Exhaust gas purifcation apparatus of internal combustion engine and catalyst for purifying exhaust gas of internal combustion engine
An exhaust gas purification apparatus for use in an internal combustion engine comprises an exhaust gas duct connected to the engine through which exhaust gas containing NOx gas passes, and a catalyst disposed in the exhaust gas duct such that it contacts the exhaust gas. The catalyst chemically adsorbs NOx when a stoichiometric amount of a gaseous oxidizing agent present in the exhaust gas is larger than that of a gaseous reducing agent present in the exhaust gas for reducing NOx, adsorbed NOx is catalytically reduced in the presence of a reducing agent when the stoichiometric amount of the oxidizing agent is not larger that of the reducing agent.
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This application is a continuation of U.S. patent application Ser. No. 10/119,075, filed Apr. 10, 2002, which is a continuation of U.S. patent application Ser. No. 09/620,650, filed Jul. 20, 2000 (now U.S. Pat. No. 6,397,582), which is a continuation of U.S. patent application Ser. No. 09/202,243, filed Dec. 10, 1998 (now U.S. Pat. No. 6,161,378).
BACKGROUND OF THE INVENTIONThis application claims the priority of Japanese patent documents No. 8-146981, filed Jun. 10, 1996; No. 8-153718, filed Jun. 14, 1996; No. 8-209587, filed Aug. 8, 1996, and 9-13655, filed Jan. 28, 1997, (PCT International Patent Application PCT/JP97/01955, filed Jun. 8, 1997) the disclosures of which are expressly incorporated by reference herein.
The present invention relates to a purification apparatus for an exhaust gas which is discharged or emitted from an internal combustion engine such as an automobile, and particularly to an apparatus which includes a catalyst for purifying an exhaust gas from an internal combustion engine that is operated under a lean air-fuel ratio (a lean burn), and from an automobile which has such a lean burn internal combustion engine.
Exhaust gas discharged from an internal combustion engine such an automobile includes carbon monoxide (CO), hydrocarbon (HC) and nitrogen oxide (NOx) etc. which pollute the environment, adversely affect the human body, and disturb the growth and the development of plants.
Accordingly, up to now a great deal of effort has gone into reducing the amount of such pollutants by improving a combustion in the internal combustion engine, and developing a method for purifying the discharged or the emitted exhaust gas using a catalyst to obtain a steady result.
Gasoline engine vehicles frequently utilize a three component catalyst in which platinum (Pt) and rhodium (Rh) are main active components. The oxidation of HC and CO and the reduction of NOx are carried out at the same time to convert the above air pollution materials to harmless materials.
It is characteristic of a three component catalyst, that it operates effectively only for exhaust gases which are generated within a range (“window”) in the vicinity of a stoichiometric air-fuel ratio.
In the conventional technique, the air-fuel ratio fluctuates in accordance with an operation condition of the automobile. A fluctuation region is principally controlled to the vicinity of the stoichiometric air-fuel ratio, which is a ratio between A (weight of air) and F (weight of fuel), being about 14.7 in case of the gasoline. Hereinafter, in the present specification, the stoichiometric air-fuel ratio is represented by A/F=14.7, but this value varies in accordance with kinds of the fuels.
However, when the engine is operated under a lean air-fuel ratio in comparison with the stoichiometric air-fuel ratio atmosphere, the fuel consumption can be improved. Therefore, the development of a lean burn combustion technique is promoted; and recently automobiles have been developed in which the engine is combusted under the lean area having the air-fuel ratio of more than 18.
However, when a conventional three component catalyst is adopted for purification of a lean burn exhaust gas, although the oxidation purification with respect to HC and CO is performed effectively, the reduction of NOx is not.
Accordingly, to promote the application of the lean burn system for large size vehicles and to enlarge the lean burn combustion time (that is, enlarge the operation area of the lean burn system), it is necessary to develop an exhaust gas purification technique which is suitable to the lean burn system. Thus, the development of a technique for purifying HC, CO and particularly NOx where a large quantity of oxygen (O2) is included in the exhaust gas, has been promoted vigorously.
Japanese patent laid-open publication No. 61,706/1988 discloses a technique in which HC is supplied upstream of a lean burn exhaust gas. The operation of a catalyst is facilitated by lowering the oxygen (O2) concentration in the exhaust gas to a concentration area for effective functioning of the catalyst.
Japanese patent laid-open publication No. 97,630/1987, Japanese patent laid-open publication No. 106,826/1987 and Japanese patent laid-open publication No. 117,620/1987, propose a technique in which N included in the exhaust gas (after the conversion of an easily absorbable NO2 by oxidizing NO) is absorbed and removed by contact with a catalyst having NOx absorbing ability. When the absorption efficiency decreases, by stopping a passing-through of the exhaust gas accumulated NOx is reduction-removed using H2, HC included in a methane gas and a gasoline etc., and so that NOx absorbing ability of the catalyst is regenerated.
Further, WO 93/07363 and WO 93/08383 discloses an exhaust gas purification apparatus in which an NOx absorbent material arranged at an exhaust gas flow passage absorbs NOx from a lean exhaust gas, and when an oxygen concentration in the exhaust gas is lowered the NOx absorbent material discharges the absorbed NOx. The exhaust gas absorbs NOx during the lean atmosphere and the absorbed NOx is discharged by lowering O2, concentration in the exhaust gas which flows into a NOx absorbent.
However, in Japanese patent laid-open publication No. 61,708/1988, to attain a composition of the exhaust gas which corresponds to the air-fuel ratio of A/F=14.7 where the catalyst can function (O2 concentration having about 0.5%), it needs a very large quantity of HC. A use of a blow-by gas in this patent document is effective, but the blow-by gas does not have an amount which is sufficient for efficient to treat an exhaust gas during an operation of an internal combustion engine. It is possible technically to throw the fuel but it eliminates the fuel consumption gains achieved by the lean burn system.
In Japanese patent laid-open publication No. 97,630/1987, Japanese patent laid-open publication No. 106,826/1987 and Japanese patent laid-open publication No. 117,620/1987, to regenerate a NOx absorbent material a flow of exhaust gas is stopped and the gaseous reducing agent of HC etc. is contacted to NOx absorbent. Further, two NOx absorbent materials are provided and the exhaust gas flows alternately to these two NOx absorbent materials. It is therefore necessary to provide an exhaust gas change-over mechanism, which complicates the structure of the exhaust gas treatment apparatus.
In WO 93/07363 and WO 93/08383, the exhaust gas is flowed continuously to an NOx absorbent material, and the NOx in the exhaust gas is absorbed during the lean atmosphere. By lowering O2 concentration in the exhaust gas, the absorbed NOx is discharged and the NOx absorbent material is regenerated. Accordingly, since the change-over of the exhaust gas flow is unnecessary, the problem in the above stated system can dissolved. However, these systems require a material which can absorb NOx during the lean condition and can discharge NOx when O2 concentration in the exhaust gas is lowered. Since the repeated NOx absorption and discharge inevitably causes a periodic change of a crystal structure of the absorbent, it is necessary to take a careful consideration about the durability of the absorbent. Further, it is necessary to treat the discharged NOx; in the case of a large quantity of the discharged NOx it may be necessary to provide a post-treatment using a three component catalyst.
SUMMARY OF THE INVENTIONIn the light of the problems in the above stated prior arts, the object of the present invention is to provide an internal combustion engine exhaust gas purification apparatus which has a simple structure, consumes a small amount of gaseous reducing agents, has superior endurance and which effectively removes harmful components such as NOx from a lean burn exhaust gas converting them to a harmless component.
Another object of the present invention is to provide a catalyst for use in an exhaust gas purification apparatus of an internal combustion engine.
According to the present invention, an exhaust gas purification apparatus for use in an internal combustion engine comprises an exhaust gas duct connected to the engine, through which the exhaust gas containing NOx gas passes, and a catalyst disposed in the exhaust gas duct so that it contacts the exhaust gas. The catalyst chemically adsorbs NOx when a stoichiometric amount of a gaseous oxidizing agent present in the exhaust gas is larger than the amount of a gaseous reducing agent present in the exhaust gas for reducing NOx, while adsorbed NOx is catalytically reduced in the presence of the reducing agent when the stoichiometric amount of the oxidizing agent is not larger that of the reducing agent.
According to the present invention, an apparatus for purifying an exhaust gas from an internal combustion engine comprises an exhaust gas duct connected to the engine, through which the exhaust gas containing NOx gas passes, and a catalyst disposed in the exhaust gas duct so that it contacts the exhaust gas. The catalyst adsorbs NOx under when the amount of a gaseous oxidizing agent present in the exhaust gas is larger than that of a gaseous reducing agent for NOx added to the exhaust gas in a stoichiometric relation, while adsorbed NOx is catalytically reduced in the presence of the reducing agent when the amount of the oxidizing agent is not larger that of the reducing agent in the stoichiometric relation.
According to the present invention, an apparatus for purifying an exhaust gas from an internal combustion engine comprises an exhaust gas duct connected to the engine, through which the exhaust gas containing NOx gas passes, and a catalyst disposed in the exhaust gas duct so that it contacts with the exhaust gas. The catalyst adsorbs NOx when a stoichiometric amount of a gaseous oxidizing agent present in a lean combustion exhaust gas is larger than that of a gaseous reducing agent present in the lean combustion exhaust gas for reducing NOx, while the adsorbed NOx is catalytically reduced in the presence of the reducing agent when a stoichiometric amount of the oxidizing agent is not larger that of the reducing agent in a stoichiometric or fuel rich combustion exhaust gas.
According to the present invention, an apparatus for purifying an exhaust gas from an internal combustion engine comprises an exhaust gas duct connected to the engine, through which the exhaust gas containing NOx gas passes, a device for controlling the air-fuel ratio of the exhaust gas, and a catalyst disposed in the exhaust gas duct so that it contacts with the exhaust gas. The air-fuel ratio is switched from a range in which the catalyst chemically adsorbs NOx in the lean combustion exhaust gas to a range in which adsorbed NOx is catalytically reduced in the presence of the reducing agent in a stoichiometric or fuel rich combustion exhaust gas.
The catalyst according to the present invention comprises a heat resistant carrier body and catalytic compounds supported thereon. The catalytic compounds comprise at least one of sodium and potassium, at least one of magnesium, strontium and calcium, and at least one of platinum, palladium and rhodium. In at least some embodiments, a base member supports the heat resistant carrier body.
According to the present invention, the reducing agent to be added to the lean combustion exhaust gas is at least one of gasoline, light oil, kerosene, natural gas, their reformed substances, hydrogen, alcohol, ammonia gas, engine blow-by gas and canister purging gas. The reducing agent is supplied to the lean combustion exhaust gas in response to signals from the stoichiometric establishing unit.
The exhaust gas purification apparatus according to the present invention further comprises a manifold catalyst which is disposed in the exhaust gas duct immediately after the engine, upstream of the catalyst, and functions as a three component catalyst and a combustion catalyst.
According to another feature of the present invention, in the exhaust gas purification apparatus, a second catalyst is disposed in the exhaust gas duct of a direct fuel injection engine.
According to yet another feature of the present invention, the exhaust gas purification apparatus further comprises a three component catalyst or a combustion catalyst is disposed in the exhaust gas duct upstream of the catalyst.
According to the present invention, an apparatus for purifying an exhaust gas from an internal combustion engine comprises an exhaust gas duct connected to the engine, through which the exhaust gas containing NOx, SOx and oxygen passes, and a catalyst which chemically adsorbs NOx when the exhaust gas is emitted from lean combustion, and in which adsorbed NOx is catalytically reduced when a gaseous reducing agent is added to the lean combustion exhaust gas in such an amount that a stoichiometric amount of oxygen is not larger than that of the reducing agent.
The catalyst adsorbs or absorbs SOx in the lean condition, and releases SOX in the stoichiometric or rich condition.
According to the present invention, a catalyst for purifying an exhaust gas from an internal combustion engine comprises a base member, a heat resistant carrier body supported on the base member, and catalyst components supported on the carrier body. The carrier body has a number of small hollows extending in the direction of gas flow of the exhaust gas.
According to the present invention, the catalyst compounds comprise at least one alkali metal, at least one alkali earth metal (other than barium), at least one noble metal and at least one rare earth metal.
According to the present invention, an exhaust gas purification apparatus for use in an internal combustion engine comprises a catalyst which chemically adsorbs NOx when the amount of a gaseous oxidizing agent is greater than that of a gaseous reducing agent in a stoichiometric relation between the gaseous oxidizing agent and the gaseous reducing agent, and catalytically reduces adsorbed NOx when the gaseous reducing agent is equal to or exceeds the gaseous oxidizing agent. The catalyst is provided in an exhaust gas flow passage for a flow of an exhaust gas generated at a lean air-fuel ratio and at a rich air-fuel ratio or a stoichiometric air-fuel ratio.
According to the present invention, an exhaust gas purification apparatus for use in an internal combustion engine comprising a catalyst for chemically adsorbing NOx under a condition where an gaseous oxidizing agent is more than a gaseous reducing agent in a stoichiometric relation between the gaseous oxidizing agent and the gaseous reducing agent and a device which controls an air-fuel ratio to switch conditions between NOx chemical adsorption to the catalyst and catalytic reduction chemically of NOx to the catalyst.
According to the present invention, an exhaust gas purification apparatus comprises a catalyst which chemically adsorbs NOx when, in a stoichiometric relation between gaseous oxidizing agent and gaseous reducing agent in an exhaust gas flowing an exhaust gas flow passage in the internal combustion engine, the amount of gaseous oxidizing agent is more than the amount of gaseous reducing agent, and catalytic-reduces adsorbed NOx when the amount of gaseous oxidizing agent equals or exceeds the amount of gaseous reducing agent. The catalyst is provided in the exhaust gas flow passage where an exhaust gas burned at a lean air-fuel ratio and an exhaust gas burned at a rich or stoichiometric air-fuel ratio flow into alternately.
The exhaust gas purification apparatus according to the present invention provides a stoichiometric relation between oxidation and reduction of gaseous oxidizing agent and gaseous reducing agent. A control means for controlling the stoichiometric relation between gaseous oxidizing agents and gaseous reducing agents comprises a timing control means for controlling the time at which the stoichiometric relation between gaseous oxidizing agent and gaseous reducing agent changes over from a first condition in which the amount of gaseous oxidizing agent is more than that of a gaseous reducing agent, to another condition in which the amount of gaseous reducing agent is equal to or exceeds the amount of gaseous oxidizing agent. It also comprises a gaseous reducing agent excess time control means for controlling a time when, in the stoichiometric relation between oxidation and reduction, the gaseous reducing agent is held to an amount equal to or greater than the gaseous oxidizing agent.
According to the present invention, the catalyst has the ability to chemical adsorb NOx, and to catalytic-reduce NOx. Even when the oxygen concentration decreases, the catalyst does not discharge NOx. These features can be obtained by a catalyst which comprises at least one element selected from among the alkali metals and alkali earth metals in the element periodic table (but not including barium (Ba)), and at least one selected from noble metals comprising platinum (Pt), palladium (Pd) and rhodium (Rh). Further, the catalyst has an ability for catalytic oxidizing HC or CO etc.
The catalyst has a high NOx absorption ability in a lean atmosphere and further under the catalyst temperature of 250-500° C. Further, to recover its NOx adsorbing ability by reduction of the absorbed NOx, the catalyst must maintain a stoichiometric atmosphere or a rich atmosphere for a time of about 30 seconds or less.
Accordingly, to perform effectively NOx adsorption and to recover NOx adsorbing ability, it is desirable to provide the catalyst at a position of an exhaust gas duct where an inlet port gas temperature of the catalyst is 250-500° C. The above temperature range is one which can obtain normally under the car-body floor.
NOx adsorbing ability of the catalyst is lowered due to poisoning by SOx originated fuel (gasoline). However, when the catalyst is maintained several (for example, ten) minutes at 400-800° C. in a stoichiometric or rich atmosphere, SOx is removed and then NOx adsorbing ability is recovered.
Accordingly, when the gasoline quality is bad (high sulfur content) and the catalyst suffers from poisoning by SOx, it is desirable to position the catalyst in an exhaust gas duct where an inlet port gas temperature of the catalyst is 400-800° C. The above temperature range is one which can obtain under the car-body floor.
When the catalyst is used for an automobile, it is desirable to form it as a honeycomb having NOx adsorption ability of more than 0.01 mol per an apparent honeycomb volume one (1) liter.
Further, it is desirable to set the specific surface area of the catalyst layer on the honeycomb substrate (the honeycomb base body), measured by absorbing nitrogen according to BET method, at more than 50 m2/g.
In the exhaust gas, the gaseous oxidizing agents are O2, NO, NO2, etc. and are mainly oxygen. The gaseous reducing agents are HC supplied in an internal combustion engine, HC (including oxygen containing hydrocarbon) generated in a combusting process as a derivative from fuel, CO, H2 etc. Furthermore, a reducing material such as HC can be added in the exhaust gas as a reducing component.
When the lean exhaust gas contacts the three component catalyst, HC, CO, H2 etc. as the gaseous reducing agents for reducing NOx to nitrogen (N2), cause a combustion reaction with oxygen (O2) as the gaseous oxidizing agent in the exhaust gas. NOx (NO and NO2) reacts with these gaseous reducing agents and is reduced to nitrogen (N2). Normally, since both reactions proceed in parallel, a utilization rate of the gaseous reducing agents for reducing NOx is low.
Particularly at a high reaction temperature of more than 500° C. (depending on the catalyst material), an occupation rate of the latter reaction becomes large. Hence, by separating NOx from the exhaust gas (at least from O2) using the catalyst, and then carrying out the catalytic-reaction with the gaseous reducing agents, it is possible to achieve an effective reduction of NOx to N2. According to the present invention, the catalyst is used to adsorb and remove NOx in the lean exhaust gas, whereby NOx in the exhaust gas is separated from O2.
Next, according to the present invention, with regard to the oxidation reduction relation, namely the stoichiometric relation between oxidation and reduction, which is constituted by the gaseous oxidizing agents (O2 and NOx etc.) and the gaseous reducing agents (HC, CO, H2 etc.) in the exhaust gas, the gaseous reducing agent is made equal to or larger than the gaseous oxidizing agent. In this manner NOx adsorbed on the catalyst is reduced to N2 according to the catalytic-reaction with the gaseous reducing agent such as HC.
NOx in the exhaust gas is substantially constituted of NO and NO2. The reaction property of NO2 is rich in comparison with that of NO. Accordingly, when NO is oxidized to NO2, the adsorption-removal and the reduction of NOx in the exhaust gas are performed easily.
The present invention includes a method of oxidizing and removing NOx in the exhaust gas to NO2 by the coexistent O2, and an oxidation means for attaining the above method (such as means having NO oxidation function and the means for providing an oxidation catalyst at a pre-stage of the catalyst).
The reduction reaction of a chemically adsorbed NO2 according to the present invention will be described generally with following reaction formulas:
MO—NO2+HCMO+N2+CO2+H2O
MCO3+N2+H2O
where M indicates a metal element and MO—NO2 indicates a combination State Of NO2 of a metal oxide surface. A reason for employing MCO3 as the reduction generation substance will be explained later.
The above reaction is exothermic. Alkali metals and alkali earth metals are used as the metal M, and the reaction heat is estimated by representing Na and Ba respectively as follows, under a standard condition (1 atmosphere, 25° C.):
2NaNO3 (s)+{fraction (5/9)}C3H6(g)
2Na2NO3(s)+N2 (g)+⅔CO2 (g)+{fraction (5/3)}CO2 (g)
[−ΔH=873 k joule]
Ba(NO3)2(s)+{fraction (5/9)}C3H6(g)
BaCO3(s)+N2 (g)+⅔CO2(g)+{fraction (5/3)}H2O(g)
[−ΔH=751 k joule]
wherein, s indicates a solid state and g indicates a gaseous state. Here, a thermodynamic value of the solid state is used, as that of an adsorbed state.
It should be noted that the combustion heat of {fraction (5/9)} mole C3H6 is 1,070 k joule, and each of the above reactions is exothermic. The heat, which matches that for the combustion beat of HC, heat is transferred to the exhaust gas, and thus a local rise in temperature of a surface of the catalyst can be restrained.
Where the catching agent for NOx is an NOx absorbent, NOx which is taken into the mass of the absorbent is reduced. Heat transfer to the exhaust gas is limited, causing a rise in temperature of the absorbent. This exothermically generated heat shifts the balance of the absorption reaction to that of NOx discharging or NOx emission.
-
- absorption
MCO3(s)+2NO2+½O2ØøM(NO3)2+CO2 - discharging
- absorption
Even though the concentration of the gaseous reducing agents is increased to reduce rapidly NOx concentration in the exhaust gas which is discharged to the outside of the absorbent, the reaction between NO2 and HC in the gaseous phase does not proceed.
Accordingly, the amount of discharged NOx cannot be reduced fully by an increment of the gaseous reducing agents. Further, at a stage where the adsorption amount of NOx is small, a reduction operation may occur; however, since the regeneration frequency of NOx absorbent increases, it is not put to practical use.
The catalyst according to the present invention generates a small absolute amount of exothermic heat so as to catch NOx near its surface in accordance with chemical adsorption. Also the rise in temperature of the catalyst is small, so as to transfer heat rapidly to the exhaust gas. Accordingly, it is possible to prevent the discharge of NOx after it is captured.
The catalyst according to the present invention utilizes a material which catches NOx at or near its surface by chemical adsorption, and does not cause NOx discharging or NOx emission in accordance with the exothermic reaction during the reduction of NOx.
Further, the catalyst according to the present invention adsorbs NOx contained in lean exhaust gas at its surface, and during the reduction of NOx it does not cause NOx discharge in accordance with the lowering of the oxygen concentration.
The inventors of the present invention have determined that the above stated features can be realized using a catalyst which is selected from at least one of alkali metals and alkali earth metals (classified in an element periodic table) and at least one of noble metals selected from platinum (Pt), rhodium (Rh) and palladium (Pd), but does not contain barium (Ba). Preferably, the catalyst according to the present invention includes at least one element selected from potassium (K), sodium (Na), and strontium (Sr), and noble metal elements.
In the exhaust gas purification apparatus according to the present invention, a catalyst arranged at an exhaust gas flow passage includes at least one element selected from potassium (K), sodium (Na), magnesium (Mg), strontium (Sr) and calcium (Ca), as well as noble metal elements.
In the exhaust gas purification apparatus, in the case of a stoichiometric relation between oxidation and reduction of each of the components included in the exhaust gas, the gaseous oxidizing agent is equal to or greater than the gaseous reducing agent, and NOx is chemically adsorbed on the catalyst. On the other hand, when the gaseous reducing agent is equal to or greater than the gaseous oxidizing agent, NOx which has been absorbed on the catalyst is reduced, according to the catalytic-reaction with the gaseous reducing agent, to harmless N2.
The catalyst in the present invention can be applied suitably in particular by following substances.
The composition is constituted of a metal and a metal oxide substance (or a complex oxide substance) which contains at least one element selected from potassium (K), sodium (Na), magnesium (Mg), strontium (Sr) and calcium (Ca), at least one selected from rare earth metals, and at least one element selected from the noble metals including platinum (Pt), rhodium, (Rh), and palladium (Pd). This composition, which is supported on a porous heat-withstanding metal oxide substance, has a superior NOx adsorbing ability.
As the earth metal element, cerium (Ce) or lanthanum (La), particularly Ce, is preferable. The earth metal element has a function for exhibiting the three component function to the catalyst under the stoichiometric atmosphere or the rich atmosphere.
At least one of titanium (Ti) and silicon (Si) can be added to the catalyst according to the present invention, improving the heat resistant property and SOx endurance property of the catalyst. Ti or Si has a function for adsorbing or absorbing SOx under the lean atmosphere, or for discharging the adsorbed or absorbed SOx in a stoichiometric atmosphere or a rich atmosphere.
In the catalyst of the present invention, alkali metals, alkali earth metals, noble metals, rare earth elements, titanium (Ti) and silicon (Si) are held on the porous support or porous carrier member, which is supported or carried on a substance body. For the purpose of heat resistance, -Al2O1 is preferably employed as the porous support. As the substance body, a cordierite, mullite, a metal, for example, a stainless steel is preferable.
As the crystal structure of Ti which is held on the porous support, an amorphous oxide state is preferable. Further, in case where the catalyst includes Si and alkali earth metals at the same time, as both the crystal structures Si and alkali earth metals, an amorphous oxide state is preferable.
In the catalyst of the present invention, it is preferable to include in the porous support (porous carrier member), alkali metals of 5-20 wt %, and alkali earth metals of 3-40 wt %. Further, it is also preferable to include Pt of 0.5-3 wt %, Rh of 0.05-0.3 wt %, and Pd of 0.5-15 wt %, respectively. Mg prevents the cohesion or condensation of the active components which are held on the porous support, such as the noble metal.
It is also preferable to include the rare earth metals of 5-30 wt %, Ti of 0.1-30 wt %, and Si of 0.6-5 wt % as silica in the porous support.
The present invention provides a catalyst which comprises, on the porous support, sodium (Na), magnesium (Mg), and at least one element selected from platinum (Pt), palladium (Pd), and rhodium (Rh), as well as at least one selected from cerium (Ce) and lanthanum (La). Further, the porous support also preferably includes Na of 5-20 wt %, Mg of 1-40 wt % under a weight ratio Mg/(Na+ Mg), Pt of 0.5-3 wt %, Rh of 0.05-0.3 wt %, and Pd of 0.5-15 wt % are included.
In the exhaust gas purification apparatus according to the present invention, to chemically adsorb NOx to the catalyst, or to catalytically reduce the chemically adsorbed NOx, means must be provided for controlling the stoichiometric relation between oxidation and reduction by the gaseous oxidizing agents and the gaseous reducing agents in the exhaust gas. By providing a means for controlling the stoichiometric relation between oxidation and reduction, it is possible to assure that the gaseous reducing agent equals or exceeds the gaseous oxidizing agent. For example, the combustion condition in the internal combustion engine can be adjusted to a stoichiometric or a rich air-fuel ratio, or a gaseous reducing agent can be added to the lean burn exhaust gas.
One method of achieving the former is to control the fuel injection amount in accordance with the output of the oxygen concentration sensor and the output of the intake air flow amount sensor provided in the exhaust gas duct. In this method, some of the cylinders are operated with a rich mixture and the remainder are operated in a lean mixture. In the mixed components of the exhaust gas all of the cylinders the gaseous reducing agent is equal to or is greater than the gaseous oxidizing agent in the stoichiometric relation between the oxidation and the reduction.
The latter can be attained by each of following methods.
One method is to add a gaseous reducing agent to the exhaust gas flow upstream of the catalyst. As the gaseous reducing agent, gasoline, light gas oil, natural gas, reforming material thoseof, hydrogen, alcohol materials and ammonium materials can be applied. It is effective to introduce the blow-by gas and the canister purging gas at the upstream of the catalyst and to add the gaseous reducing agent such as hydrocarbon (HC) contained in the above materials. In an internal combustion engine with direct fuel injection, it is effective to inject the fuel during the exhausting process and to add the fuel as the gaseous reducing agent.
As the catalyst in the present invention, various shapes can be applied. In addition to a honeycomb shape which is obtained by coating the catalyst components onto a honeycomb shaped member comprised of cordierite or metal materials such as a stainless steel, a pellet shape, a plate shape, a particle shape and a powder shape can be applied.
In the present invention, the apparatus can provide means for establishing the time when the gaseous reducing agent is equal to or is greater than the gaseous oxidizing agent. The above timing is obtained by each of following methods.
In one technique, in accordance with the air-fuel ratio setting signal which is determined by ECU (engine control unit), the engine rotation number signal, the intake air amount signal, the intake air pipe pressure signal, the speed signal, the throttle valve opening degree signal, the exhaust temperature etc., the NOx discharging amount during lean operation is estimated and the integration value thereof is exceeds over a predetermined setting value.
In another method, in accordance with the signal of the oxygen sensor (or A/F sensor) arranged upstream or downstream of the catalyst in the exhaust gas flow passage, the accumulated oxygen amount is detected, and the accumulated oxygen amount exceeds over a predetermined amount. As a modified embodiment, the accumulated oxygen amount during the lean operation time exceeds a predetermined amount.
In another approach, in accordance with the signal of NOx sensor arranged at the upstream of the catalyst in the exhaust gas flow passage, the accumulated NOx amount is detected, and the accumulated NOx amount during the lean operation time exceeds over a predetermined amount.
In still another method, in accordance with the signal of NOx sensor arranged at the downstream of the catalyst in the exhaust gas flow passage, NOx concentration is detected, and NOx concentration exceeds over a predetermined concentration.
According to the present invention, further the apparatus provides the means for establishing the maintenance time where the gaseous reducing agent is equal to or exceeds the gaseous oxidizing agent. The time during which the gaseous reducing agent excess condition and the throw-in gaseous reducing agent amount is maintained can be determined taking into consideration the specifications and characteristics of the adsorbent and the internal combustion engine. The above methods can be realized by adjusting the stroke, the injection time and the injection interval of the fuel injector.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF DRAWINGS
Hereinafter, one embodiment of an exhaust gas purification apparatus and an exhaust gas purification catalyst for use in an internal combustion engine according to the present invention will be explained. However, the present invention will not be limited within the following embodiments.
Characteristics and Representative Embodiments of Catalyst
The characteristics of a catalyst for use in an internal combustion engine in accordance with the present invention will now be explained.
(Catalyst Preparation Method)
A catalyst N-N9 was obtained according to a following method.
In a first embodiment, nitric acid alumina slurry was obtained by mixing alumina powders with alumina-sol obtained by peptizing boehmite by nitric acid. Then a cordierite honeycomb was immersed in the slurry and the cordierite honeycomb was pulled up rapidly. The slurry enclosed in a cell was removed by performing an air-blow process, and after drying of the honeycomb the honeycomb was calcined at 450° C.
The above processes was carried out repeatedly and alumina of 150 g per liter of an apparent volume of the honeycomb was coated.
On this alumina coated honeycomb catalyst active components were held and then a honeycomb shape catalyst was obtained.
In another example, the alumina coated honeycomb was immersed in a cerium nitrate (Ce(NO3)2) solution and the honeycomb was dried at 200° C. After drying, the honeycomb was calcined for 1 (one) hour at 600° C. In succession, it is immersed in a mixture liquid comprised of sodium nitrate (NaNO3) solution, titania-sol solution and magnesium nitrate (Mg(NO3)2) solution. The honeycomb was then dried at 200° C. and calcined for 1 (one) hour at 600° C.
In still another example, the honeycomb was immersed in a solution comprised of dinitrodiamime Pt nitrate solution and rhodium nitrate (Rh(NO3)2) solution. The honeycomb was then dried at 200° C. the honeycomb, and calcined for 1 (one) hour at 450° C. Finally, it was immersed in a magnesium nitrate (Mg(NO3)2) solution, dried at 200° C., and calcined for 1 (one) hour at 450° C.
With the above process, a honeycomb shaped catalyst was obtained, in which Ce, Mg, Na, Ti, Rh and Pt were held on alumina (Al2O3) and is 2Mg-(0.2Rh, 2.7Pt)-(18Na, 4Ti, 2Mg)-27ce/Al2O3. Herein, /Al2O3 shows that the active component was held on Al2O3; the numerical value preceding the element is the weight (g) of the indicated metal component which was supported per 1 (one) liter of the apparent volume of the honeycomb.
An expressed order shows a support order or a carrier order and the elements were held in accordance with an order of the component for separating from the expressed component near to Al2O3, namely, on Al2O3, 27Ce, (18Na, 4Ti, 2Mg), (0.2Rh, 2.7Pt), and 2Mg are held in sequence, and the component bound up with parenthesis were supported at the same time. The amount of each of the respective active components which was deposited onto the carrier can be varied by varying the active component concentration in the immersed solution.
A catalyst N-K9 was prepared according to the following method.
In place of sodium nitrate (NaNO3) solution used in the preparation for the catalyst N-N9, potassium nitrate (KNO3) solution was used; otherwise a method was used which was similar to that for preparing the catalyst N-N9. As a result, a catalyst N-K9 comprised of 2Mg-(0.2Rh, 2.7Pt)-(18K, 4Ti, 2Mg)-27Ce/Al2O3, was obtained.
Further, with a similar method, a comparison catalyst N-R2 comprised of 2Mg-(0.2Rh, 2.7Pt)-27Ce/Al2O3 was obtained.
(Performance Evaluation Method)
After the catalysts obtained by the above stated methods were thermally treated at 700° C. under an oxidizing atmosphere for 5 (five) hours, the characteristics were evaluated using the following methods.
On an automobile in which a lean burn gasoline engine was mounted having the displacement volume of 1.8 liters, the honeycomb shape catalysts having a volume of 1.7 liters prepared using the above stated methods were mounted, and the NOx purification characteristics were evaluated.
(Characteristics of Catalysts)
When the catalyst N-N9 was mounted, and a 30 second period of rich operation (having A/F=13.3) and an about 20 minutes period of a lean operation (having A/F=22) were repeated alternately, the NOx purification characteristics shown in
When the fuel is gasoline, a mass composition of the gasoline comprises carbon (C) of about 85.7% and hydrogen (H) of about 14.3%. Herein, when the gasoline of F (g) is burned, carbon (C) of 0.857×F (g) reacts with oxygen (O2) of 0.857F/12 mol and hydrogen (H) of 0.143×F (g) reacts with oxygen (O2) of 0.143F/4 mol. A necessary air amount A (g) is expressed as following:
A=((0.857/12+0.143/4)F×28.8)/0.21=14.7F
wherein, 28.8 is air molecular amount (g/mol) and 0.21 is oxygen (O2) amount rate in air. A/F=14.7 indicates a stoichiometric air-fuel ratio.
Accordingly, when A/F=13.3, to the fuel (a gaseous reducing agent) of F (g), it shows an insufficient amount (a reduction atmosphere) of the air (the gaseous oxidizing agent) of 1.39F (g). On the other hand in case of A/F=22, to the fuel of F (g), it shows an excess (an oxidization atmosphere) of the air (the gaseous oxidizing agent) of 7.31F (g).
As shown in
The NOx purification rate during lean operation decreased gradually; that is, the initial purification rate of 100% decreased to about 40% after 20 minutes. However, the reduced purification rate recovered to 100% after 30 seconds of rich operation. When lean operation was carried out again, NOx purification performance was recovered and the above stated change in time lapse was repeated.
Even when the lean operation and the rich operation were repeated in plural times, the velocity of the lowering in time lapse of NOx purification rate during the lean operation was unchanging. Thus, the NOx absorption performance was fully regenerated according to the rich operation.
The vehicle speed was constant at about 40 km/h (the exhaust gas space velocity (SV) was constant at about 20,000 /h) and NOx concentration in the exhaust gas was varied by varying the ignition periods. The relationship between NOx concentration and NOx purification rate in the lean exhaust gas was determined, and is shown in
NOx purification rate decreased with time; however, the more NOx concentration lowered, the lower the rate of decrease. The amount of NOx that was removed prior to NOx purification rates of 50% and 30% was estimated through
NOx amounts which were caught were substantially constant, regardless of NOx concentration. The absorption amount did not depend to the concentration (pressure) of the adsorbent, which is a feature of the chemical adsorption.
In the test catalysts, first Pt particles were used as an NOx absorption medium. A CO adsorption amount evaluation which is frequently used as means for evaluating the exposed Pt amount was carried out; and CO adsorption amount (at 100° C.) was found to be 4.5×10−4 mol. This value was about {fraction (1/100)} of the above stated NOx adsorption amount; and therefore it was clear that Pt does not work as a main role for NOx adsorbent.
On the other hand, BET surface area (measured by nitrogen adsorption) of this catalyst (including cordierite as a substrate) was measured about 25 m2/g and was 28,050 m2 per the honeycomb 1.7 liters. Further, the chemical structure of the Na contained in the catalyst according to the present invention was studied. From the facts that CO2 gas was generated and dissolved in an inorganic acid, and from a value of a point of inflection in a pH neutralization titration curve line, it was determined that Na existed mainly as Na2CO3.
Supposing all of the surface was occupied by Na2CO3, Na2CO3 of 0.275 mol would be exposed on the surface. (As the specific gravity of Na2CO3 is 2.533 g/mol, the volume of one molecular of Na2CO3 can be estimated. Supposing Na2CO3 is a cube, an area of one face of Na2CO3 was estimated and the estimated area was used as the occupation area of the surface Na2CO3).
In accordance with the above stated reaction formula, Na2CO3 of 2.75 mol has an ability to adsorb NO2 of 0.55 mol. However, the amount of NOx which had been removed by the catalyst according to the present invention is on the order of 0.04 mol, which is less than {fraction (1/10)} of the ability.
The above difference attributed the cause that BET method evaluated the physical surface area and the surface area of Al2O3 with the surface area of Na2CO3 was evaluated.
The above stated evaluations show the adsorbed NOx amount was far greater than the NOx catching power of Na2CO3 bulk, and at least NOx was caught at a limited area of the surface or the vicinity of the surface of Na2CO3.
Further, in
Regeneration starts immediately after the stoichiometric change-over. Since the exhaust gas NOx concentration in the exhaust gas of A/F=14.2 is high at that time, the inlet port NOx concentration in the stoichiometric operation increases substantially, and at the same time the outlet NOx concentration increases in a transient manner. However, the outlet port NOx concentration is always substantially lower than the inlet port NOx concentration. The regeneration proceeds rapidly, and the outlet port NOx concentration approaches zero (0) within a short time.
As clearly understood from the above, the A/F value during regeneration affects the time required for regeneration. A/F value, the time and gaseous reducing agent amount suitable for the regeneration are influenced by the composition (such as the shape, temperature and SV value) of the catalyst, the kind of the gaseous reducing agent, and the shape and the length of the exhaust gas flow passage. Accordingly, the regeneration condition is determined overall by all of the above stated items.
Similarly to case of the above catalyst N-N9, the outlet port NOx concentration is always much less than the inlet port NOx concentration, further the regeneration of the catalyst proceeds within a short time.
(Basic Characteristics of Catalyst)
Using a model gas, the basic characteristics (in particular, the effect of oxygen concentration on the NOx purification rate) were evaluated.
The cordierite honeycomb of the catalyst N-N9 having 6 ml was filled up in a silica reaction tube having an inner diameter of 28 mm and the model gas was passed through the tube. The oxygen concentration in the model gas was varied, and the effect on the NOx purification rate was studied. The reaction temperature was 300° C. at the inlet port gas temperature of the catalyst.
Initially, the gas composition comprises of O2 of 5% (volume ratio: same hereinafter), NO of 600 ppm, C3H4 of 500 ppm (1,500 ppm as Cl), CO of 1,000 ppm, CO2 of 10%, H2O of 10%, and the balance of N2. After ten (10) minutes, when NOx purification rate has been stable, the oxygen concentration was lowered to a predetermined value and maintained for twenty (20) minutes. Finally, the gas mixture was then returned again to its initial composition. NOx concentration change for the above time interval was varied with six different O2 concentrations, (0%, 0.5%, 0.7%, 1%, 2% and 3%), and the graphs shown in
Further, in
Next, a gas comprising O2 of 5%, NO of 600 ppm, and the balance of N2 was used, and the oxygen concentration was similarly varied.
In
An Exhaust Gas Purification Apparatus
ECU comprises an I/O LSI as an input/output interface, an execution processing unit MPU, memory units (RAM and ROM) for storing many control programs, and a timer counter, etc.
The above stated exhaust gas purification apparatus functions as follows. After the intake air to the engine 99 is filtered through an air cleaner 1, it is metered by the air flow sensor 2. Further, the air passes through the throttle valve 3, is received for fuel injection through an injector 5, and supplied to the engine 99 as an air-fuel mixture. The signals of the air flow sensor 2 and others are inputted into ECU (engine control unit).
In the ECU, by the latter stated method the operation conditions of the internal combustion engine and of the catalyst are evaluated, and an air-fuel ratio is determined. By controlling the injection period etc. of the injector 5, the fuel concentration of the air-fuel mixture is established at a predetermined value.
The air-fuel mixture sucked into the cylinders is ignited and burned by means of an ignition plug 6, which is controlled according to signals from ECU. The combustion exhaust gas is led to an exhaust gas purification system, which includes a catalyst 18. During stoichiometric operation NOx, HC and CO are purified according to the three component catalyst function. During lean operation NOx is purified by adsorption and at the same time HC and CO are purified by combustion.
Further, in accordance with the judgment and the control signal of the ECU, the NOx purification ability of the catalyst 18 is monitored continuously during lean operation, and when its NOx purification capacity lowers, the air-fuel ratio etc. is shifted to the rich side, so that the NOx purifying ability is recovered. With the above stated operation, in this apparatus, the exhaust gas is purified effectively under all engine combustion conditions, including lean operation and stoichiometric operation (including rich operation).
The fuel concentration (the air-fuel ratio) of the air-fuel mixture supplied to the engine is controlled as shown in the block diagram of
Based on signals from an accelerator pedal depression sensor, an intake air amount metered by the air flow sensor 2, an engine rotational speed detected by a crank angle sensor, a throttle sensor signal for detecting the throttle valve opening, an engine water coolant temperature signal, a starter signal etc., ECU 25 determines the air-fuel ratio (A/F), and this signal is compensated according to a signal which is fed-back from the oxygen sensor.
In cases of low temperature, an idling time and a high load time etc., the above feed-back control according to the signal of the respective sensor and the respective switching means is stopped. Further, the apparatus has an air-fuel ratio compensation leaning function which enables the apparatus to adapt accurately to both delicate and abrupt changes of the air-fuel ratio.
When the determined air-fuel ratio is stoichiometric (A/F=14.7) or rich (A/F<14.7), the injection conditions for the injector 5 are determined by the ECU, and thereby the stoichiometric operation and the rich operation are carried out.
On the other hand, when lean operation (A/F>14.7) is detected, the NOx adsorbing ability of the catalyst 18 is evaluated. When it is judged that the apparatus has adsorbing ability, the fuel injection amount for carrying out lean operation is determined. When, however, it is judged that the apparatus has no adsorbing ability, the air-fuel ratio is shifted to the rich side for a predetermined period, and the catalyst 18 is regenerated.
The stoichiometric air-fuel ratio used for this comparison, to put it more precisely, is the air-fuel ratio in which the velocity of the catalytic reduction reaction of NOx in the catalyst exceeds the NOx pick-up velocity in accordance with the adsorption. This stoichiometric air-fuel ratio is determined by evaluating the characteristics of the catalyst in advance, and the air-fuel ratio of the vicinity of the stoichiometric air-fuel ratio is selected.
Herein, when the established air-fuel ratio is equal to or less than the stoichiometric air-fuel ratio, processing advances to step 1006, and without regeneration operation of the catalyst the air-fuel ratio operation followed by the indication is carried out.
If the established air-fuel ratio is greater than the stoichiometric air-fuel ratio, the NOx adsorption amount is estimated in step 1007, and in step 1008, the estimated amount is compared with a predetermined limitation amount.
The limitation adsorption amount is set to a value which permits NOx in the exhaust gas to be fully purified, based on experimentally determined NOx removal characteristics of the catalyst, taking into account the exhaust gas temperature and the catalyst temperature etc.
If the apparatus retains NOx adsorbing ability, processing advances to step 1006, without the regeneration of the catalyst the air-fuel ratio operation followed by the indication is carried out. If, however, the apparatus has no NOx adsorbing ability, processing goes to step 1009, and the air-fuel ratio is shifted to the rich side. In step 1010, the rich shift time is counted, and when the elapsed time Tr exceeds a predetermined time (Tr)c, the rich shift finishes.
The evaluation of NOx adsorbing ability of the catalyst will be carried out as following.
In step 1007-EO1, the signals relating to the working conditions of the catalyst such as the exhaust gas temperature and various kinds of engine operation conditions which affect to NOx concentration in the exhaust gas are read in, and NOx amount En that is adsorbed in a unit time is estimated.
In step 1007-EO2, NOx amount En is accumulated, and in step 1008-EO1 the accumulated value En is compared with the upper limitation value (En).
When the accumulated value En is equal to or is less than the upper limitation value (En)c, the accumulation is continued; but if the accumulated value En exceeds the upper limitation value (En)c the accumulation is released in step 1008-EO2 and the process advances to step 1009.
In step 1007-HO1, the lean operation time is accumulated, and in step 1008-HO1 the value HL is compared with an upper limitation value (HL)c.
When the accumulated value HL is equal to or is less than the upper limitation value (HL)c accumulation is continued; however, when the accumulation value HL exceeds the upper limitation value (HL)c the accumulation is released in step 1008-HO2, and processing goes to step 1009.
In step 1007-001, the oxygen amount Qo is accumulated, and in step 1008-001 the accumulated value Qo is compared with an upper limitation value (O)c.
If the accumulated value QN is equal to or is less than the upper limitation value (O)c, the accumulation is continued, but when the accumulation value QO exceeds the upper limitation value (O)c the accumulation is released in step 1008-002, and processing advances to step 1009.
In step 1007-NO1, the NOx amount QN in the inlet port of the catalyst is accumulated based on NOx concentration sensor signal. In step 1008-NO1 the accumulated value QN is compared with the upper limitation value (QN)c. If the accumulated value QN is equal to or is less than the upper limitation value (QN)c, the accumulation is continued; but when the accumulation value QN exceeds the upper limitation value (QN)c the accumulation is released in step 1008-002, and processing goes to step 1009.
In step 1007-CO1, NOx amount CN in the outlet port of the catalyst is accumulated according to NOx concentration sensor signal. In step 1008-CO1 the size between the accumulation value CN and the upper limitation value (CN)c of the accumulated NOx amount is compared.
When the accumulated value CN is equal to or is less than the upper limitation value (CN)c the accumulation is continued; but if the accumulated value CN is more than the upper limitation value (CN)c, the process advances to step 1009.
Reinforcement of the discharging regulation of the exhaust gas in the automobile is necessary to purify the harmful materials such as HC which are discharged immediately after the engine starting time. In the prior technique, however, harmful materials are discharged without treatment until the catalyst reaches to the working temperature. It is thus necessary to reduce substantially the non-treated amount of the harmful materials. A method for abruptly heating the catalyst to the working temperature is effective for this purpose.
In the construction shown in
During stoichiometric operation both the manifold catalyst 17 and the catalyst 18 function, and purification for HC, CO and NOx is carried out. During lean operation the catalyst 18 adsorption-purifies NOx.
For regeneration of the catalyst 18, the air-fuel ratio is shifted to the rich side. Because HC and CO (gaseous reducing agents) are largely chemically changed by the manifold catalyst 17, they can reach the catalyst 18 and regenerates it. The above stated construction, which includes the catalyst 18 is thus an important advantageous feature.
Hereinafter, the effects achieved by the present invention will be explained by reference to the graphic depictions in
The exhaust gas purification performance of the catalyst and of the exhaust gas purification apparatus according to the present invention were evaluated as follows: A first test catalyst and a comparison catalyst were mounted on a lean burn specification automobile having a displacement volume of 1.8 liters; and the automobile was run on a chassis dynamometer. Both the test catalysts were of a honeycomb shape, having 400 cell/in2 and a volume of 1.7 liters, they were heat-treated at 700° C. under an oxidization atmosphere and were put below the floor.
The running speed was kept constant at 10-15 modes running, based on the Japanese exhaust gas regulation measurement method. The exhaust gas was analyzed using two methods. In a first method, NOx, HC, and CO concentrations in the exhaust gas were measured and analyzed directly using the automobile exhaust gas measurement apparatus. The second method provided for measuring CVS (constant volume sampling) value, using the automobile constant volume dilution sampling apparatus.
Further, in 10-15 mode running, the A/F ratio was maintained in the lean range (A/F=22-23) during constant speed running time, during acceleration from 20 km/h to 40 km/h at 10 mode, and acceleration time from 50 km/h to 70 km/h at 15 mode. The rest of the running was performed at the stoichiometric A/F ratio.
In
Tables 2 and 3 show the CVS value obtained by the various kinds of the catalyst and the comparison catalyst, together with the catalyst compositions. The preparations for the catalyst and the comparison catalyst were performed by the above stated methods. However, as the preparation raw materials, barium nitrate was used as barium (Ba) and silica-sol was used as silicon (Si). It is assumed that Si exists a silica (SiO2) or a complex oxide thereof.
For the various kinds of the catalyst, the exhaust gas purification performances were measured using a model exhaust gas.
Modified Catalysts
Experiment 1:
(Preparation Method)
The alumina powders and alumina nitrate slurry as a precursor thereof were coated on a cordierite honeycomb (400 cell/in2), and the honeycomb had deposited thereon an alumina coating of 150 g per liter of apparent volume of the honeycomb. The alumina coated honeycomb was then impregnated with a cerium nitrate solution, dried at 200° C., and calcined for 1 (one) hour at 600° C. Thereafter, the honeycomb was impregnated with a mixture liquid comprised of sodium nitrate (NaNO3) solution and magnesium nitrate (MgNO3) solution was similarly dried and calcined.
Next, the honeycomb was impregnated by a mixture solution comprised of dinitrodiamime platinum nitrate solution and rhodium nitrate (Rh(NO3)2) solution, dried at 200° C. and calcined for 1 (one) hour at 450° C. Finally, a magnesium nitrate (Mg(NO3)2) solution was impregnated, and the honeycomb was dried at 200° C. and calcined for 1 (one) hour at 450° C.
With the above stated method, Embodiment Catalyst 1 was obtained, in which to 100 wt % Al2O3, 18 wt % Ce, 12 wt % Na, and 1.2 wt % Mg were held at the same time. In addition this Embodiment Catalyst 1 also contained 1.6 wt % Pt, 0.15 wt % Rh, and 1.5 wt % Mg.
Using a similar method, Embodiment Catalysts 2-4 were obtained.
As clearly shown in above, an NOx adsorption catalyst is provided in the exhaust gas flow passage, and under the oxidization atmosphere of a lean exhaust gas, NOx is caught according to the chemical adsorption. Thus, a reduction atmosphere is formed and the adsorption catalyst is regenerated. Accordingly, NOx etc. in the lean burn exhaust gas can be purified with high efficiency, without significantly affecting the fuel consumption.
The compositions of the prepared catalysts are shown in Table 4. The support order in this Table 4 indicates that after a first component has been applied, a second component and then the third and the fourth were applied, with the amount of each being indicated preceding the symbol.
(Experimentation Manner)
(1) honeycomb shape catalyst of 6 cc (17 mm square; 21 mm length) was filled up in a Pyrex reaction tube.
(2) The reaction tube was put into a ring shaped electric furnace and heated to the temperature of 300° C. (As the reaction temperature, the honeycomb inlet port gas temperature was measured.) After the temperature stabilized at 300° C., a flow of a model exhaust gas of the stoichiometric ratio (a “stoichiometric model exhaust gas”) was started. After 3 (three) minutes, the flow of the stoichiometric model exhaust gas was stopped, and a flow of a lean ratio model exhaust gas (a “lean model exhaust gas”) was started.
NOx in the gas discharged from the reaction tube was measured by the chemical luminescence detection method, and HC was measured by the FID method.
NOx purification performance and HC purification performance obtained by this method were made as an initial period performance.
(3) The reaction tube where the honeycomb catalyst used in (2) above was filled up, put into the ring shaped electric furnace and raised to the temperature of 300° C. (As the reaction temperature, the honeycomb inlet port gas temperature was measured.)
After the temperature stabilized at 300° C., a flow of the stoichiometric model exhaust gas which contains SO2 gas as a catalyst poison was started. The SO2 poisoning operation was finished by flowing the poisoning gas SO2 gas for five hours.
After the above stated SO2 poisoning using the honeycomb catalyst, a test similar to (2) above was carried out and NOx purification performance and HC purification performance of after SO2 poisoning were obtained.
(4) The honeycomb catalyst used in (2) above was put into a baking furnace and under the air atmosphere the honeycomb catalyst was calcined at 300° C. for five hours. After the cooling of the honeycomb catalyst, NOx purification performance and HC purification performance similar to (2) above were measured.
As the stoichiometric model exhaust gas, the gas comprised of 0.1 vol % NO, 0.05 vol % C3H6, 0.6 vol % CO, 0.6 vol % O2, 0.2 vol % H2, 10 vol % water vapor and the balance of N2.
Further, as the lean model exhaust gas, the gas comprised of 0.06 vol % NO, 0.04 vol % C3H6, 0.1 vol % CO, 10V01% CO2, 5 vol % O2, 10 vol % water vapor and the balance of N2.
In the above stoichiometric model exhaust gas, C3H6, CO, H2 are the gaseous reducing agents and O2 and NO are the gaseous oxidizing agents. The gaseous oxidizing agent amount is 0.65% for converting into O2 and the gaseous reducing agent amount is 0.575% for converting into O2 consumption ability. Accordingly, both were balanced.
In the lean mode exhaust gas, C3H6 and CO are the gaseous reducing agents and O2 and NO are the gaseous oxidizing agents. The gaseous oxidizing agent amount is 5.03% for converting into O2 and the gaseous reducing agent amount is of 0.23% for converting into O2 consumption ability. Accordingly, there is an excess amount of oxygen (O2) of 4.8%.
As the gas used for catalyst poisoning, the gas comprised of 0.1 vol % NO, 0.05 vol % C3H6, 0.6 vol % CO, 0.005 vol % SO2, 10 vol % water vapor and the balance of N2.
The space velocities of the above three kinds gases were 30,000 /h in the dry gas base (not containing the water vapor).
Table 5 shows the purification rate of the honeycomb catalyst of the initial period and after the poisoning by SO2. Here, NOx purification rate was obtained after 1 (one) minute where the stoichiometric model exhaust gas was changed over to the lean model exhaust gas.
NOx purification rate and HC purification rate were calculated according to following formula.
NOx purification rate=(NOx concentration in inlet port gas−NOx concentration in outlet port gas)×100/(NOx concentration in inlet port gas) Equation (1)
HC purification rate=(HC concentration in inlet port gas−HC concentration in outlet port gas)×100/(HC concentration in inlet port gas) Equation (2)
Embodiment Catalysts 1-4 had a high initial period performance and a heat resistant ability and a SOx endurance ability.
Embodiment Catalyst 5 was obtained by replacing the support material of Embodiment Catalyst 1 with La and Al complex oxide material (La-β-Al2O3) where the composition ratio of La—Al was 1-20 mol % La and 100 mol % sum of La and Al. The performances of Embodiment Catalyst 5 are shown in Table 6.
As the support was constituted by La—Al complex oxide material (La-β-Al2O3) the heat resistant ability was improved.
In Embodiment Catalyst 1, the initial period performance of NOx purification rate at 400° C. was measured, while the support amount of Na of the second component was varied. The catalyst preparation was similar to Embodiment Catalyst 1 and the experimentation manner was similar to Experiment 1. The results are shown in
In Embodiment Catalyst 1, the initial period performance of NOx purification rate at 400° C. was measured, while the supported amount of Mg of the second component was varied. The results are shown in
In Embodiment Catalyst 1, the initial period performance of NOx purification rate at 400° C. was measured, while the supported amount of Ce of the first component was varied. The results are shown in
In Embodiment Catalyst 1, the initial period performance of NOx purification rate at 400° C. was measured, while the supported amounts of Pt and Rh were varied. The results are shown in
In Embodiment Catalyst 1, the initial period performance of NOx purification rate at 400° C. was measured, while the supported amounts of Pt and Pd were varied. The results are shown in
In Embodiment Catalyst 2, initial period NOx purification rate at 400° C., after calcination at 800° C., was measured. The results are shown in
Experiment 2:
(Preparation Method)
Water and dilute nitric acid were added to boehmite powers to form a slurry, which was wash-coated to a cordierite made honeycomb. After drying, the honeycomb was calcined for 1 (one) hour at 600° C., thereby obtaining an alumina coating of 150 g per liter.
The alumina coated honeycomb was immersed in Ce nitrate solution, dried and calcined for 1 (one) hour at 600° C. Next, the honeycomb was immersed in Sr nitrate solution, dried and calcined for 1 (one) hour at 600° C. Thereafter, the honeycomb was immersed in titaniasol solution as a precursor for titania, dried and calcined for 1 (one) hour at 600° C.
The honeycomb was then immersed in a solution containing dinitrodiamime Pt nitrate and Rh nitrate. After drying, it was calcined for 1 (one) hour at 450° C. Finally, the honeycomb was immersed in Mg nitrate solution, dried and calcined for 2 (two) hours at 450° C., forming honeycomb A.
The catalyst composition of the honeycomb catalyst A was comprised of alumina (Al2O3) of 100 Wt %' Mg of 1 wt %, Rh of 0.15 wt %, Pt of 1.9 wt %, Ti of 5 wt %, Sr of 15 wt %, and Ce of 18 wt %, which is the standard for other Embodiment Catalysts.
Further, for manufacturing the honeycomb catalyst, as an alternative to the above method of impregnating the catalyst components to the alumina coated honeycomb, it is possible to employ a method where the catalyst components are immersed into the aluminum powders and after the catalyst powders are prepared they are made into the slurry, which is coated onto the honeycomb substrate (honeycomb base body). Further, as the precursor of titania, in addition to the above titania-sol, an organo titanium compound, the titanium sulfate and the titanium chloride etc. can be used. As the alkali earth metals in place of Sr nitrate (Sr(NO3)2) using Ca nitrate (Ca(NO3)2), a honeycomb catalyst B was obtained.
Except for as the rare earth metals in place of cerium nitrate (Ce(NO3)2) using lanthanum nitrate (La(NO3)2), and a method similar to that used for honeycomb catalyst A, a honeycomb catalyst C was obtained. Further, using iridium nitrate, a honeycomb catalyst D was obtained.
By varying the concentration of the titania-sol used in the preparation of the honeycomb catalyst A, three kinds of honeycomb catalysts E, F and G having different Ti supported amounts were obtained.
By varying the concentration of strontium nitrate (Sr(NO3)2) used in the preparation of the honeycomb catalyst A, three kinds of honeycomb catalysts H, I and J having different Sr supported amounts were obtained.
By varying the concentration of dinitrodiamime Pt solution used in the preparation of the honeycomb catalyst A, three kinds of honeycomb catalysts K, L and M having different Pt supported amounts were obtained.
By varying the concentration of rhodium nitrate solution used in the preparation of the honeycomb catalyst A, three kinds of honeycomb catalysts N, O and P having different Rh supported amounts were obtained.
By varying the concentration of cerium nitrate solution used in the preparation of the honeycomb catalyst A, three kinds of honeycomb catalysts Q, R and S having different Ce supported amounts were obtained.
A honeycomb catalyst T was also obtained, which did not contain titanium (Ti) such as in the honeycomb catalyst A.
The catalyst compositions of the honeycomb catalysts A-T are shown in Table 7.
Test Manner 1:
As to the honeycomb catalysts A-T, under following conditions, NOx purification reaction activity was evaluated.
A honeycomb catalyst having 6 cc was filled up in a quartz reaction tube having an inner diameter of 25 mm and was arranged in an electric furnace.
The reaction tube was heated by the electric furnace, the inlet port gas temperature of the reaction tube was set at 300° C. constant and the following model gas was let flow.
As the exhaust gas for a condition where an internal combustion engine was operated with the stoichiometric air-fuel ratio, the model gas comprised 0.1% (volume ratio) NO, 0.05% C3H6, 0.6% CO, 0.5% O2, 0.2% H2, 10% H2O, and the balance of N2, and flowed at a space velocity of 30,000 /h.
As the exhaust gas for a condition where an internal combustion engine was operated with the lean air-fuel ratio, the model gas comprised 0.06% (volume ratio) NO, 0.04% C3H6, 0.1% CO, 5% O2, 10% H2O, and the balance of N2, and flowed at a space velocity of 30,000 /h. The above model gases for the stoichiometric and lean air-fuel ratios were flowed alternately every three (3) minutes each.
In these model exhaust gases, the gaseous oxidizing agent amount is 0.55 vol % for converting into O2 and the gaseous reducing agent amount of 0.625 for converting into O2 consumption ability. Accordingly, both were substantially balanced.
The model gas for the stoichiometric air-fuel ratio and the model gas for the lean air-fuel ratio were flowed alternately every three (3) minutes each, and the inlet port NOx concentration and the outlet port NOx concentration of the catalyst at this time were measured according to the chemical luminescence detection NOx analyzer. And NOx purification rate one minute after the stoichiometric air-fuel ratio model exhaust gas was changed to the lean air-fuel ratio model exhaust gas was calculated according to the formula shown in Experiment 1.
Test Manner 2:
Except that the inlet port gas temperature was heated by the electric furnace at 400° C. constant, for each of the honeycomb catalysts A-T, NOx purification reaction activity was evaluated in a manner similar to Test Manner 1.
Test Manner 3:
Similar to Test Manner 1, the inlet port gas temperature was heated by the electric furnace at 300° C. constant. The gas, in which to the model gas used for the lean air-fuel ratio 0.005% SO2 gas was added, was flowed at a space velocity of 30,000 /h for 3 (three) hours. After that, for each of the honeycomb catalysts A-T, NOx purification reaction activity under the inlet port gas temperature of 300° C. was evaluated in a manner similar to Test Manner 1.
Test manner 4:
Similar to Test Manner 3, the gas, in which to the model for the lean air-fuel ratio 0.005% SO2 gas was added, was flowed at 300° C. for 3 (three) hours. After that, for each of the honeycomb catalysts A-T, NOx purification reaction activity under the inlet port gas temperature of 400° C. was evaluated in a manner similar to Test Manner 2.
With respect to the honeycomb catalysts A-T, the results of the evaluations according to Test Manners 1 and 3 are shown in Table 7 and the results of the evaluations according to Test Manners 2 and 4 are shown in Table 8.
Each of Embodiment catalysts A-S has a high NOx purification rate after SO2 endurance and a strong SO2 resistivity in comparison with the catalyst T which does not contain titanium (Ti).
As to the honeycomb catalyst A, an X-ray analyzing spectrum was measured and the crystallization structure was identified. In the X-ray analyzing spectrum of the honeycomb catalyst A, there was no peak caused by titania (TiO2) and it was considered that titania (TiO2) had maintained a non-crystalline structure. It was understood that strontium (Sr) as alkali earth metals was held as carbonate.
Experiment 3:
Cerium nitrate (Ce(NO3)2) solution was impregnated in alumina (Al2O3) and after drying at 200° C. the alumina was calcined at 600° C. for 1 hour. In succession, a mixture solution obtained by mixing strontium nitrate (Sr(NO3)2) with silica-sol was impregnated, similarly in the cerium (Ce) coated alumina was dried and calcined. With the above process, the catalyst powders were obtained, such catalyst powders were comprised of, to 100 wt % alumina (Al2O3), 18 wt % Ce, 15 wt % Sr, 4 wt % SiO2, 1.6 wt % Pt, 0.15 wt % Rh, and 1.5 wt % Mg. Alumina-sol and aluminum nitrate (Al(NO3)2) were added to the catalyst powders and the slurry was obtained by agitating and mixed with them and the obtained slurry was coated to a cordierite made honeycomb (400 cell/in2). The calcination temperature was about 450° C. and Embodiment Catalyst 100 having a final coating amount of 200 g/l.
According to a method similar to the above, Embodiment Catalysts 100-105 were obtained.
The composition of the prepared catalysts are show in Table 9. The support order in this Table 9 indicates that after a first component has applied, a second component is applied and next a third component and a fourth component are applied successively. Further, the supported amount is indicated before the supported metal symbol.
The testing manner was similarly to (1), (2) and (3) shown in Experiment 1 and further the composition of the model gas was similarly to that of shown in Experiment 1.
Table 10 shows the NOx gas purification rate at one minute after the start of flow of the stoichiometric model exhaust gas, and the purification rate one minute after the start of the lean model exhaust gas, obtained by the honeycomb catalyst during the initial period and after SO2 poisoning. The NOx gas purification rate was calculated according to the formula shown in Experiment 1.
Further, the decrease of the lean NOx gas purification rate by SO2 poisoning was calculated by the following formula.
Lowering rate of NOx gas purification rate=(initial period NOx gas purification rate−NOx gas purification rate after SO2 poisoning)/(initial period NOx gas purification rate formula (2)
The decrease of the lean NOx gas purification rate by SO2 poisoning according to the support of SiO2 is improved at −5%-−15%.
In Embodiment Catalyst 100, the NOx gas purification rate was measured while the SiO2 supported amount was varied. The catalyst preparation manner and the experimental manner were similarly to those of Embodiment Catalyst 100. The results are shown in Table 11. By supporting SiO2, the initial period NOx gas purification rate is improved. Further, the support amount of SiO2′ was 0.6 wt %-5 wt %, NOx gas purification rate after SO2 poisoning can obtain 60%.
The foregoing disclosure has been set forth merely to illustrate the invention and is not intended to be limiting. Since modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed to include everything within the scope of the appended claims and equivalents thereof.
Claims
1. An exhaust gas purification apparatus using a catalyst, wherein the catalyst comprising alumina and as catalytic components at least two of Rh, Pt and Pd, at least one of Ce, La and Y, at least one of Na, K and Sr.
2. The apparatus according to claim 1, which further contains Mg.
3. The apparatus according to claim 2, wherein the catalyst is supported on a honeycomb base body, an amount of catalytic components being 18 to 36 g/L of the honeycomb structure.
4. The apparatus according to claim 3, wherein an amount of at least one of the Na, Sr and K is larger than that of at least one of Mg, Ti and Si.
5. The apparatus according to clam 1, which further contains at least one of TI and Si and Mg.
6. The apparatus according to claim 5, wherein the catalyst is supported on a honeycomb base body, an amount of Mg being 2 to 4 g/L of the honeycomb structure.
7. The apparatus according to claim 1, wherein the catalyst contains Ce, Rh, Pt, Mg, Na and Ti.
8. A catalyst for purification of exhaust gas from an internal combustion engine, which comprises alumina, a rare earth element, at least one of Na, Sr, K, and at least one of Mg, Ti and Si.
9. The catalyst according to claim 8, wherein the catalyst contains Mg and at least one of Ti and Si.
10. The catalyst according to claim 8, wherein the rare earth element is supported on the alumina, at least two of Na, Sr, K, Mg, Ti and Si, and Mg are supported on the rare earth element.
11. The catalyst according to claim 10, wherei the catalyst contains Mg, and at least two of Na, Sr, K, Mg, Ti and Si, at least one of Na, Sr and K, and at least one of Ti and Si.
12. A method of manufacturing a catalyst for exhaust gas from an internal combination engine, which comprises:
- coating alumina on a honeycomb base body;
- coating Ce on the alumina; and
- impregnating the Ce coating with at least one of Na, Sr and K, at least one of Mg, Ti and Si, at least two of Pt, Rh and Pd, at least one of Mg, Ti and Si, and Mg.
Type: Application
Filed: Jul 28, 2004
Publication Date: Apr 28, 2005
Applicant: HITACHI, LTD. (Chiyoda-ku)
Inventors: Hiroshi Hanaoka (Kodaira-shi), Osamu Kuroda (Hitachi-shi), Ryouta Doi (Naka-gun), Hidehiro Iizuka (Hitachinaka-shi), Toshio Ogawa (Takahagi-shi), Hisao Yamashita (Hitachi-shi), Shigeru Azuhata (Hitachi-shi), Yuichi Kitahara (Hitachinaka-shi), Toshifumi Hiratsuka (Hitachinaka-shi), Kojiro Okude (Hitachi-shi), Norihiro Shinotsuka (Hitachinaka-shi), Toshio Manaka (Hitachinaka-shi)
Application Number: 10/900,320
