Patent Application
20100058742
The present invention relates to an exhaust emission control apparatus for an internal combustion engine.
It is known that a conventional exhaust emission control apparatus disclosed, for instance, in JPA-2002-89246 includes an NOx Storage-Reduction catalyst (hereinafter referred to as an “NSR catalyst”). More specifically, the NSR catalyst comprises a catalyst function which purifies nitrogen oxide (NOx) and hydrocarbons (HC) contained in the combustion gas exhausted in the internal combustion engine, and a storage function which stores NOx in the catalyst. Before the catalyst activates, such as when there is a cold startup of the internal combustion engine, or while the exhaust gas is lean, and when the reducing agent is in short supply, NOx may be emitted into the atmosphere without being purified in the catalyst. NSR catalyst is capable of storing NOx in the catalyst, and performing a purifying treatment by reacting the stored NOx and reducing agents such as HC under a situation where the catalyst has been activated and rich or stoichiometric driving is performed.
Moreover, during a cold startup operation of the internal combustion engine in which the NSR catalyst does not reach its activation temperature, the above mentioned storage reaction may not occur with a high degree of efficiency because oxidation reaction of NOx is not activated. In the above described conventional system, therefore, it is decided to add ozone to exhaust gas. NOx reacts with ozone in the gas-phase. Therefore, the system can effectively oxidize NOx even before the catalyst is fully activated so as to increase the NOx storage amount.
Patent Document 1: JP-A-2002-89246
Patent Document 2: JP-A-6-185343
Patent Document 3: JP-A-10-169434
NOx stored in the catalyst is decomposed to N2, H2O, CO2, and others by reducing agents in the exhaust gas such as HC or CO. During stoichiometric operation, therefore, the reducing agent for reducing the stored NOx may be in short supply, thereby NOx purification may not be performed effectively.
The present invention has been made to solve the above problem. One object of the present invention is to provide an exhaust emission control apparatus for an internal combustion engine that is capable of improving the NOx purification performance.
First aspect of the present invention is an exhaust emission control apparatus being placed in an exhaust path of an internal combustion engine, comprising:
an NOx retention material;
ozone injection means for injecting ozone into an exhaust gas being positioned upstream from the NOx retention material;
an HC adsorbent adsorbing HC contained in the exhaust gas; and
a catalyst being placed in a region where desorbed NOx and desorbed HC contact each other;
wherein, said HC adsorbent is prepared so as to desorb adsorbed HC at the same time as NOx being stored in the NOx retention material is desorbed.
Second aspect of the present invention is the exhaust emission control apparatus according to the first aspect, wherein the HC adsorbent and the NOx retention material are integrated with the catalyst.
Third aspect of the present invention is the exhaust emission control apparatus according to the first aspect, wherein the NOx retention material is separated from the HC adsorbent,
wherein the HC adsorbent is positioned upstream from the NOx retention material, and
wherein the ozone injection means injects ozone into the exhaust gas being positioned downstream from the NOx retention material.
Fourth aspect of the present invention is the exhaust emission control apparatus according to the third aspect, wherein the NOx retention material is separated from the catalyst, and
wherein the NOx retention material is positioned upstream from the catalyst.
Fifth aspect of the present invention is the exhaust emission control apparatus according to the third aspect, wherein the NOx retention material is combined with the catalyst.
Sixth aspect of the present invention is the exhaust emission control apparatus according to any one of the first to the fifth aspects, further comprising:
control means for controlling the ozone injection means so that a molar quantity of ozone to be injected into the exhaust gas becomes greater than a molar quantity of nitrogen monoxide contained in the exhaust gas.
Seventh aspect of the present invention is the exhaust emission control apparatus according to the sixth aspect, wherein the control means controls the ozone injection means so that the molar quantity of ozone to be injected into the exhaust gas becomes at least two times the molar quantity of nitrogen monoxide contained in the exhaust gas.
According to the first aspect of the present invention, an HC adsorbent which adsorbs HC is placed in an exhaust path of an internal combustion engine. The HC adsorbent is prepared so that the adsorbed HC might be desorbed when the NOx being stored by the NOx retention material reaches its desorbed temperature. Therefore, the present invention can make the NOx desorbed from the NOx retention material along with the HC desorbed from the HC adsorbent to react with the catalyst so as to be purified, thereby preventing the reducing agents from being in short so as to improve the NOx purification performance.
According to the second aspect of the present invention, it is possible to make the desorbed HC and the desorbed NOx react in the catalyst with a high degree of efficiency since the HC adsorbent and the NOx retention material are integrated with the catalyst. Further, it is possible to hold down production costs since the number of parts is reduced by the integration.
According to the third aspect of the present invention, ozone is introduced into downstream from the NOx retention material. Therefore, the present invention makes it possible to prevent ozone from reacting with HC which is adsorbed into the HC adsorbent, thereby improving the oxidation efficiency of NOx.
It is thought that the storage element which is supported by the NOx retention material could be a catalyst poison for a noble metal of the catalyst. According to the forth aspect of the present invention, since the NOx retention material is separated from the catalyst, it is possible to enhance the activation of the catalyst. Furthermore, since the catalyst is positioned downstream from the NOx retention material, it is possible to purify NOx, which has not been stored by the NOx retention material, in the catalyst after a certain level of catalyst activation has been reached. Therefore, this makes it possible to improve the NOx purification performance.
According to the fifth aspect of the present invention, the NOx retention material is combined with the catalyst. Therefore, this makes it possible to make the desorbed NOx react in the catalyst with a high degree of efficiency. Furthermore, the number of parts is reduced by combining them into a single unit. Therefore, this makes it possible to save on production costs.
Embodiments of the present invention will now be described with reference to the accompanying drawings. Like elements in the drawings are designated by the same reference numerals and will not be redundantly described. It should be understood that the present invention is not limited to the embodiments described below.
An exhaust path 14 is attached to an exhaust side of the engine 12. An exhaust purification catalyst 20 is installed in the exhaust path 14. The exhaust purification catalyst 20 supports platinum (Pt) that is a noble metal and barium carbonate (BaCO3) on a ceramic carrier. Pt functions as an active site that activates the oxidation reaction of CO, HC, and others or the reduction reaction of NOx. Further, BaCO3 functions as an NOx storage substance which stores NOx in the form of nitrate salt.
Zeolite based ZSM-5 is supported by a ceramic carrier of the exhaust purification catalyst 20. ZSM-5 functions as an HC adsorbent that adsorbs HC. The following explanation assumes that the terms “catalyst” refers to a portion of the carrier that supports Pt. Further, it is also assumed that the term “NOx retention material” refers to a portion of the carrier that supports BaCO3. Furthermore, it is also assumed that the term “HC adsorbent” refers to a portion of the carrier that supports ZSM-5.
The exhaust emission control apparatus 10 according to the first embodiment includes an ozone supply device 30. The ozone supply device 30 includes a system that generates ozone by performing a creeping discharge into oxygen taken from an air inlet 32. The configuration, function, and other characteristics of the ozone supply device 30 will not be described in detail because they are not main parts of the present invention and are well-known.
The ozone supply device 30 includes an ozone injection orifice 34 that injects ozone toward the exhaust purification catalyst 20. The ozone injection orifice 34 is placed so that the injected ozone might be uniformly mixed with the exhaust gas which is streamed into the exhaust purification catalyst 20.
As shown in
An operation of the present embodiment will now be described with reference to
In view of the above circumstances, the present embodiment prevents the unpurified NOx from being emitted into the atmosphere by storing them into the exhaust purification catalyst 20. Ozone is injected into the exhaust gas as a means for storing the NOx in the exhaust purification catalyst 20. More specifically, the ozone generated by the ozone supply device 30 is injected from the ozone injection orifice 34 toward the exhaust purification catalyst 20.
NO+O3→NO2+O2 (1)
NO2+O3→NO3+O2 (2)
NO2+NO3→N2O5 (3)
(NO2+NO3←N2O5)
The NOx oxidized to NO2, NO3, or N2O5 is stored in the NOx retention material in the form of nitrate such as Ba(NO3)2. Thereby, it is possible to store the NOx effectively. Therefore, it is possible to effectively prevent the NOx from being emitted into the atmosphere, even when the exhaust purification catalyst 20 is not fully activated.
Moreover, according to the gas-phase reaction of ozone as shown in the above formulas (1) and (2), the region in which NOx is oxidized is not limited to a region on catalyst. Therefore, for instance, it is possible to support the NOx storage substance and noble metal separately in the exhaust purification catalyst 20. Therefore, the NOx storage substance which could be a catalyst poison for the noble metal can be separated from the noble metal, thus improving the purification efficiency of the catalyst.
According to the aforementioned NOx storage reaction, the forms of NO2, NO3, N2O5, or HNO3 which is generated when the former nitrogen oxides react with water can be stored. However, there is a limitation of NOx storage amount as for the form of NO2. Therefore, it is possible to dramatically increase the storage amount of NOx if the reaction as shown in the above formula (2) occurs actively so as to convert large amounts of NO2 into NO3.
However, the activation energy necessary to take place the reaction as shown in the above formula (2) is higher than the energy required in the reaction as shown in the above formula (1). Therefore, the reaction of the above formula (1) takes priority over the reaction of the above formula (2). Therefore, all reactions occurring are just the reactions of the above formula (1) so that the final form of oxidized NO becomes NO2 when the molar quantity of ozone contained in the exhaust gas is smaller than the molar quantity of NO.
In view of the above circumstances, the injection quantity of ozone is controlled so that the molar quantity of ozone to be injected into the exhaust gas might be greater than the molar quantity of NO contained in the exhaust gas. This make it possible to be oxidized from NO2 to NO3. Therefore, it is possible to increase the storage amount of NOx.
Further, it is preferred that the injection quantity of ozone is controlled so that the molar quantity of ozone to be injected into the exhaust gas might be more than twice the molar quantity of NO contained in the exhaust gas. This makes it possible for most of the NO to be oxidized to NO3. Therefore, it is possible to increase the storage amount of NOx dramatically.
As described above, according to the present embodiment, the ozone is injected toward the exhaust purification catalyst 20. This makes it possible to store the NOx, which is exhausted with a cold startup of the engine 12, effectively. Therefore, it is possible to prevent the NOx from being emitted into the atmosphere.
After the exhaust purification catalyst 20 activates, the stored NOx is purified by reacting with a reducing agent such as HC contained in the exhaust gas.
However, NOx may be emitted into the atmosphere without being purified in the catalyst during a stoichiometric operation of the internal combustion engine 12 since the reducing agent for purifying the desorbed NOx may be in short supply. In view of the above circumstances, an HC adsorbent is placed into the exhaust purification catalyst 20 in the present embodiment. The HC adsorbent is configured by making the carrier support a zeolite based adsorbent that adsorbs HC at low temperatures and desorbs the HC at high temperatures. Desorption temperature characteristics of the adsorbed HC vary depending on the substance of the adsorbent. According to the present embodiment, the HC adsorbent is prepared so that the desorption start temperature of HC might coincide with the desorption start temperature of NOx which is stored in the exhaust purification catalyst 20.
The HC contained in the exhaust gas is adsorbed by the HC adsorbent during a cold startup of the engine 12. The adsorbed HC is desorbed at the time when desorption of the stored NOx is started after a rise in the temperature of the exhaust purification catalyst 20. Therefore, it is possible to reliably purify the NOx stored before the catalyst activation by additionally supplying HC that functions as a reducing agent during the desorption period of NOx when reducing agents are apt to be in short supply.
The first embodiment, which has been described above, assumes that ozone is generated by the ozone supply device 30 and injected toward the exhaust purification catalyst 20 from ozone injection orifice 34. However, the configuration of the ozone supply device 30 is not limited to the above-described one. That is, an ozone generation device may be installed in the exhaust path 14 or the ozone supply device 30 may inject ozone into the exhaust path 14 upstream from the exhaust purification catalyst 20, as long as ozone can be added to the exhaust gas introduced into the exhaust purification catalyst 20.
Furthermore, although BaCO3 is used as an NOx storage substance in the above described first embodiment, the material is not limited to this. For example, alkali metals such as Na, K, Cs and Rb, alkali earth metals such as Ba, Ca and Sr, and rare earth elements such as Y, Ce, La and Pr may be used as needed. Also, the material of the catalyst is not limited to Pt. For example, noble metals such as Rh and Pd may be used as needed. Furthermore, the material of the HC adsorbent is not limited to ZSM-5. For example, various publicly known HC adsorbent may be used as needed.
In the first embodiment, which has been described above, the ozone supply device 30 corresponds to the “ozone supply means” according to the first aspect of the present invention; and the exhaust purification catalyst 20 corresponds to the “catalyst” according to the first aspect of the present invention.
Next, evaluation test for confirming the advantage of the invention showing the first embodiment will now be described with reference to
A catalyst test piece 200 is installed a path which is placed downstream from the model gas generator 100. An electric furnace, which controls the temperature of the catalyst test piece 200 to a desired temperature, is installed around the catalyst test piece 200. The configuration of the catalyst test piece 200 will be described in detail below.
Exhaust gas analyzers 110, 112 and an ozone analyzer 114 are attached a path which is placed downstream from the catalyst test piece 200. The simulant gas which is generated by the model gas generator 100 is gone through inside of the catalyst test piece 200 and then it is analyzed its gas components by these analyzers.
Further, the experiment shown in
Following measuring instruments are used for the present evaluation test.
Next, a specific configuration of the catalyst test piece 200 will now be described in detail.
First, γ-Al2O3 was dispersed in ion-exchange water. An aqueous solution of barium acetate was then added in it. The resulting mixture heated to remove water from it, dried at 120 degrees Celsius, and pulverized to powder. The powder was then burned for two hours at 500 degrees Celsius. After burning, the burnt powder was immersed in a solution containing ammonium hydrogen carbonate, and then dried at 250 degree Celsius. As a result of that, barium-supported catalyst was obtained.
Next, the barium-supported catalyst was dispersed in ion-exchange water. An aqueous solution containing dinitro-diammine platinum was then added to support Pt. The resulting mixture was dried, pulverized, and burned for one hour at 450 degrees Celsius. According to this catalyst, the supported quantity of barium was 0.1 mole per 120 g of γ-Al2O3, and the supported quantity of Pt was 2 g.
H+ ion of ZSM-5 type zeolite (Si/Al ratio=40, H-type) was exchanged ion using silver nitrate, dried, and then burned at 450 degrees Celsius to prepare Ag ion-exchange ZSM-5. The Ag ion-exchange ZSM-5 was mixed with γ-Al2O3 being supported Pt and Ba to obtain a catalyst. The mixture ratio (ZSM-5: Al2O3) was 5:12.
A 30 mm diameter, 50 mm long, 4 mil/400 cpsi cordierite honeycomb was coated with the catalyst being prepared earlier and burned for one hour at 450 degrees Celsius. The coating amount was such that Al2O3 was coated at a rate of 120 g/L. Therefore, the Ag ion-exchange ZSM-5 would be coated at a rate of 50 g/L.
Meanwhile,
First, γ-Al2O3 was dispersed in ion-exchange water. An aqueous solution of barium acetate was then added in it. The resulting mixture heated to remove water from it, dried at 120 degrees Celsius, and pulverized to powder. The powder was then burned for two hours at 500 degrees Celsius. After firing, the burnt powder was immersed in a solution containing ammonium hydrogen carbonate, and then dried at 250 degree Celsius. As a result of that, barium-supported catalyst was obtained.
Next, the barium-supported catalyst was dispersed in ion-exchange water. An aqueous solution containing dinitro-diammine platinum was then added to support Pt. The resulting mixture was dried, pulverized, and burned for one hour at 450 degrees Celsius. According to this catalyst, the supported quantity of barium was 0.1 mole per 120 g of γ-Al2O3, and the supported quantity of Pt was 2 g.
A 30 mm diameter, 50 mm long, 4 mil/400 cpsi cordierite honeycomb was coated with the catalyst being prepared earlier and burned for one hour at 450 degrees Celsius. The coating amount was such that Al2O3 was coated at a rate of 120 g/L.
Following experiment conditions are used for the present evaluation test.
Temperature: control a temperature in the range 30 degrees Celsius-500 degrees Celsius
Temperature rise rate: 10 degrees Celsius/min.
Simulant gas compositions:
Simulant gas flow rate: 30 L/Min.
Injection gas compositions:
Injection gas flow rate: 6 L/min.
The electrical furnace being placed around the catalyst test piece 200 was controlled so that its temperature might be raised from low-temperature side. The injection gas was injected when the temperature was in the range of 30 degrees Celsius-300 degrees Celsius. Moreover, when the temperature was 300 degrees or higher, only simulant gas was injected without supplying the injection gas. The experiments was performed both the first experiment being used the catalyst sample 204 and the second experiment being used the catalyst sample 206. An exhaust gas purification efficiency was calculated as a percentage by subtracting the amount of NOx being emitted into downstream from the catalyst test piece 200 (hereinafter referred to as an “NOx outlet flow”) from the amount of NOx being introduced into the catalyst test piece 200 (hereinafter referred to as an “NOx inlet flow”) within the test time and then being divided by the NOx inlet flow within the test time.
NOx inlet flow=NOx concentration of simulant gas×simulant gas flow rate×test time (4)
NOx outlet flow=NOx concentration of downstream from the catalyst 200×gas flow rate (simulant gas and injection gas)×test time (5)
purification efficiency=(NOx inlet flow−NOx outet flow)/NOx inlet flow×100 (6)
Next, the second Embodiment of the present invention will now be described with reference to
As shown in
An HC adsorbent 46, in which zeolite based ZSM-5 is supported by a ceramic carrier, is placed in the exhaust purification catalyst 42 upstream from the NSR catalyst 44. The ZSM-5 functions as an HC adsorbent which adsorbs HC.
The exhaust emission control apparatus 40 according to the second embodiment includes an ozone supply device 30. The ozone supply device 30 includes an ozone injection orifice 34. The ozone injection orifice 34 is placed upstream from the NSR catalyst 44 and downstream from the HC adsorbent 46, and injecting ozone toward the NSR catalyst 44.
In the exhaust emission control apparatus 10 according to the above described first embodiment, it is assumed that the exhaust purification catalyst 20 in which the HC adsorbent, the NOx storage substance and the noble metal are supported on the common carrier is provided so that the NOx exhausted during a cold startup of the engine 12 is effectively stored in order to be prevented from being emitted into the atmosphere. However, according to the aforementioned configurations, the ozone is also injected into the HC adsorbent which is placed inside of the exhaust purification catalyst 20. Therefore, the injected ozone may react not only with the NOx but also with the HC adsorbed in the HC adsorbent, thereby decreasing an oxidized rate of NOx.
In view of the above circumstances, the second embodiment uses the exhaust purification catalyst 42, in which the HC adsorbent is separated from the NOx retention material. In the exhaust purification catalyst 42, the introduced ozone is effectively prevented from reacting with the HC adsorbed in the HC adsorbent 46 since the HC adsorbent 46 is positioned upstream from the ozone injection orifice as shown in
Further, according to the exhaust purification catalyst 42, since the NSR catalyst 44 is positioned downstream from the ozone injection orifice 34, all of the injected ozone is used for reacting with NOx. Therefore, it is possible to improve the oxidation rate of NOx and increase the storage amount of NOx.
Although the NSR catalyst 44 in which the noble metal Pt and BaCO3 functioning as an NOx storage substance are supported by the common ceramic carrier is used in the second embodiment, the configuration of the NSR catalyst 44 is not limited to this. For example, according to the gas-phase reaction of the above formulas (1) and (2), the region for oxidizing the NOx is not limited to a region on catalyst. Thus, it becomes possible, for instance, to support the NOx storage substance and noble metal separately in the NSR catalyst 44. More concretely, the NOx storage substance and the noble metal may be supported separately, for instance, at the upstream side and the downstream side of the carrier, respectively.
According to the aforementioned configurations, it is possible to improve the purification performance of the catalyst since the three-way catalyst in which the noble metal is supported and the NOx retention material 64 in which the NOx storage substance that can be a catalyst poison is supported are installed separately. Further, the NOx that is not stored by the NOx retention material 64 can be purified in the three-way catalyst 66 after the catalyst is activated for some extent since the three-way catalyst 66 is positioned downstream from the NOx retention material 64, whereby the NOx purification performance is improved.
Further, the interior configuration of the NSR catalyst 44 is not limited to the configuration in which the NOx storage substance and the noble metal are supported separately at the upstream side and the downstream side of the carrier; a configuration in which an upper layer side and a lower layer side are used for supporting them separately can be also used as the interior configuration. It should be noted that, in a case where the layered configuration is employed, it is preferable that the noble metal is arranged as the upper layer on the NOx storage substance so that the NOx desorbed from the NOx storage substance is reduced by the noble metal.
Although the exhaust purification catalyst 42 that has the HC adsorbent 46 and the NSR catalyst 44 therein is used in the above described second embodiment, the configuration of the catalyst is not limited to this. For example, the HC adsorbent 46 and the NSR catalyst 44 may be installed into the exhaust path 14 respectively without combining them into a single unit. Further, in this case, the various kinds of configurations can be taken as the ozone supply device 30. For instance, in order to add ozone to the exhaust gas which is flown into the NSR catalyst 44, an ozone generation device may be installed in the exhaust path 14 or the ozone may be injected from the ozone supply device 30 into a certain part of the exhaust path 14 which is positioned downstream from the HC adsorbent 46 and upstream from the NSR catalyst 44.
Further, although BaCO3 is used as the NOx storage substance in the second embodiment, the material of the NOx storage substance is not limited to this. For example, alkali metals, such as Na, K, Cs and Rb, alkali earth metals such as Ba, Ca and Sr, and rare earth elements such as Y, Ce, La and Pr may be used as needed. Further, the material of the catalyst is not limited to Pt. For example, noble metals such as Rh and Pd may be used as needed. Furthermore, the material of the HC adsorbent is not limited to ZSM-5. For example, various publicly known substances for adsorbing HC may be used as needed.
It should be noted that in the above described second embodiment, the ozone supply device 30 corresponds to the “ozone supply means” according to the first aspect of the present invention; and the exhaust purification catalyst 42 corresponds to the “catalyst” according to the first aspect of the present invention.
Next, evaluation test for confirming the advantage of the invention showing the second embodiment will now be described with reference to
As shown in
Next, concrete configurations of the catalyst test pieces 300, 310 will now be described in detail.
First, H+ ion of ZSM-5 type zeolite (Si/Al ratio=40, H-type) was exchanged ion using silver nitrate, dried, and then burned at 450 degrees Celsius to prepare Ag ion-exchange ZSM-5. Next, A 30 mm diameter, 50 mm long, 4 mil/400 cpsi cordierite honeycomb was coated with the catalyst being prepared earlier and burned for one hour at 450 degrees Celsius. The coating amount was 50 g/L.
First, γ-Al2O3 was dispersed in ion-exchange water. An aqueous solution of barium acetate was then added in it. The resulting mixture heated to remove water from it, dried at 120 degrees Celsius, and pulverized to powder. The powder was then burned for two hours at 500 degrees Celsius. After burning, the burnt powder was immersed in a solution containing ammonium hydrogen carbonate, and then dried at 250 degree Celsius. As a result of that, barium-supported catalyst was obtained.
Next, the barium-supported catalyst was dispersed in ion-exchange water. An aqueous solution containing dinitro-diammine platinum was then added to support Pt. The resulting mixture was dried, pulverized, and burned for one hour at 450 degrees Celsius. According to this catalyst, the supported quantity of barium was 0.1 mole per 120 g of γ-Al2O3, and the supported quantity of Pt was 2 g.
A 30 mm diameter, 50 mm long, 4 mil/400 cpsi cordierite honeycomb was coated with the catalyst being prepared earlier and burned for one hour at 450 degrees Celsius. The coating amount of Al2O3 was 120 g/L.
Following experiment conditions are used for the present evaluation test.
Temperature: control a temperature in the range 30 degrees Celsius-500 degrees Celsius
Temperature rise rate: 10 degrees Celsius/min.
Simulant gas compositions:
Simulant gas flow rate: 30 L/Min.
Injection gas compositions:
Injection gas flow rate: 6 L/min.
The electrical furnaces which are placed around the catalyst test pieces 300 and 310 were controlled so that its temperature might be raised from low-temperature side. The injection gas was injected when the temperature was in the range of 30 degrees Celsius-300 degrees Celsius. Moreover, when the temperature was 300 degrees or higher, only simulant gas was injected without supplying the injection gas. The experiments were performed both the first experiment being used the catalyst samples 304, 314 and the second experiment being used the catalyst sample 306. An exhaust gas purification efficiency was calculated by using above formula (5).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-355741 | Dec 2006 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2007/074539 | 12/20/2007 | WO | 00 | 10/23/2009 |
