Patent Application
20060040824
1. Field of the Invention
This invention relates to a material and a device for removing nitrogen oxides (NOx) which are present in the gas discharged from an internal combustion engine, such as an automobile engine, or from an industrial plant, and more particularly to the technology for removing the NOx in the exhaust gas without using a reducing agent, such as ammonia.
1. Description of the Prior Art
The exhaust gases of combustion discharged from the automobiles and the marine structures which have an internal combustion engine as a source of actuation or from the blasting furnaces, incinerators, thermal power plants and crude oil refineries which produce hot environments by burning substances never fail to form nitrogen oxides in the air without reference to their sizes of volume.
The methods which are directed toward diminishing the amounts of NOx to be discharged are broadly classified into two kinds, (1) the methods which remove the NOx formed in the exhaust gases and (2) the methods which suppress the formation of NOx by improving the technique of combustion. The methods of (1) comprise a dry method and a wet method. The dry method consists in reducing the NOx thereby detoxifying it. The wet method consists in detoxifying the NOx by mainly causing it to be absorbed in a liquid and consequently converted into by-produced nitrates. The wet method has been enjoying an advanced research mainly in the removal of the NOx in boilers and heating furnaces. In contrast, the dry method has encouraged the advance of a research regarding the treatment of the NOx in the exhaust gas from an automobile, for example, because this method does not give rise to any by-product and is effective for a mobile source of generation or a small source of generation.
In this dry method, particularly the version which is called the catalytic reduction method has been renowned. This method comprises adding a reducing gas, such as methane, carbon monoxide or ammonia, to the gas containing NO or NO2 and reducing the NO2 to NO and this NO to a harmless N2 by a catalytic action. This catalytic reduction method is known in two kinds, the selective catalytic reduction process and the non-selective catalytic reduction process. When a gas containing NOx adds ammonia as a reducing agent and undergoes the action of a Pt catalyst at 200 to 300° C., for example, the NOx in the gas is selectively reduced to N2. As a concrete example, the method of ammonia selective reduction (SCR method) using an oxide-based catalyst, such as V2O5+TiO2, has been already adopted actually for the exhaust gas from a large boiler of a thermal power plant.
In these circumstances, the research aimed at detoxifying the nitrogen oxides in the exhaust gas from a gasoline engine using gasoline as a fuel is being pursued energetically using a precious metal catalyst. As regards the suppression of the nitrogen oxides, for example, the technique of reducing the nitrogen oxides, NOx, formed from the nitrogen and the oxygen in the air by the high-temperature combustion in the engine up to nitrogen by using a catalyst called a ternary catalyst developed for treating the exhaust gas of an automobile equipped with a gasoline engine and also using the unburned hydrocarbon and carbon monoxide in the exhaust gas as a reducing agent has been finding extensive utility. The ternary catalyst is a catalyst which is obtained by having noble metals, such as Pt, Pd and Rh, deposited as dispersed in the form of ultrafine particles on the surface of an alumina substrate and mounting the substrate carrying the noble metals on a refractory ceramic base. Incidentally, the term “ternary” used herein means capable of simultaneous removal of hydrocarbon, carbon monoxide and nitrogen oxides. When the ternary catalyst is used in the presence of excess oxygen, the catalytic effect is markedly suppressed and the reduction of NOx is obtained only with difficulty.
By the catalytic reduction processes mentioned above, however, the NOx will not be effectively detoxified unless the reducing agent and the catalyst, such as Pt, are both present constantly. Since the exhaust gas of lean-burn according to the method of highly efficient combustion (the exhaust gas of a gas turbine, a diesel engine or a lean-burn gasoline engine) contains a large amount of oxygen, it does not allow application of the method of ternary catalyst which is a non-selective catalytic reduction process.
JP-A 2001-73745 discloses an exhaust gas purifying system which consists in using a catalyst for removing with high efficiency the nitrogen oxides in a lean-burn exhaust gas containing oxygen excessively. The exhaust gas purifying system has disposed in the exhaust gas passageway of an internal combustion engine or a combustion device a NOx removing catalyst for giving a reducing treatment to the NOx with a reducing agent and an exhaust gas composition adjusting means for forming a low hydrocarbon reduced gas having the concentration of the hydrocarbon (HC) decreased in the neighborhood of a theoretical air-fuel ratio and in an atmosphere of excess oxygen. The exhaust gas composition adjusting means is disposed on the upstream side of the NOx removing catalyst in the exhaust gas passageway. Even the invention which is disclosed in JP-A 2001-73745, however, is not different from the conventional catalytic reduction method in respect that it essentially necessitates a low HC reduced gas as the reducing agent.
This invention has for an object thereof the provision of a material suitable for removing nitrogen oxides without requiring use of a reducing agent, such as HC gas or ammonia, and a nitrogen oxides-removing device formed of this material.
A first aspect of the invention provides a nitrogen oxides-removing material having fixed onto surfaces of metal fibers a complex compound containing at least one element selected from the group consisting of Group VIII elements, Group IX elements and Group X elements in the periodic table of the elements and at least one element selected from the group consisting of Group I elements, Group II elements, Group XIII elements and Group XIV elements in the periodic table of the elements.
A second aspect of the invention provides the nitrogen oxides-removing material according to the first aspect of the invention, wherein the complex compound contains at least one element selected from the group consisting of Group VIII elements, Group IX elements and Group X elements in the periodic table of the elements, at least one of Group I elements in the periodic table of the elements, at least one of Group II elements in the periodic table of the elements, at least one of Group XIII elements in the periodic table of the elements and at least one of Group XIV elements in the periodic table of the elements.
A third aspect of the invention provides a nitrogen oxides-removing device comprising the nitrogen oxides-removing material of the first or second aspect of the invention and a temperature elevating means for elevating a temperature of the nitrogen oxides-removing material to 100° C. or more.
A fourth aspect of the invention provides a nitrogen oxides-removing device having disposed on an upstream side of the nitrogen oxides-removing material of the first or second aspect of the invention a means to decrease a concentration of oxygen contained in an exhaust gas of combustion being introduced into the nitrogen oxides-removing device of the first or second aspect of the invention.
The nitrogen oxides-removing material of this invention and the nitrogen oxides-removing device using the nitrogen oxides-removing material can obviate the necessity for a plant unit intended to introduce a reducing agent and maintain an excellent removing performance for a long time at a low cost because they are capable of thoroughly removing the nitrogen oxides without using a reducing agent, such as an HC gas or ammonia.
Further, the nitrogen oxides-removing device of this invention is provided with a means to elevate the temperature of the nitrogen oxides-removing material to 100° C. or more. Even when the effect of removing the nitrogen oxides is lowered, therefore, the function of removing the nitrogen oxides can be recovered by heating the nitrogen oxides-removing material.
Furthermore, the nitrogen oxides-removing device of this invention has disposed on the upstream side of the nitrogen oxides-removing material mentioned above the means to lower the concentration of oxygen contained in the exhaust gas of combustion being introduced into the nitrogen oxides-removing device. Even when the exhaust gas happens to contain oxygen excessively, therefore, the device is highly effective in removing the nitrogen oxides contained in the gas and detoxifying the gas.
The above and other objects, characteristic features and advantages of the present invention will become apparent to those skilled in the art from the description made herein below with reference to the accompanying drawings.
The nitrogen oxides-removing material contemplated by this invention is produced by fixing onto the surfaces of metal fibers a complex compound containing at least one element selected from the group consisting of Group VIII elements, Group IX elements and Group X elements in the periodic table of the elements and at least one element selected from the group consisting of Group I elements, Group II elements, Group XIII elements and Group XIV elements in the periodic table of the elements. As concrete examples of Group VIII elements which are usable in this invention, ruthenium (Ru) and iron (Fe) may be cited. As concrete examples of Group IX elements, cobalt (Co), rhodium (Rh) and iridium (Ir) may be cited. As concrete examples of the Group X elements, nickel (Ni), palladium (Pa) and platinum (Pt) may be cited. The complex oxide to be fixed onto the surfaces of metal fibers is preferred to contain at least one of these elements. In this invention, the total content of the elements mentioned above is preferred to be in the range of 0.1 to 50 weight % of the complex oxide to be fixed onto the surfaces of metal fibers.
As Group I elements in the periodic table of the elements, lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs) are cited. The complex oxide to be fixed onto the surfaces of metal fibers is preferred to contain at least one of Group I elements. In this invention, the total content of Group I elements is preferred to be in the range of 0.1 to 30 weight %.
As Group II elements in the periodic table of the elements to be used in this invention, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba) are cited. At least one of Group II elements is preferred to be contained. In this invention, the total content of Group II elements is preferred to be in the range of 0.1 to 30 weight % of the complex oxide to be fixed onto the surfaces of metal fibers.
As Group XIII elements in the periodic table of the elements to be used in this invention, boron (B), aluminum (Al), gallium (Ga) and indium (In) are cited. The complex oxide to be fixed onto the surfaces of fibers contains at least one of Group XIII elements. Then, in the present invention, the total content of Group XIII elements is preferred to be in the range of 0.1 to 30 weight % of the complex oxide to be fixed onto the surfaces of metal fibers.
As Group XIV elements in the periodic table of the elements to be used in this invention, carbon (C), silicon (Si), tin (Sn) and lead (Pb) are cited. The complex oxide to be fixed onto the surfaces of metal fibers contains at least one of Group XIV elements. In this invention, the total content of Group XIV elements is preferred to be in the range of 0.1 to 30 weight % of the complex oxide to be fixed onto the surfaces of metal fibers.
Thus, in the nitrogen oxides-removing material of this invention, the complex compound which is an essential component substance is preferred to contain at least one element selected from the group consisting of Group VIII elements, Group IX elements and Group X elements in the periodic table of the elements, at least one element of Group I elements in the periodic table of the elements, at least one element of Group II elements in the periodic table of the elements, at least one element of Group XIII elements in the periodic table of the elements, and at least one element of Group XIV elements in the periodic table of the elements. The complex oxide is preferably prepared so that the total content of these elements falls in the range of composition mentioned above.
The complex compound of which the nitrogen oxides-removing material of this invention is formed can be manufactured by a varying method. The selected element from Group VIII element, Group IX elements and Group X elements, Group I element, Group II element, Group XIII element, and Group XIV element are prepared each in the form of oxide, nitrate, sulfate or carbonate and converted into slurry or a solution such that the contents of the individual elements may fall in the ranges specified above in the target complex compound. The slurry or solution thus prepared is dried and subsequently fired in the ambient atmosphere at 300° C. to 900° C. for at least one minute and at most six hours to obtain the complex compound mentioned above.
Then, the complex compound consequently obtained is pulverized by the use of a jet pulverizer or by means of milling, for example, till the average particle diameter reaches below the diameter of the short fibers of the metal fibers to be used and below 20 μm as well. The pulverized particles of the complex compound thus obtained are dispersed in a solvent, such as water, to prepare slurry. Alternatively, the pulverized particles of the complex compound and a binder optionally added thereto are together mixed with a solvent, such as water, so as to acquire proper viscosity and prepare slurry. As the binder, silica sol or alumina sol may be preferably used. The metal fibers are coated with the slurry thus prepared and the coated metal fibers are subsequently dried and fired to produce the nitride oxides-removing material of this invention.
The complex compound, when the short fibers of the metal fibers to be used happen to have a diameter greater than 20 μm, is preferably pulverized till the average particle diameter of the resultant particulates falls below 20 μm. When slurry of the particulates of the complex compound is to be prepared, the particulates that have an average particle diameter of 20 μm or less bring about satisfactory dispersibility in the slurry and permit manufacture of homogeneous slurry. At the same time, the particulates can be fixed in a stabilized state onto the surfaces of the metal fibers. If the particulates of the complex compound have an average particle diameter exceeding 20 μm, the overage will possibly result in preventing the object of this invention from being attained as expected by depriving the particulates in the slurry of the uniform dispersibility and disposing them to peel off readily from the surfaces of the metal fibers.
The manufacture of the particulates of the complex compound into the slurry is preferred to be carried out so that the concentration of the particulates in the slurry may fall in the range of 30 weight % to 70 weight %. As the means to coat the metal fibers with the slurry, a method which comprises immersing the metal fibers in the slurry, lifting them up and drying the wet metal fibers, a method which comprises directly applying the slurry to the metal fibers, and a method which comprises directly spraying the slurry to the metal fibers are available. These methods may be carried out either singly or properly combined. When the surfaces of metal fibers are to be coated with the particulates of the complex compound, though the coating may cover the surfaces of the metal fibers either wholly or partly, it is preferred that the particulates of the complex compound form a uniform coat on the surfaces of the metal fibers.
The content of the complex compound in the nitrogen oxides-removing material of this invention is preferred to be in the range of 0.1 to 50 weight %. If this content falls short of 0.1 weight %, the shortage will result in preventing the inherent effect of this invention from being manifested fully. If the content exceeds 50 weight %, the overage will bring no proportionate addition to the effect and therefore prove wasteful.
The nitrogen oxides-removing material of this invention can be produced by another method of production, besides the method enumerated above. To be specific, the nitrogen oxides-removing material contemplated by this invention can be obtained by the method comprising wet-mixing the particulates of a compound containing the elements, such as Group VIII elements, Group IX elements or Group X elements, with a binder containing at least one of Group I elements of the periodic table of the elements, at least one of Group II elements of the periodic table of the elements, at least one of Group XIII elements of the periodic table of the elements and at least one of Group XIV elements of the periodic table of the elements, thereby preparing a slurry, coating the surfaces of metal fibers with the slurry, drying the metal fibers, and subsequently firing them in the air at a temperature in the range of 300° C. to 900° C.
The binder to be used in the method of production described above is obtained by preparing an alkali metal element, an alkaline earth metal element, a Group III-B element and a Group IV-B element each in the form of an oxide, a nitrate, a sulfate or a carbonate and compounding the salts thus prepared and a commercially available silica sol or alumina sol in properly adjusted amounts such that the contents of the individual elements in the target complex compound may fall in the relevant ranges mentioned above.
The complex compound of which the nitrogen oxides-removing material of this invention is formed is used particularly advantageously when it is so prepared that it may acquire a configuration having the lattice spacing (d value) in the powder X-ray diffraction in at least any one of the ranges (1) 4.72 to 5.28 Å, (2) 3.39 to 3.66 Å, (3) 3.19 to 3.43 Å, (4) 3.03 to 3.24 Å, (5) 2.79 to 2.97 Å, (6) 2.46 to 2.60 Å, (7) 2.18 to 2.28 Å, (8) 1.99 to 2.08 Å, (9) 1.85 to 1.92 Å, (10) 1.66 to 1.71 Å, (11) 1.56 to 1.61 Å, (12) 1.49 to 1.53 Å, (13) 1.43 to 1.46 Å and (14) 1.28 to 1.31 Å.
The metal fibers onto which the complex compound is fixed are preferred to be stainless steel fibers. The stainless steel fibers which are particularly advantageously used contain iron in an amount of 50 weight % or more and, at the same time, contain at least one metal selected from the group consisting of nickel, chromium, carbon, silicon, manganese, phosphorus, sulfur, molybdenum, aluminum, nitrogen, selenium, copper, titanium, niobium and zirconium.
The nitrogen oxides-removing material contemplated by this invention can be used in its unmodified form. It may be optionally used as molded by using or not using a commercially available binder in a definite form of bulk, pellets, honeycombs or felt each in a spherical, cylindrical or polygonal shape. Otherwise, the nitrogen oxides-removing material of this invention may be tentatively pulverized in a powdery state and subsequently molded in a fixed form by using the ordinary procedure or deposited in the form of a coat on a supporting structure. As concrete examples of the supporting structure, the carrier bases made of ceramic substances, such as cordierite, titania, zirconia, zeolite and alumina, and the carrier bases made of metals, such as stainless steel, may be cited.
Now, the embodiment of the nitrogen oxides-removing material of this invention will be described below. This purifying device comprises an oxide purifying material of this invention and a temperature elevating means for heating the nitrogen oxides-removing material to a temperature of 100° C. or more. Even when the nitrogen oxides-removing material suffers the function thereof to be lowered in consequence of a prolonged continuous service for purification, it can recover the function using the temperature elevating means to heat the nitrogen oxides-removing material. Incidentally, the recovery of the function of the nitrogen oxides-removing material may be accomplished by providing the nitrogen oxides-removing device with a means to control the temperature of the exhaust gas of combustion being introduced into the nitrogen oxides-removing device in the range of 300 to 900° C. either in the place of the temperature elevating means mentioned above or in combination with this temperature elevating means.
As regards the nitrogen oxides-removing device of this invention, the idea of disposing the means to decrease the concentration of oxygen contained in the exhaust gas of combustion being introduced into this nitrogen oxides-removing device on the upstream side of the nitrogen oxides-removing material constitutes a preferred embodiment. The means to decrease the concentration of oxygen contained in the exhaust gas of combustion is highly effective in removing the nitrogen oxides in the exhaust gas of combustion and consequently detoxifying the exhaust gas because it can manifest the function of removing nitrogen oxides even when the exhaust gas of combustion happens to contain oxygen excessively. As the means to decrease the concentration of oxygen contained in the exhaust gas of combustion, a combustion exhaust gas passageway having fine titanium particles fixed which is disposed on the upstream side of the nitrogen oxides-removing material proves preferable.
Now, this invention will be described more specifically below with reference to examples. It should be noted, however, that this invention is not limited to these examples.
(1) Preparation of slurry of complex compound: SrCO3 (powder 99.99%) and RuO2 (powder 99.9%) were added at a molar ratio of 2:1, mixed thoroughly while continuously pulverized in an agate mortar, and sintered in the air at 900° C. for 6 hours. The resultant sinter was again pulverized and mixed and again sintered in the air at 1200° C. for 6 hours to afford a powdered oxide. The powdered oxide and a powdered binder composed of silicon oxide, sodium oxide, calcium oxide and boron oxide were added at a weight ratio of 1:1 and mixed while pulverized fully finely in an agate mortar. Then, the resultant powdered mixture composed of the powdered oxide and the powdered binder was made to add water at a (powdered mixture):(water) weight ratio of 20:10 and suspended thoroughly in the added water to prepare slurry of complex compound.
(2) Manufacture of nitrogen oxides-removing material: A stainless steel wool having an iron content of 70 weight %, a nickel content of 8 weight % and a chromium content of 18 weight % was prepared. When this stainless steel wool was tested for specific electric resistance at about 25° C. with a commercially available tester, the magnitude was found to be 0.01 Ωcm or less. The slurry prepared above was uniformly applied to the whole surface of the stainless steel wool. Then, this stainless steel wool was sintered in the air at 860° C. for 10 minutes to obtain the nitrogen oxides-removing material contemplated by this invention.
(3) Test 1 for evaluating capacity for removal of nitrogen oxides: First, an evaluating system 1 configured as illustrated in
(4) X-ray diffraction measurement: The stainless steel wool was removed from the nitrogen oxides-removing material of Example 1 and the complex compound fixed onto the stainless steel wool was exclusively recovered. The recovered complex compound was thoroughly pulverized in an agate mortar till it formed fine particles having a homogenous particle diameter. Then, the complex compound transformed into the fine particles was uniformly fixed onto a glass plate designed for the measurement of X-ray diffraction by means of a double-sided adhesive tape. Then, this glass plate was set in a powder X-ray diffraction device and tested for X-ray diffraction in a range of 2θ from 5° through 90° by using a Cu—KαX-ray. The results of this test are shown in
Five (5) g of the stainless steel wool forming the nitrogen oxides-removing material of Example 1 was prepared and it was used as a sample of Comparative Example 1. The sample of Comparative Example 1 was tested for evaluation of the performance of removing nitrogen oxides by following the procedure of Example 1 while carrying out an operation of maintaining the electric furnace 6 with a temperature controlling function constantly at 600° C. and 700° C. and performing a heating treatment at 800° C. for 10 minutes up to several repetitions. The results are shown in
RuO2 (powder 99.9%) and the powdered binder formed of silicon oxide, sodium oxide, calcium oxide and boron oxide and used in Example 1 were mixed in a weight ratio of 1:1 and the resultant mixture was thoroughly mixed while continuously pulverized in an agate mortar. Then, the powdered mixture formed of the powdered oxide and the powdered binder was thoroughly suspended in water added thereto in an amount satisfying a weight ratio of (powdered mixture):(water)=20:10 to prepare slurry of a complex compound. Separately, the stainless steel wool used in Example 1 was prepared. The slurry was applied homogeneously to the whole stainless steel wool. Subsequently, the stainless steel wool coated with the slurry was sintered in the air at 860° C. for 10 minutes to obtain a nitrogen oxides-removing material of Example 2.
Pt (powder 99.9%) and the powdered binder formed of silicon oxide, sodium oxide, calcium oxide and boron oxide and used in Example 1 were mixed at a weight ratio of 1:1 and the resultant mixture was thoroughly mixed while continuously pulverized in an agate mortar. A nitrogen oxides-removing material of Example 3 was manufactured by following the procedure of Example 2 while changing the conditions excepting the composition of a starting substance.
SrCO3 (powder 99.99%) and Pt (powder 99.9%) were added at a molar ratio of 4:1 and thoroughly mixed while continuously pulverized in an agate mortar. Then, a nitrogen oxides-removing material of Example 4 was manufactured by following the procedure of Example 1 while changing the conditions excepting the composition of a starting substance.
The powdered binder formed of silicon oxide, sodium oxide, calcium oxide and boron oxide and used in Example 1 was thoroughly suspended in water added thereto in an amount satisfying a weight ratio of (powdered binder):(water)=20:10 to manufacture slurry. Separately, the stainless steel wool used in Example 1 was prepared. The slurry was homogeneously applied to the whole stainless steel wool. Subsequently, this stainless steel wool was sintered in the air at 860° C. for 10 minutes to obtain a nitrogen oxides-removing material of Comparative Example 2.
Test 2 for evaluation of removal of nitrogen oxides: In the case of effecting the reaction with a nitrogen oxides-containing nitrogen fed at a larger flow rate than in the Test 1 for the evaluation of the capacity for the removal of nitrogen oxides, the nitrogen oxides-removing materials of Examples 1 to 4 and Comparative Example 2 were tested for the capacity for removing NOx in the nitrogen oxides-containing nitrogen fed at the larger flow rate mentioned above.
For the purpose of evaluating the performance of removing NOx in the nitrogen oxides-containing nitrogen fed at a high flow rate with respect to the examples and the comparative example mentioned above, the following system was prepared. In the evaluating system 1 configured as illustrated in
Then, 1000 g of a sample subjected to the evaluation was placed substantially at the center of the reaction vessel. Subsequently, 430 ppm of nitrogen monoxide diluted with nitrogen gas (N2) was introduced as controlled to a flow rate of 1.0 liter/min into the reaction vessel controlled to a prescribed temperature. The hot gas emanating from this reaction vessel was cooled with water across the stainless steel pipe of a gas flow path. The cooled gas was tested for the NOx concentration with the NOx analyzer. By the method described above, the samples of the nitrogen oxides-removing materials of Examples 1 to 4 and comparative Example 2 were tested for the capacity for removing NOx. The results of this test are shown in FIGS. 5 to 9.
It is found from the results of
The nitrogen oxides-removing material of Example 2 is found from the results of
The nitrogen oxides-removing material of Example 3 is found from the results of
The nitrogen oxides-removing material of Example 4 is found from the results of
In contrast, the nitrogen oxides-removing material of Comparative Example 2 began the removal of NOx at a temperature of about 240° C. and completed the removal of NOx at about 500° C. and nevertheless began to lose the effect within about 20 minutes of beginning the removal. These results indicate that the nitrogen oxides-removing material of Comparative Example 2 suffered the effect of removing nitrogen oxides to be lost within an extremely short time as compared with the samples of Examples 1 to 4.
The following experiment was carried out with the object of deciding the question of what effects titanium (Ti) would manifest to the combustion gas containing oxygen excessively.
(1) Preparation of Ti-fixed filtering material: Ti (powder 99.9%) and the powdered binder formed of silicon oxide, sodium oxide, calcium oxide and boron oxide and used in Example 1 were added at a weight ratio of 1:1 and thorough mixed while continuously pulverized in an agate mortar. A filtering material having Ti fixed onto the surface thereof was obtained by following the procedure of Example 2 while changing the conditions excepting the composition of a starting substance.
(2) Test for evaluating the capacity for removing nitrogen oxides in the presence of oxygen: Five (5) g of the Ti-fixed filtering material and 15 g of the nitrogen oxides-removing material of Example 1 were individually prepared. The filtering material and nitrogen oxides-removing material were placed in the miniature quartz tube 9 of the evaluation device 1 illustrated in
From the results of
One thousand (1000) g of the nitrogen oxides-removing material of Example 1 was prepared and the reaction vessel was packed with the material. This reaction vessel was used for the removal of nitrogen. Separately, Ti (powder 99.9%) and a silicon-based high temperature-curing sealing material were added in a weight ratio of 1:1 and the resultant mixture was applied to the inner wall of a separate reaction vessel. This reaction vessel was used for the absorption of oxygen. The nitrogen oxides-removing device of Example 5 was manufactured by having the reaction vessel for the absorption of oxygen disposed in series on the upstream side of the reaction vessel for the removal of nitrogen.
Test for evaluation of capacity for removal of nitrogen oxides in the presence of oxygen: The following system was prepared for the purpose of evaluating the nitrogen oxides-removing device of Example 5 for the performance of removing nitrogen oxides in the combustion gas containing oxygen excessively. In the evaluating system 1 configured as illustrated in
It is noted from
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-242125 | Aug 2004 | JP | national |
