of the present embodiment, soot can be continuously oxidized and NO _x can also be purified. Therefore, since the DPF 1 can be continuously regenerated, problems such as melting of the DPF 1 can be avoided, and an increase in pressure loss can be suppressed.

In this embodiment, although supplying NH ₃ at all times from the NH ₃ supply nozzle 3 may be pulsed supplied. Further, H ₂ may be supplied instead of NH ₃ . Further, when the amount of NH ₃ or H ₂ supplied is sufficient for desorption of acidic compounds but not sufficient for purifying NO _x , DPF1 and NO _x selective reduction catalyst 30 are used. NH _3, H _2, or HC can be supplied between the _two . In this case, HC is prevented from flowing into DPF1. Since generation of acidic compounds does not adversely affect soot oxidation, HC can be supplied at the downstream side of DPF1. Further, in order to reliably prevent the discharge of NH _3, it may be provided NH ₃ purifying catalyst on the downstream side of the NO _x selective reduction catalyst 30.

In addition, the mechanism of the oxidation reaction of soot by ceria was investigated in detail by diffuse reflection type FT-IR. The obtained results are shown in FIGS. Incidentally, by using CeO ₂ -Ag60 as an acidic compound adsorbent is a diffuse reflective FT-IR spectrum in the case where the oxidation of soot, both measured in a nitrogen atmosphere, measurement temperature was 300 ° C..

The measurement of the spectrum at the time of “acidic compound adsorption” shown in FIG. 25 is performed by adsorbing the acidic compound produced by the soot oxidation by adsorbing the 10% O ₂ atmosphere for 10 minutes immediately at 300 ° C. It was measured immediately after switching to. In addition, the spectrum after “desorption of acidic compound” shown in FIG. 25 is measured in the nitrogen atmosphere after the acidic compound is adsorbed after being held for 10 minutes in the nitrogen atmosphere after the measurement at the time of adsorption of the acidic compound. It is measured. Comparing both spectra shown in FIG. 25, it was confirmed that the intensity in the vicinity of 1450 cm ⁻¹ increased when the acidic compound was adsorbed.

FIG. 26 is a graph showing a change in spectrum obtained from a spectrum after desorption of an acidic compound as a background from a spectrum during adsorption of the acidic compound. Peak around above 1450 cm ^-1, since attributed to carbonate _(CO ^{3 2-),} acidic compound _CO ^{3 2-} adsorbs an acidic compound during adsorption, _CO ³ after acidic compound desorption ^2- Was confirmed to be detached. Incidentally, observed since the only shed CO ₂ was no change in the spectrum, the above _CO ^{3 2-} peaks are those CO ₂ or CO produced by the soot oxidation is adsorbed as _CO ^{3 2-} .

Thus, when the CeO ₂ -Ag composition is used as the acidic compound adsorbent according to the present invention, a very strong carbonate peak appears, so that the acidic compound generated by soot oxidation is quickly extracted from the soot. It was confirmed that it is possible to promote soot oxidation by repeating such adsorption and desorption of acidic compounds.

Moreover, in the diffuse reflection type FT-IR spectrum, a change was observed in the wave number region of 1200 to 1700 cm ⁻¹ of ceria, and it became clear that a carboxyl group or a carbonyl group was formed on the ceria surface during soot oxidation. .

On the other hand, Applied Catalysis B: Environmental 50 (2004) 185-194 Table 3 or Carbon Vol. 36 No. 9 pp1269 and so on describe the oxidation mechanism of soot. According to this, the surface of the soot is first oxidized to form an oxide having a complicated structure, and at the same time, acidic compounds such as CO and CO ₂ are generated. This confirms the results of the diffuse reflection type FT-IR described above, and the soot oxidation mechanism is such that the surface is first oxidized to produce an acidic compound, and when the acidic compound is discharged, the next surface is oxidized and becomes acidic again. It is thought that the whole is oxidized when a compound is formed and continues.

That is, in the exhaust purification apparatus of the present embodiment, the surface of the soot is oxidized by the active oxygen supplied by the oxygen absorbing / releasing ability of ceria, and the acidic compound produced thereby is adsorbed on the ceria. The adsorbed acidic compound is positively extracted out of the reaction system by the supplied acidic compound desorbing agent such as NH ₃ . Thereby, the oxidation reaction of soot is accelerated | stimulated and soot can be oxidized continuously. Therefore, the pressure loss does not easily increase, and therefore forced regeneration is unnecessary or the number of times can be greatly reduced. At the same time, NO _x can be purified, and since no precious metal is used, the apparatus is inexpensive. Needless to say, noble metals can be used for purposes not related to soot oxidation.

Example 4
FIG. 27 shows the exhaust emission control device of this example. This exhaust purification device does not use the NH ₃ supply nozzle 3, except that a hydrogen generation catalyst 31 is disposed upstream of the DPF 1 and a NO _x storage reduction catalyst 32 is disposed in place of the NO _x selective reduction catalyst 30. The configuration is the same as that of the third embodiment.

  The hydrogen generation catalyst 31 is formed by forming 150 g of a coating layer made of ceria-alumina composite oxide per 1 L of a base material on a honeycomb substrate having a straight flow structure, and carrying 1.5 g of Pt per 1 L of the base material on the coating layer. It is.

The NO _x storage reduction catalyst 32 is formed by forming 100 g of alumina coating layer per liter of substrate on a honeycomb substrate having a straight flow structure, supporting 1.5 g of Pt per liter of substrate on the coating layer, and using Ba as a base. It is formed by carrying 0.1 mol per liter of material, 0.1 mol of K per liter of base material, and 0.1 mol of Li per liter of base material.

In this exhaust gas purification device, when exhaust gas flows into the DPF 1, the surface of the soot comes into contact with the ceria of the coat layer 20 to oxidize the surface, and acidic compounds such as CO and CO ₂ are generated. Since this acidic compound is adsorbed and removed by ceria almost simultaneously with the generation, oxidation further proceeds on the surface of the soot, and a new acidic compound is generated and adsorbed on ceria.

In the hydrogen generation catalyst 31, H ₂ is generated by the steam reforming reaction and flows into the DPF 1, so that the H ₂ comes into contact with the coat layer 20 and desorbs the acidic compound adsorbed on the ceria. As a result, the ability of ceria to adsorb acidic compounds is recovered, and soot oxidation proceeds smoothly. Furthermore, since HC is consumed in the hydrogen generation catalyst 31, inhibition of the soot oxidation reaction in the DPF 1 is suppressed. The H _{2 that} has passed through the DPF 1 is consumed for NO _x reduction and purification in the NO _x storage reduction catalyst 32. Hence oxidation of soot proceeds continuously, can greatly reduce the unnecessary or number of times the forced regeneration is the pressure loss is less likely to increase, it is possible to purify NO _x simultaneously.

Furthermore, you may arrange | position an alkali metal or an alkaline-earth metal with Ceria in DPF1. Then, these metals function as acidic compound adsorbents and may prevent thermal runaway when a large amount of particulate matter is deposited on the DPF 1 unexpectedly. This is because the supply of oxygen to particulate matter such as soot is blocked by receiving a large amount of acidic compounds such as CO ₂ adsorbed on these metals by receiving the heat of natural oxidation. .

Incidentally, as shown by a dotted line in FIG. 24, for _the NO _x reduction, between DPF1 and _the NO _x storage-reduction catalyst 32, further _{NH 3,} H 2, HC, etc. may be supplied.

(Example 5)
FIG. 28 shows the exhaust purification system of the present embodiment. A DPF 1 similar to that in the third embodiment is disposed in the exhaust passage. Further, the same NH ₃ supply nozzle 3 as that in the third embodiment is arranged, and NH ₃ can be supplied to the exhaust flow path on the upstream side of the DPF 1. The driving of the NH ₃ supply nozzle 3 is controlled by the control means 5.

In this exhaust purification system, when the exhaust gas flows into the DPF 1, the surface of the soot comes into contact with the ceria of the coat layer 20 to be oxidized, and acidic compounds such as CO and CO ₂ are generated. This acidic compound is adsorbed and removed by ceria almost at the same time as the generation, so that oxidation further proceeds on the surface of the soot and a new acidic compound is generated. However, when the amount of acidic compound adsorbed by ceria is saturated, the soot oxidation stops at that point.

Therefore, NH _{3 is} supplied into the exhaust gas from the NH ₃ supply nozzle 3 before the adsorption amount of the acidic compound by ceria is saturated. NH ₃ comes into contact with the coating layer 20 and desorbs the acidic compound adsorbed on the ceria from the ceria. As a result, the ability of ceria to adsorb acidic compounds is recovered, and soot oxidation proceeds smoothly.

The control contents of the control means 5 will be described below with reference to FIG. While the engine is being driven, the detection signal of the temperature sensor 4 is constantly input to the control means 5. First, when the engine is driven, in step 101, the control means 5 reads the temperature (Td) stored in the ROM. Td is a temperature at which acidic compounds such as CO and CO ₂ adsorbed on ceria are smoothly desorbed, and is higher than the temperature at which desorption starts. This temperature (Td) is determined in advance as a temperature at which the continuous oxidation amount of soot is sufficient for each engine system. For example, when a coat layer is formed from a composition obtained by coprecipitation, aging, and baking at a Ce: Ag ratio of 40:60 (molar ratio) as in Example 1, for example, Td = 260 ° C. There are cases where it is possible.

Next, in step 102, the actual temperature (T) of the DPF 1 is input from the temperature sensor 4 to the control means 5, and Td and T are compared in step 103. If T> Td, since the acidic compound has already been desorbed from ceria, the driving of the NH ₃ supply nozzle 3 is stopped in step 105 and the process returns to step 102. On the other hand, when T ≦ Td, since the acidic compound is adsorbed on the ceria, the control unit 5 drives the NH ₃ supply nozzle 3 in step 104. The NH ₃ supply nozzle ₃ supplies NH ₃ to the exhaust upstream of the DPF 1, and the process returns to Step 102.

Therefore, while the temperature T of the DPF 1 is lower than Td (T ≦ Td), NH ₃ is always supplied, so that the acidic compound is desorbed immediately after generation and the soot is smoothly oxidized and purified. Further, when the temperature (T) of the DPF 1 is higher than Td (T> Td), NH ₃ is not supplied, and the soot is smoothly oxidized and purified by the ceria oxidizing power and the high-temperature exhaust. Thereby, according to the exhaust gas purification system of the present embodiment, the soot can be smoothly oxidized and purified from a low temperature range of less than 300 ° C., and an increase in pressure loss is also suppressed. And, since no precious metal or catalyst is used, it is inexpensive.

As for the amount of NH ₃ added, it is desirable to prepare a map of the required amount of NH _{3 with} respect to the soot discharge amount and the exhaust temperature, and supply NH ₃ within that range.

(Example 6)
FIG. 30 shows the exhaust purification system of the present embodiment. In the present embodiment, in addition to the apparatus of the fifth embodiment, the driving status of the engine is input to the control means 5. The control means 5 performs the control shown in FIG. 31 in parallel with the control of FIG.

  When traveling, first, a predetermined value (X) preset in step 201 and a preset time (Y) are read. When the engine torque and the rotational speed are read in step 202, in step 203, the control means 5 reads the relationship between the torque stored in advance in the ROM and the soot discharge amount with respect to the rotational speed from the map. The soot amount (Q) in the exhaust at is read. In step 204, the soot accumulation amount (A) so far is calculated, and in step 205, a preset predetermined value (X) is compared with the temporal change amount (dA / dt) of the soot accumulation amount. .

If dA / dt ≧ X, it is determined that the vehicle has entered a travel mode in which the engine load is large and the amount of soot discharged is large, such as on a mountain road. In step 206, the NH ₃ supply nozzle 3 is driven, and the process returns to step 202. Therefore, even if the state where the amount of soot discharged is continued thereafter, the acidic compound is smoothly desorbed by the supply of NH ₃ , so that the soot can be smoothly oxidized and purified.

On the other hand, if dA / dt <X, the time during which dA / dt <X continues in step 207 is compared with a preset time (Y). If the time during which the dA / dt <X state continues is equal to or longer than the preset time (Y), the driving of the NH ₃ supply nozzle 3 is stopped at step 208 and the process returns to step 202. However, when the duration of the dA / dt <X duration is shorter than the preset time (Y), the NH ₃ supply nozzle 3 is in a state where the amount of soot discharge is large, such as mountain road running continuously. The process returns to step 202 without stopping the driving of.

  Therefore, according to the exhaust purification system of the present embodiment, in addition to the control according to the temperature of the fifth embodiment, control is performed in which the amount of soot discharged from the engine is predicted, so that the soot oxidation purification can be performed with higher accuracy. it can.

(Example 7)
FIG. 32 shows an exhaust purification system of the present embodiment. In the present embodiment, in addition to the apparatus of the fifth embodiment, pressure sensors 6 are disposed in the exhaust passages upstream and downstream of the DPF 1, respectively, and the exhaust pressure on both sides of the DPF 1 is input to the control means 5. . The control means 5 performs the control shown in FIG. 33 in parallel with the control of FIG.

  When the engine is started, in step 301, the control means 5 reads a predetermined differential pressure value Pc stored in advance in the ROM and a preset time (Z). Next, in step 302, detection values of the pair of pressure sensors 6 are input, and in step 303, a differential pressure ΔP between the two pressures is calculated. In step 304, the differential pressure ΔP and Pc are compared.

If ΔP ≧ Pc, it is determined that the soot accumulation amount in the DPF 1 has exceeded a predetermined amount, the NH ₃ supply nozzle 3 is driven in step 305, and the process returns to step 302. Therefore, even if the soot deposition amount increases, the acidic compound is smoothly desorbed by the supply of NH ₃ and the soot can be smoothly oxidized and purified, so that an increase in pressure loss can be reliably suppressed.

On the other hand, if ΔP <Pc, the time during which ΔP <Pc continues in step 306 is compared with a preset time (Z). When the time for which the state of ΔP <Pc continues is equal to or longer than the preset time (Z), the driving of the NH ₃ supply nozzle 3 is stopped in Step 307 and the process returns to Step 302. However, when the duration of the state of ΔP <Pc is shorter than the preset time (Z), the state in which the soot accumulation amount is large continues, so the driving of the NH ₃ supply nozzle 3 is stopped. The process returns to step 302 without.

  Therefore, according to the exhaust purification system of the present embodiment, control according to the amount of soot accumulated in the DPF 1 is performed in addition to the control according to the temperature of the fifth embodiment, so that it is possible to reliably suppress an increase in pressure loss. it can.

(Example 8)
FIG. 34 shows the exhaust purification system of the present embodiment. In the present embodiment, in addition to the apparatus of the sixth embodiment, the oxidation catalyst 7 is disposed on the upstream side of the DPF 1, and the NO _x purification means 8 is disposed on the downstream side of the DPF 1. The oxidation catalyst 7 is formed by forming a coat layer in which Pt is supported on alumina on a honeycomb substrate having a straight flow structure. The NO _x purification means 8 is composed of a NO _x storage reduction catalyst in which a coat layer formed by supporting Pt, Ba and K on alumina is formed on a honeycomb substrate having a straight flow structure.

In this exhaust purification system, the acidic compound is smoothly desorbed by the supply of NH ₃ by being controlled in the same manner as in FIG. Further, NO in exhaust gas is oxidized by the oxidation catalyst 7 to become NO ₂ , and NO ₂ having high oxidation activity flows into the DPF 1 as soot oxidation promoting means. Therefore, soot oxidation purification is further promoted. Even if NO _x is generated by oxidation of NH ₃ in addition to NO _x contained in the exhaust gas, the NO _x is occluded or reduced and purified by the NO _x purification means 8, so that NO _x is discharged. Can be prevented. In the oxidation catalyst 7, HC in the exhaust is oxidized and removed. Therefore, the oxidation catalyst 7 functions as soot oxidation promoting means and HC removing means.

Note that NO is generated by the reaction between soot and NO ₂ , but NO _x selective reduction catalyst makes it difficult to reduce and purify NO, so the NO _x purification means 8 can store NO _x by being oxidized by oxidizing NO. A reducing catalyst is used. By supplying NH ₃ as a desorbing agent, the exhaust atmosphere becomes a stoichiometric to rich atmosphere, and NO _x can be efficiently reduced and purified in the NO _x purification means 8.

In the case of this embodiment, the map of exhausted NO amount with respect to the torque of the engine speed, leave calculated NH ₃ amount required to reduce and purify the NO, NH ₃ supplied by the control of FIG. 29 The amount of is preferably within the range of the calculated amount of NH ₃ .

  As described above, according to the exhaust gas purification apparatus and the exhaust gas purification system of the present invention, soot can be continuously oxidized from a low temperature range at low cost by positively desorbing acidic compounds. Therefore, the exhaust purification device and the exhaust purification system of the present invention are very useful as an exhaust purification device and an exhaust purification system for purifying particulate matter containing soot discharged from an internal combustion engine such as a diesel engine.

It is explanatory drawing which shows the effect | action of the exhaust gas purification apparatus of this invention. It is a block diagram which shows the exhaust gas purification apparatus of one Example of this invention. It is sectional drawing of DPF used for the exhaust gas purification apparatus of one Example of this invention. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between the temperature and the soot oxidation rate. Is a graph showing the pore distribution of the various _CeO 2 -Ag composition. Is a graph showing the pore distribution of the various _CeO 2 -Ag composition. Is an XRD chart of various _CeO 2 -Ag composition. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between the temperature and the soot oxidation rate. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between the temperature and the soot oxidation rate. At the time of various CeO 2 _-Pr composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. At the time of various CeO 2 _-Fe composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. Is an XRD chart of various _CeO 2 -Pr composition. Is an XRD chart of various _CeO 2 -Fe composition. At the time of various CeO 2 _-Ag composition and a mixture of soot and pyrolysis is a graph showing the relationship between temperature and CO ₂ generation intensity. It is a block diagram which shows the exhaust gas purification apparatus of the 2nd Example of this invention. It is a block diagram which shows the exhaust gas purification apparatus of the 3rd Example of this invention. It is sectional drawing of DPF used for the exhaust gas purification apparatus of the 3rd Example of this invention. Using _CeO 2 -Ag60 as an acidic compound adsorbent is a graph showing the diffuse reflection type FT-IR spectrum in the case where the oxidation of soot. It is a graph which shows the spectrum change obtained by subtracting the spectrum after acidic compound desorption as a background from the spectrum at the time of acidic compound adsorption. It is a block diagram which shows the exhaust gas purification apparatus of the 4th Example of this invention. It is a block diagram which shows the exhaust gas purification system of the 5th Example of this invention. It is a flowchart explaining the control content of the exhaust gas purification system of the 5th Example of this invention. It is a block diagram which shows the exhaust gas purification system of the 6th Example of this invention. It is a flowchart explaining the control content of the exhaust gas purification system of the 6th Example of this invention. It is a block diagram which shows the exhaust gas purification system of the 7th Example of this invention. It is a flowchart explaining the control content of the exhaust gas purification system of the 7th Example of this invention. It is a block diagram which shows the exhaust gas purification system of the 8th Example of this invention.

Explanation of symbols

1: DPF (base material), 2: acidic compound adsorption means, 3: NH ₃ supply nozzle (acidic compound desorption means), 4: temperature sensor (detection means), 5: control means, 6: pressure sensor (detection means) ), 7: oxidation catalyst, 8: NO _x purification means, 20: coat layer (acidic compound adsorption means), 30: NO _x selective reduction catalyst, 31: hydrogen production catalyst, 32: NO _x storage reduction catalyst.

Claims (12)

A base material capable of collecting particulate matter discharged from an internal combustion engine;
An acidic compound adsorption means for adsorbing an acidic compound contained in or present on the substrate;
Acidic compound desorption means for desorbing the acidic compound adsorbed on the acidic compound adsorption means;
Tona is, and,
The acidic compound adsorption means is obtained by baking the precipitate after obtaining a precipitate in the presence of a base from a solution containing Ce and Ag, and the ratio of Ag to the total amount of Ce and Ag is 35-60. A composition containing ceria that is mol%, or ceria obtained by impregnating ceria into a solution containing Ag and calcining, and the ratio of Ag to the total amount of Ce and Ag is 10 to 40 mol% A composition comprising
An exhaust purification device characterized by the above.   The exhaust emission control device according to claim 1, wherein the acidic compound desorbing means is an acidic compound desorbing agent supplying means for supplying an acidic compound desorbing agent into the exhaust gas.   The exhaust emission control device according to claim 2, wherein the acidic compound desorbing agent is at least one of ammonia and hydrogen.   The exhaust emission control device according to claim 1, wherein the acidic compound desorbing means is a heating means for heating the acidic compound adsorbing means.   The exhaust emission control device according to claim 4, wherein the heating unit is at least one of a rich exhaust gas with excessive reducing components and a heater.   The exhaust emission control device according to any one of claims 1 to 5, further comprising soot oxidation promoting means for promoting oxidation of soot in the exhaust gas flowing into the base material.   The exhaust emission control device according to claim 6, wherein the soot oxidation promoting means is an oxygen release material that releases active oxygen.   The exhaust emission control device according to any one of claims 1 to 7, further comprising contact promoting means for promoting contact between the acidic compound adsorbing means and soot.   The exhaust emission control device according to any one of claims 1 to 8, further comprising HC removal means for removing HC in exhaust gas on an exhaust upstream side of the base material. The exhaust emission control device according to any one of claims 1 to 9, further comprising at least one selected from a three-way catalyst, a NO _x selective reduction catalyst, and a NO _x storage reduction catalyst. The exhaust emission control device according to any one of claims 1 to 10 , wherein the composition containing ceria further contains Al. An exhaust emission control device according to any one of claims 1 to 11 ,
Detecting means for detecting a physical quantity related to at least one selected from the temperature of the base material, the amount of soot in the exhaust gas flowing into the base material, and the amount of soot deposited on the base material;
Control means for controlling the driving of the acidic compound detachment means based on the detection value of the detection means;
An exhaust purification system comprising:

Images