| Title of Invention | HONEYCOMB CARRER FOR EXHAUST GAS CLARIFICATION CATALYST AND METHOD FOR PRODUCTION TREREOF |
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| Abstract | to provide a honeycomb carrier to support a catalyst to clean e.g. an exhaust gas of an automobile particularly containing NOx, which is excellent in heat 5 resistance, thermal shock, resiatance, mechanica1 strength and thermal decomposition resistance and has a great corrosion resistance to a catalyst, and is thus capable of being used with stability for a long period of time, and a procege for its production. 10 The material for the honeycojnb carrier is an aluminum magnesium titanate sintered product obtained by firing at from 1,000 to l,700°C a molded product formed from a raw material mixcture eomprising 100 parts by mass, as calculated as oxides, of a mixture comprising a Mg- 15 containing compound, an Al-containing compound and a Ti- containing compound in the same metal component ratio as the metal component ratio ot Mg, Al and Ti in an aluminium magnesium titanate represented by the empirical formula MgxAl2(1+x)Ti(1+x)O5 fwherein 0<X<l) , and from 1 to 10 parts 20 by mass of an alkali feldspar represented by the empirical formula (NayK1-y)AlSi3O8 (wherein XXX) . |
| Full Text | 1 DESCRIPTION HONEYCOMB CARRIER FOR EXHAUST GAS-CLEANING CATALYST AND METHOD FOR PRODUCTION THEREOF 5 TECHNICAL FIELD The present invention relates to a carrier to support a catalyst to clean various exhaust gases particularly an exhaust gas ot an automobile containing 10 NOx, and a process for its production. BACKGROUND ART The chief characteristics required of a honeycomb carrier to support a catalyst to be used for an apparatus 15 for cleaning an automobile exhaust gas which, is particularly widely used at present among various apparatuses for cleaning an exhaust combustion gas, are gol-called heat resistance and thermal shock resistance. A high, heat reaistance is required since the honeycomb 20 carrier will be exposed to a high temperature of 650º C or higher by sudden heat generation due to a catalytic oxidation reaction of unburned hydrocarbons or carbon monoxide in the exhaust gas. Further, the thermal shock resistance is a quality to be resistant to cracks or 25 breakage by a thermal stress caused in the honeycomb due to a temperature increase by such sudden heat generation. With respect to the thermal shock resistance, the smaller 2 the therma1 expansion coefficient, the greater the endurance temperature difference. So as to meet such requirements as heat resistance and thermal shock resistance various ceramics have been 5 proposed, as a material for a honeycomb carrier, but a cordierite material has been chiefly used. The primary reason why a cordierite material is used is that cordierite has a so high thermal resistance as l,400ºC, and it has an extremely small thermal expansion 10 coefficient and high thermal shock resistance among ceramics as well. However, although a cordierite material as a material for a honeycomb carrier has rather excellent quality with respect to heat resistance and thermal shock 15 resistance, it is highly disadvantageous when used as a catalyst carrier for cleaning an exhaust gas containing a nitrogen oxide (NOx) , the removal of which is "urgently required from an environmental viewpoint. That is, usually a catalyst containing an alkali metal or alkaline 20 earth metal component is used as a catalyst to remove NOx in the exhaust gas. In such a case, a part of the alkali metal or alkaline earth metal is infiltrated into cordierite as a carrier and reacts with cordierite at a high temperature, and such leads to a deterioration of 25 cordierite and loss of the catalyst as well, and thus causes a decrease of removal of NOx in the exhaust gas. In order to prevent such a phenomenon, a method of 3 covering the surface of the catalyst with silica (SiO2), and the like, have been proposed, but an extra step will be required, and an increase in the cost will be inevitable. 5 On the other hand, in a system wherein a fuel is directly jetted into an engine or in a system wherein a fuel is diluted and burned, which is becoming the main stream of a burning system of an automobile in recent years from a viewpoint of improvement in mileage and from 10 an environmental, viewpoint, removal of NOx in the exhaust gas is a particularly important concern as compared with removal of hydrocarbons and carbon monoxide. Accordingly, as a material for a honeycomb carrier to support a catalyst to clean an exhaust gas, a material which 15 replaces cordierite has been strongly desired. As materials other than cordierite, WO01/037971 discloses ceramics such as silicon carbide, silicon nitride, mullite, aluminum titanate and lithium aluminum silicate. However, they are all insufficient as a 20 material for the honeycomb Carrier. That is, silicon nitride, mullite, etc. have a high thermal expansion coefficient and are poor in thermal shock resistance. Further, silicon nitride, lithium aluminum silicate, etc. are insufficient in view of heat resistance. 25 Aluminum titanate has excellent stability even at a high temperature exceeding l,700ºC, an extremely email thermal expansion coefficient and excellent thermal shock 4 resistance. However, it has such a drawback as small mechanical strength, since the anisotropy of its crystal structure is significant, whereby slip is likely to occur at the crystalline interface by a thermal stress. 5 Resultingly, a honeycomb having a small wall thickness and a high cell density is hardly produced with it, and its use as a carrier for an exhaust gas-cleaning catalyst to which a load of mechanical vibration will be applied at a high temperature, tends to be difficult. Further, 10 such aluminum titanate, etc usually have decomposition points within a temperature range Of from 800 to l,200ºC, and they can not be used continuously for a long time in a region including such a temperature range. 15 DISCLOSURE OF THE INVENTION The present invention provides a honeycomb carrier which is a carrier tc support a catalyst to clean particularly an exhaust gas of an automobile containing NOx, which is excellent in heat resistance, thermal shock 20 resistance, mechanical strength and thermal decomposition resistance and has corrosion resistance against a catalyst containing an alkali component, and which is thereby excellent in durability so that it will not deteriorate even in a long term use, and a process for 25 its product ion. In order to solve the above problems, the present inventors have conducted extensive studies on aluminum 5 magnesium titanate and aluminum titanate and as a result, made the fallowing discoveries. That is, a sintered product obtained by firing a mixture comprising a mixture comprising a Ti-containing compound, an Al-containing 5 compound and a Mg-containing compound in a predetermined ratio to form aluminum magnesium titanate, or a mixture comprising a Ti-containing compound and an Al-containing compound in a predetermined ratio to form aluminum titanate, and a specific alkali feldspar, an oxide of a 10 spinel structure containing Mg, or MgO or a Mg-containing compound which can be converted to MgO by firing added in a predetermined ratio, is very excellent as a carrier to support a catalyst to clean an exhaust gas of an automobile. 15 Accordingly, it has been found that a honeycomb carrier made of the above sintered product of the present invention has high heat resistance and thermal shock resistance attributable to low thermal expansion properties and further has high mechanical strength and 20 high thermal decomposition resistance as different from a conventional aluminum magnesium titanate sintered product or aluminum titanate sintered product, and that the sintered product can be used with stability for a long period of time without deterioration as a conventional 25 cordierite material, even when a catalyst containing an alkali metal or alkaline earth metal component is used as a catalyst for removal of NOx. 6 The present invention has been accomplished on the basis of these discoveries and provides the following: (l) A honeycomb carrier for an exhaust gas-cleaning catalyst which is a honeycomb carrier to support a 5 catalyst to clean an exhaust gas, characterized in that the material for the honeycomb carrier is an aluminum magnesium titanate sintered product obtained by firing at from 1,000 to l,700ºc a mixture comprising 100 parts by mass, as Calculated as oxides, of a mixture comprising a 10 Mg-containing compound, an Al-containing compound and a Ti-containing compound in the, same metal component ratio as the metal component ratio of Mg, Al and Ti in an aluminum magnesium titanate represented by the empirical formula MgxAl2(1-x)O5 (wherein O empirical formula (NayK1-y) AlSi9O8 (where in ***OXXXyXXXl). (2) A honeycomb carrier fox an exliaust gas-cleaning catalyst which is a honeycomb carrier to aupport a catalyst to clean an exhaust gas, characterised in that 20 the material for the honeycomb carrier is an aluminum titanate sintered product obtained by firing at from 1,250 to l,700ºC a raw material mixture comprising 100 parts by mass of a mixture (hereinafter referred to as component X) comprising TiO2 and Al2O3 in a molar ratio of 25 the farmer/the latter being 40 to 60/60 to 40, and from 1 to 10 parts by mass of an alkali feldspar represented by the empirical formula (NayK1-y)AlSi3O8 {wherein XXX), an 7 oxide of a spinel structure containing Mg, or MgO or a Mg-containing compound which can be converted to MgO by firing (hereinafter referred to as component Y). (3) The honeycomb carrier according to the above (2), 5 wherein the component Y is a mixture comprising an alkali feldspar represented by {NayK1-y) AlSi3O8 (wherein XXX), and an oxide of a spinel structure containing Mg and/or MgO or a Mg-containing compound which can be converted to MgO by firing. 10 (4) The honeycomb carrier according to any one of the above (1) to (3), which has a wall thickness of from 0.05 to 0.6 mm, a cell density of from 15 to 124 cells/cm2, a porosity of the partition wall of from 20 to 50%, and a thermal expansion coefficient of at most 3.O x lO-6K-1. 15 (5) The honeycomb carrier according to any one of the above (1) to (4), wherein the catalyst contains an alkali metal or alkaline earth metal component to remove NOx in the exhaust gas. (6) The honeycomb carrier according to any one of the 20 above (1) to (5), wherein the exhaust gas is an axhaust gas of an automobile of a system wherein a fuel is directly jetted into an engine or of a system wherein a fuel is diluted and burned. (7) A process for producing a honeycomb carrier for an 25 exhaust gas-cleaning catalyst, characterized by preparing a raw material mixture comprising 100 parts by mass, as calculated as oxides, of a mixture comprising a Mg- 8 containing compound, an A1-containing compound and a Ti- containing compound in the same metal component ratio as the metal component ratio of Mg, Al and Ti in an aluminum magnesium titanate represented by the empirical formula 5 MgxAl2(2-x)Ti(1+x)O5 (wherein O empirical formula (NayK1-y)AlSi3O8 (wherein ***XXX), adding a molding assistant to the raw material mixture, followed by kneading to plasticize the raw material mixture to 10 make it extrueion-processable, and then extrusion processing it into a honeycomb body, followed by firing at from 1,000 to 1,700ºC. (8) A process for producing a honeycomb carrier for an exhaust gas-cleaning catalyst, characterized by preparing 15 a mixture comprising 100 parts by mass of a mixture (hereinafter referred to as component X) comprising TiO2 and A12O3 in a molar ratio of the former/the latter being 40 to 60/60 to 40, and from 1 to 10 parts by mass of an alkali feldspar represented by the empirical formula 20 (NayK1-y) AlSi3O8 (wherein XXX), an oxide of a spinel structure containing Mg, or MgO or a Mg-containing compound which can be converted to MgO by firing (hereinafter referred to as component Y), adding a molding assistant to the mixture, followed by kneading to 25 plasticize the mixture to make it extrusion-procesable, and extrusion processing it into a honeycomb body, followed by firing at from l,250 to l,700ºC. 9 (9) The process for producing a honeycomb carrier for an exhaust gas-cleaning catalyst according to the above (7) or (8), wherein the average particle size of each component contained in the raw material mixture is at 5 most 10 µm. (10) A method for cleaning an exhaust gas, which comprises contacting the exhaust gas to a honeycomb carrier Supporting a catalyst to clean an exhaust gas, characterized in that the material for the honeycomb 10 carrier is an aluminum magnesium titanate sintered product obtained by firing at from 1,000 to l,700ºC a mixture comprising 100 parts by mass, as calculated as oxides, of a mixture comprising a Mg-containing compound, an Al-containing compound and a Ti-containing compound in 15 the same metal component ratio as the metal component ratio of Mg, Al and Ti in an aluminum magnesium titanate represented by the empirical formula MgxAl2(1-x)Ti(1+x)O5 (Wherein O alkali feldspar represented by the empirical formula 20 (NAYK1-Y)ALSI3O8 (wherein XXX). (11) A method for cleaning an exhaust gas, which comprises contacting the exhaust gas to a honeycomb carrier supporting a catalyst to clean an exhaust gas, characterized in that the material for the honeycomb 25 carrier is an aluminum titanate aintered product obtained by firing at from 1,250 to l,700ºC a raw material mixture comprising 100 parts by mass of a mixture (hereinafter 10 referred to as component X) comprising TiO2 and Al2O3 in a molar ratio of the former/the latter being 40 to 60/60 to 40, and from l to 10 parts by mass of an alkali feldspar represented by the empirical formula (NayK1-Y) AlSi3O8 5 (wherein XXX), an oxide of a spinel structure containing Mg, or MgO or a Mg-containing compound which can be converted to MgO by fixing (hereinafter referred to as component Y). 10 EFFECTS OP THE INVENTION The honeycomb carrier of the present invention has high heat resistance and thermal shock resistance attributable to low thermal expansion properties and further, has high mechanical strength and excellent 15 thermal decomposition resistance as different from a conventional aluminum magnesium titanate sintered product or aluminum titanate sintered product, and ia further excellent in corrosion resistance against a catalyst, Reaultingly, it is useful as a carrier to support a 20 catalyst to clean any exhaust gas from a combustion source of either a stationary body or a mobile body, particularly an exhaust gas of an automobile containing NOx. The reason why the honeycomb carrier of the present 25 invention has high heat resistance and thermal shock resistance and further has excellent mechanical strength and thermal decomposition resistance, and does not 11 deteriorate even when used as a carrier Eor a catalyst containing an alkali metal component to clean an exhaust gas containing NOx, is not necessarily clearly understood. However, the following reasons are estimated, 5 respectively in a case where the honeycomb carrier of the present invention is made of an aluminum magnesium titanate sintered product and a case where the honeycomb carrier of the present invention is made of an aluminum titanate sintered product. 10 (A) In a case where the honeycomb carrier of the present invention is made of an aluminum magnesium titanate sintered product, the crystals of aluminum magnesium titanate as the basic structure are formed in a state where, by the presence of an alkali feldspar in their 15 production process, the alkali feldspar becomes a liquid phase, whereby dence crystals will be formed, and the mechanical strength will be improved, And, the Si component containt in the alkali feldspar will be solid salubilized in the crystal lattice of aluminum magaesium 20 titanate when, aluminum magnasium titanate is formed by firing, and as the Si solid-aolutoilization state, two types, i.e. si having a coordination number of 6 and solid-solubillized in the interior of the crystal grains and Si having a coordination number of 4 and solid 25 solubilized at the surface portion of the crystal grains, are considered. This is confirmed also by results by NMR (nuclear magnetic resonance) measurement such that si in 12 the aluminum magnesium titanate crystals is present in two states of one having a coordination number of 6 and one having a coordination number of 4. Namely, Si to be solid-solubilized in the interior 5 of the crystal grains of aluminum magnesium titanate has a coordination number of 6 and is tetravalent, and will form a pair with bivalent Mg which also has a coordination number of 6 so that the pair will be aexivalent in total and will be substituted for adjacent 10 two trivalent Al (sexivalent in total having a coordination number of 6). The reason for this will be explained from the correlation of ionic radii in addition to the maintained balance of electrical charge. That is, the ionic radii of Si2+ and Mg2+ are 0.54 Å and 0.86 Å, 15 respectively. The average ionic radius of the two will be 0.70 Å which is close to 0.68 Å i.e. the ionic radius of Al3+, whereby the occupation of two Al3+ by the pair of Si0+ and Mg2+ will be in a solid solution state which is more stable from the viewpoint of energy. Thus, it is 20 considered that by the simultaneous presence of si and Mg, diffusion of ions among the respective cations in aluminum magnesium titanate can be suppressed even at a high temperature, and a stable crystal structure can be secured, whereby excellent thermal decomposition 25 resistance will be obtained. On the other hand Si to be solid-solubilized at the surface portion of the crystal grains of aluminum 13 magnesium titanate has a coordination number of 4 not 6. This is considered to be because Si at the surface portion has a coordination, number of 4, to which oxygen is more stably bonded, since the number of cations with 5 which oxygen is shared, Which are so-called counterparts, is small. Accordingly, Si to be solid-solubilized at the surface portion of the crystal grains is in a state of mimetically coating the crystals of aluminum magnesium titanate. Thus, it is considered that the honeycomb 10 carrier of the present invention, even when used as a carrier for a catalyst containing an alkali metal, has excellent corrosion resistance against erosion of the carrier by an alkali component at a high, temperature, whereby it will not deteriorate even in a long term use. 15 (B) In a case where the honeycomb carrier of the present invention is made of an aluminum titanate sintered product, by incorporation of an alkali feldspar to the mixture for forming aluminum titanate, the alkali feldspar which becomes a liquid phase in the vicinity of 20 the temperature for forming aluminum titanate is present, and thus the reaction for forming aluminum titanate will take place in the liquid phase, whereby dense crystals will be formed, and the mechanical strength will be improved. And, the Si component contained in the alkali 25 feldspar will be solid-salubilized in the crystal lattice of aluminum titanate and substitute for Al. Si has a smaller ionic radius than Al, whereby the bond length 14 with surrounding oxygen atoms is shorter, and the lattice constant tends to be small as compared with pure aluminum titanate. Accordingly, it is considered that the sintered product to be obtained will have a stabilized 5 crystal structure and exhibit very high thermal stability, and have significantly improved thermal decomposition resistance. Further, when an oxide of a spinel structure containing Mg, ot MgO or a Mg-containing compound which 10 can be converted to MgO by firing is added to the mixture forming aluminum titanate, a dense sintered product will be obtained, and a sintered product having very high mechanical strength as compared with pure aluminum titanate will be formed. 15 Still furthar, when an alkali feldspar, and an oxide of a spinel structure and/or MgO or a Mg-containing compound. which can be converted to MgO by firing are simultaneously added to the mixture forming aluminum titanate, Si contained in the alkali feldspar and Mg 20 contained in the oxide of a spinel structure and MgO or the Mg-containing compound which can be converted to MgO by firing, will be substituted for mainly Al sites in aluminum titanate. When such elements are added by themselves, a bivalent (Mg) or tetravalent (Si) element 25 will be substituted for Al sites where a fundamentally trivalent electrical charge balsance is maintainad. Accordingly, it is considered that so as to maintain the 15 electrical charge balance, when Mg is added, oxygen is discharged out of the system to cause an oxygen defect to maintain the electrical charge balance, and when Si is added, as si is tetravalent, fundamentally tetravalent Ti 5 is reduced to trivalent to maintain the alectrical change balance. On the other hand, Mg has an electrical charge amaller by 1 than Al and Si has an electrical charge larger by 1 than Al. Accordingly, it is considered that 10 the electrical charge balance can be maintained by simultaneously adding the alkali feldspar and the oxide of a spinel structure and MgO or the Mg-containing compound which can be converted to MgO by firing, whereby Si can be solid-solubilized without influence over other 15 sintered product-constituting elements. Particularly, in such a case, it is considered that when the alkali feldspar, the oxide of a spinel structure and MgO or the Mg-containing compound which can be converted to MgO by firing are added in a ratio close to 20 an equimolar ratio, the additives can be present more stably as compared with a case where they are added by themselves. It is considered that from these reasons, they synergiscically function, whereby an aluminum titanate sintered product, which has significantly 25 improved. strength as compared, with a case where the additives are used by themselves, low thermal expansion, properties which aluminum titanate fundamentally has, and 16 high mechanical strength, and yet has improved thermal decomposition resistance, will be formed. Further, the reason, why the honeycomb carrier of the present invention has excellent corrosion resistance 5 against a catalyst containing an alkali component is estimated as follows. Firstly, in the case of a honeycomb carrier made of aluminum titanate obtained by firing a raw material mixture containing an alkali feldspar, when aluminum titanate is formed, the potassium 10 component contained in the alkali feldspar has been already present outside the aluminum titanate crystal system (present at the Crystalline interface). Accordingly, when a catalyst containing an alkali component is supported so that the alkali component is in 15 contact wich the honeycomb carrier, the osmotic pressure of potassium to the honeycomb carrier tends to be low, and resultingly infiltration of potassium into the carrier will be inhibited. On the other hand, in the case of aluminum titanate 20 obtained by firing a raw materia1, mixture containing an oxide or a spinel structure containing Mg, or MgO or a Mg-containing compound which can be converted to MgO by firing, by the presence of a Mg (one of alkaline earth metals) component which is a basic element, the aluminum 25 titanate sintered product tends to have a decreased acidity, whereby its reactivity with the alkali component which is a base (one of alkali metals) in the catalyst 17 tends to be low. Further, in the case of aluminum titanate obtained, by firing a raw material mixture containing both an alkali feldspar, and an oxide of a spinel structure 5 containing Mg, or MgO or a Mg-containing compound which can be converted to MgO by firing, it is considered that both the above mechanisms will synergistically function, whereby very excellent corrosion resistance against an alkali component will be achieved. 10 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the changes with time of the remaining ratios a of aluminum magnesium titanate with respect to the sintered products in Example l-l of the present 15 invention and Comparative Example l-l. Fig. 2 shows the changes with time of the remaining ratios β of aluminum titanate with respect to the eintered products in Examples 2-1 and 2-2 of the present invention and Comparative Example 2-1. 20 BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as the material for the honeycomb structure catalyst carrier, the following aluminum magnesium titanate sintered product (A) or 25 aluminum titanate sintered product (B) ie used. (A) Aluminum magnesium titanate sintered product. An aluminum magnesium titanate sintered product 18 obtained by firing at from 1,000 to l,700ºC a raw material mixture comprising 100 parts by mass, as calculated as oxides, of a mixture comprising a Mg- containing compound, an Al-containing compound and a Ti- 5 containing compound in the same metal component ratio as the metal component ratio of Mg, Al and Ti in an aluminum magnesium titanate represented by the empirical formula MgxAl2(1-x)Ti(1+x)O5 (Wherein 0 10 empirical formula (NayK1-y)AlSi3O8 (wherein XXX). The above Mg-containing compound, Al-containing compound and Ti-containing compound to be used as the raw materials, are not particularly limited so long as they are components capable of synthesizing aluminum magnesium 15 titanate by firing. The Mg-containing compound, Al. containing compound and Ti-containing compound may not necessarily be separate compounds respectively, and may be a compound containing two or more metal components. Such, raw material compounds may usually be suitably 20 selected among those to be used as raw materials for various ceramics, such as alumina ceramics, titania ceramics, magnesia ceramics, aluminum titanate ceramics, magnesium titanate ceramics, spinel ceramics and aluminum magnesium titanate ceramics. Specific examples of such 25 compounds include oxides such, as Al2O3, TiO2 and MgO, composite oxides cantaining at least two types of metal components, such as MgAl2O4, Al2TiO3, MgTi2O3, and various 19 spinel structures containing Mg and Ti, compounds containing one or more metal components selected from the group consisting of Al, Ti and Mg (such as carbonates, nitrates or sulfatas). 5 The blend ratio of the Mg-containing compound, the Al-containing compound and the Ti-containing compound is such that the ratio of the metal components contained in these compounds would be a ratio similar to, preferably the same ratio as, the metal component ratio of Mg, Al 10 and Ti in aluminum magnesium titanate represented by the above empirical formula MgxAl2(1-x)Ti(1+x)O5 (wherein O a ratio, it is possible to obtain aluminum magnesium titanate having the same metal component ratio as the 15 metal component ratio in the mixture used as the raw material. When a honeycomb filter of the present invention is to be obtained, it is necessary to incorporate an alkali feldspar as an additive to the above mentioned mixture 20 comprising the Mg-containing compound, the Al-containing compound and the Ti-containing compound. The alkali feldspar not only serves as a sintering assistant for aluminum magnesium titanate, but also plays a role of adding a Si component to the aluminum magnesium titanate, 25 and it is represented by the empirical formula (NayK1-y)AlSi3O5. IN the formula,y satisfies XXX), preferably 0.lXXX), particularly preferatoly 0.l5XXX0+85 20 An alkali feldspar having value y within this range, has a low melting point and is particularly effective for promoting the sintering of aluminum magnesium titanate. The amount of the alkali feldspar to be used, is 5 usually from about 1 to 10 parts by mass, preferably from about 3 to about 5 parts by mass, per 100 parts by mass of the total amount of the Mg-containing compound, the Al-containing compound and the Ti-containing compound to be used as the raw materials, as calculated as the 10 respective oxides. In such a case, the total amount of the raw material mixture as calculated as oxides, is the mass after carrying out heat treatment to remove moisture or organic substances contained in the above raw material mixture, or when pres in tearing is carried out, the mass 15 before the main firing after the presintering. To the raw material mixture having an alkali feldspar added to the mixture comprising the Mg- containing compound, the Al-containing compound and the Ti-containing compound, other sintering assistants may be 20 added, if necessary, whereby the nature of the sintered product thereby obtainable, can be improved. As such other sintering assistants, SiO2, ZrO2, Fe2O3, CaO and Y2O3 may, for example, be mentioned. The above raw material mixture is thoroughly mixed 25 and pulverised. The mixing and pulverization of the raw material mixture are not particularly limited and can be carried out by known methods. For example, they may be 21 carried out by means of a ball mill, a medium-stirring mill, etc. The pulverization degree of the raw material mixture is not particularly limited, but the average particle size is preferably at most 10 µm, particularly 5 preferably from 1 to 5 µm. The smaller the average particle size of the raw material mixture, the better, so long as it is within a range where no secondary particles will be formed. Molding assistants may preferably be incorporated to 10 the law material mixture. As such molding assistants, known agents such as a binder, a pore-forming agent, a release agent, a defoaming agent and a peptizer may be employed. As the binder, polyvinyl alcohol, microwax emulsion, methylcellulose or carboxymethylcellulose may, 15 for example, be preferred. As the pore-farming agent, activated carbon, coke, a polyethylene resin, starch or graphite may, for example, be preferred. As the release agent, a stearic acid emulsion may, for example, be preferred; as the defoaming agent, n-octyl alcohol or 20 octylphenoxyethanol may, for example, be preferred, and as the peptizer, diethylamine or triethylamine may, for example, be preferred. The amounts of the molding assistants are not particularly limited. However, in the case of the 25 present invention, they are preferably within the following ranges, respectively, as calculated as solid contents, per the total content of 100 parts by mass of 22 the Mg-containing compound, the Al-containing compound and the Ti-containing compound to be used as the raw materials, as calculated as the respective oxides. Namely, it is preferred to use the binder in an amount of 5 from about 0.2 to about 0.6 part by mass, the pore- forming agent in an amount of from about 20 to about 5O parts by mass, the release agent in an amount of from about 0.2 to about 0.7 part by maas, the deforming agent in an amount of from about 0.5 to abot 1.5 parts by mass 10 and the peptizer in an amount of from about 0.5 to about 1.5 parts by mass. The raw material mixture having such molding assistants incorporated, is mixed, kneaded and plasticized so that it is extrusion-processable, followed 15 by extrusion processing to form a honeycomb body. As the method for extrusion, a known method may be used, and the cross-sectional shape of each cell of the honeycomb may be circular, oval, tetragonal or triangular. Further, the entire configuration of the honeycomb body may be 20 either cylindrical or square tubular. The molded honeycomb is preferably dried and then fired at from 1,000 to l,700º C preferably from l,250 to 1,450ºC. The firing atmoephere is not particularly limited and is preferably an oxygen-containing atmosphere such as in the 25 air which is commonly employed. The firing time is not particularly limited so long as the firing can be done until the eintering proceeds sufficiently, and it is 23 usually at a level of from 1 to 20 hours. Also with respect to the temperature raising rate or the temperature lowering rate at the time of the above firing, there is no particular restriction, and such 5 conditions may be suitably set so that no cracks will be formed in the obtainable sintered product. For example, it is preferred to gradually raise the temperature without rapid rise of the temperature to sufficiently remove moisture, the molding assistants such as a binder, 10 etc. contained in the raw material mixture. Further, if neceasary, prior to heating at the above-mentioned tiring tamparature, presintering may be carried out preferably within a temperature range of from 500 to 1,000ºC for from 10 to 30 hours by mild temperature raise, whereby 15 the thermal stress in the sintered product during the formation of aluminum magnesium titanate, can be relaxed, and formation of cracks in the sintered product can be suppressed. The sintered product thus obtainable will be 20 aluminum magnesium titanate represented by the empirical formula NgxAl2(1-x)Ti(1+x)O5 (wherein O solubilized in the crystal lattice of aluminum magnesium titanate. Such a sintered product has high heat 25 resistance and high thermal shock resistance and yet has a crystal structure stabilized, as mentioned above, and will thus be a wintered product having excellent 24 mechanical strength and high heat decomposition resistance. (B): Aluminum titanate sintered product An aluminum titanate sintered product obtained by 5 firing at from 1,250 to l,700ºC a raw material mixture comprising 100 parts by mass of the component X comprising TiO2; and A12O3 in a molar ratio of the former/the latter being 40 to 60/60 to 40, and from 1 to 10 parts by mass of the component y. 10 The above TiO2 and A12O3 to be used for forming aluminum titanate may not necessarily be pure TiO2 and A12O3, respectively, and they are not particularly limited so long as they are components capable of synthesizing aluminum titanate by firing. Such 15 components may usually be suitably selected among those to be used as raw materials for various ceramics, such as alumina ceramics, titania ceramics and aluminum titanate ceramics. For example, a composite oxide, a carbonate, a nitrate and a sulfate containing Al and Ti as metal 20 components may also be used. TiO2 and Al2O3 are used in a molar ratio of the former/the latter of 40 to 60/60 to 40, preferably 45 to 5 0/55 to 50. Particularly, when the molar ratio of Al2O3/TiO2 is 1 or above within the above range, the 25 eutectic point of the sintered product can be avoided. In the present invention, Al2O3 and TiO2 are used as a mixture, and they will sometimes be collectively referred 25 to as component X. In the case of the honeycomb carrier of the present invention, it is necessary to add, in addition to the above component X, the component Y as an additive. As 5 the alkali feldspar which is one member of the component. Y, one represented by the empirical formula (NayK1-y)AlSi3O8 is used. In the formula, y satisfies XXX), preferably O.lXXX), particularly preferably 0.15XXX)0.85. An alkali feldspar having value y within 10 this range, has a low melting point and is particularly effective for promoting the sintering of aluminum titanate. As the oxide of a spinel structure containing Mg which is another member of component Y, MgAl2O4 or MgTi3O4 15 may, for example, be used. Such an oxide of a spinel structure may be a natural mineral, or a substance containing MgO and Al2O3, a substance containing MgO and TiO2 or an oxide of a spine1 structure obtained by firing such a substance. Further, a mixture of two or more 20 oxides of different spinel structure may be used. Further, the MgO precursor is not limited so long as it is capable of synthesizing MgO by firing, and it may, for example, be MgCO3, Mg(NO3)2, MgSO4 or a mixture thereof. The proportions of the component x and the component 25 Y are important. Prom 1 to 10 parts by mass of the component Y is used per 100 parts by mass of the component X. These proportions are proportions as oxides 26 of the components X and Y, respectively, and if a raw; material other than an oxide is used, the proportion is calculated as an oxide. If the proportion of the component Y per 100 parts by mass of the component x is 5 smaller than 1 part by mass, the effect by addition of the component Y will be insufficient to improve characteristics of the sintered product. On the other hand, if it exceeds 10 parts by mass, the amount of the Si or Mg element will be considerably in excess of the 10 limit of solid-solubilization in the aluminum titanate crystals, whereby the excessive added surplus component will be present as an oxide by itself in the sintered product, which may lead to a significant increase in the thermal expansion coefficient. The proportion of the 15 component Y per 100 parts by mass of the component X is particularly preferably from 3 to 7 parts by mass. In the present invention, it is preferred to use as the component Y a mixture of an alkali feldspar represented by the empirical formula (NayK3-y)AlSi3O8, and 20 an oxide of a spiNel structure containing Mg and/or MgO or its precursor, in combination. When such a mixture is used, the above synergistic improvement of functions will be achieved. In the mixture of an alkali feldspar, and an oxide of a spinel structure containing Mg and/or MgO 25 or its precursor, the mass ratio of the former/the latter is preferably 20 to 6O/80 to 40, particularly preferably 35 to 45/65 to 55. Within the above range, Si/Mg are 27 present in an equimolar ratio, and one of this range, eynergistic effects by simultaneous solid-solubilization of Si and Mg in aluminum titanate will hardly be obtained. In the present invention, in addition to the above 5 components X and Y, if necessary, other sintering assistants may be used, thereby the nature of the sintered product thereby obtainable, can be improved. As such other sintering assistants, SiO2, ZrO2, Fe2O3, CaO or Y2O3, may, far example, be mentioned. 10 The raw material mixture comprising the components X and Y is thoroughly mixed and pulverized. The mixing and pulverization of the raw material mixture are not particularly limited and can be carried out by known methods. For example, they may be carried out by means 15 of a ball mill, a medium-stirring mill, etc. The pulverisation degree of the raw material mixture is not particularly limited, but the average particle size is preferably at most 30 µm particularly preferably from 8 to 15 µm. The smaller the average particle size, the 20 better, so long as it is with in a range where no secondary particles will be formed. The amounts of molding assistants are not particularly limited. However, in the case of the present invention, they are preferably within the 25 following ranges, respectively, as calculated as solid contents, per the total content of 100 parts by mass of the component X and the component y (as calculated as 28 oxides) to be used as the raw materials. Namely, it is preferred to use a binder in an amount of from about 0.2 to about 0.6 part by mass, a pore-forming agent in an amount of from about 20 to about 50 parts by mass, a 5 release agent in an amount of from about 0.2 to about 0.7 part by mass, a deforming agent in an amount of from about 0.5 to about 1.5 parts by mass and a peptizer in an amount of from about 0.5 to about 1.5 parts by mass. The raw material mixture having such molding 10 assistants incorporated, is mixed, Kneaded and plasticized so that it is extrusion-pracessable, followed by extrusion processing to form a honeycomb body. As the method for extrusion, a known method may be used, and the cross-sectional shape of each cell of the honeycomb may 15 be circular, oval, tetragonal or triangular. Further, the entire configuration of the honeycomb body may be either cylindrical or square tubular. The molded honeycomb is preferably dried and then fired at from 1,250 to 1,700ºC, preferably from 1,300 to l,450ºC. The 20 firing atmosphere is not particularly limited and is preferably an oxygen-containing atmosphere such as in the air which is commonly employed. The firing time is not particularly limited so long as the firing can be done until the aintering proceeds sufficiently, and it is 25 usually at a level of from 1 to 20 hours. Also with respect to the temperature, raising rate or the temperature lowering rate at the time of the above 29 firing, there is no particular restriction, and such conditions may be suitably set so that no cracks will be formed in the obtainable sintered product. For example, it is preferred to gradually raise the temperature 5 without rapid rise of the temperature to sufficiently remove moisture, the molding assistants such as a binder, etc. contained in the raw material mixture. Further, if necessary, prior to heating at the above-mentioned firing temperature, presintering may be carried out preferably 10 within a temperature range of from 500 to l,000ºC for from 10 to 30 hours by mild temperature raise, whereby the thermal stress in the sintered product during the formation of aluminum titanate, can be relaxed, and formation of cracks in the sintered product can be 15 suppressed. The sintered product thus obtainable will be aluminum titanata formed from the component X wherein the 5 1 component contained in an alkali feldspar and the Mg component derived from an oxide of a spinel structure 20 containing Mg, MgO or a Mg-containing compound which can be converted to MgO by firing, as the component Y, are solid-solubilized in the crystal lattice of aluminum titanate. Such a sintered product has high mechanical strength, and a low thermal expansion coefficient and yet 25 has a crystal structure stabilized, as mentioned above, and will thus be a sintered product having excellent thermal decomposition resistance. 30 A. honeycomb body made of the above aluminum magnesium titanate sintered product (A) or aluminum titanate sintered product (B) has a thin wall honeycomb structure having a wall thickness of e.g. from 0.05 to 5 0.6 mm and a cell density of e.g. from 15 to 124 cells/cm2. And, the porosity of the partition wall is e.g. from 20 to 50%, and the thermal expansion coefficient is e.g. at most 3.0xl0-6K-1. Such a honeycomb body can be usad with stability, at from room temperature 10 to such a high temperature as above l,600°C as the thermal decomposition reaction of aluminum magnesium titanate or aluminum titanate is suppressed. The honeycomb body is used as a carrier for a catalyst to clean various exhaust gases containing 15 harmful components such as hydrocarbons, carbon monoxide, NOx and SOx, particularly an exhaust gas of an automobile containing NOx. Particularly, the honeycomb carrier of the present invention is stable against an alkali at a high temperature, whereby it is effective against an 20 exhaust gas of an automobile of a system wherein a fuel is directly jetted into an engine or of a system wherein a fuel is diluted and turned, an exhaust gas from which contains NOx at a relatively high concentration. As a catalyst supported by the carrier, various 25 known catalysts may be used such as a conventional so- called three way catalyst to remove hydrocarbons and carbon monoxide. However, the carrier of the present 31 invention is particularly effective for a catalyst containing an alkali metal ox alkaline earth metal component to remove NOx in an exhaust gas, The carrier of the present invention is effective for a catalyst 5 containing potassium or barium effective for removal of NOx, particularly potassium, amoivg alkali metals and alkaline earth metals. As a method of making the catalyst be supported by the honeycomb body of the present invention, a known 10 means may be employed. When a catalyst is to be supported, a material having a large specific surface area, such as alumina or silica, may be interposed, as the case requires, so as to improve the supporting ratio- That is, alumina or silica may be supported by the is honeycomb carrier, and a catalyst is supported fay alumina or silica thus supported. The honeycomb body by which a catalyst is supported, is preferably set in an can body by means of a suitable supporting material. 20 EXAMPLE NOW, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means thereby restricted. 35 EXAMPLE 1 1 To 100 parts by mass of a mixture comprising 26.7 mass% (2o mol%} of easily sinterable α-alumina, 62.8 32 maes% (60 mol%) of anatase-type titanium oxide and 10.5 mass% (2 0 mol%) of periclase-type magnesium oxide present as a natural mineral, 4 parts by mass of an alkali feldspar represented "by (Na0-6K0-4)AlSi3O8, 0.25 part by 5 mass of polyvinyl alcohol as a binder, 1 part by mass of diethylamine as a peptizer, 0.5 part by mass of polypropylene glycol as a defoaming agent, and 35 parts by mass of activated carbon having a particle size of at most 30 µm as a. pore-forming agent, were added and mixed in for 3 hours in a ball mill and then dried in a dryer at 120°C for at least 12 hours to obtain a raw material powder. The obtained raw material powder was pulverized to an average particle size of about 5 µm and extruded, by a IS vacuum extruder (manufactured by Miyazaki Iron Works Co., Ltd.) to obtain a cylindrical honeycomb body having a diameter of 129 mm and a length of 150 mm, and having cross-sectianally square cells with a wall thickness of 0.1 mm and a. cell density of 93 cells/cm2 . This 20 honeycomb body was dsied and then, fired in the atmosphere at 1,400°C fox 4 hours and then left to cool, to obtain a sintered product. A honeycomb sintered product made of an aluminum 25 magnesium citanata sintered product was obtained in. the. same manner as IN Example 1-1 except that no alkali feldspar was used. 33 COMPARATIVE EXAMPLE 1-2 A honeycomb having the game shape as that in Example 1 -1 -was prepared by using as the material for a honeycomb carrier a cordierite powder (2MgO-2Al2O3.5SiO2) by a known 5 method. PROFERTY TESTS WITH RESPECT TO HOMEYCOMB SINTERED PRODUCTS With respect to the honeycomb sintered products obtained in the above Example l-l and Comparative 10 Examples 1-1 and 1-2, the porosity (%), the thermal expansion coefficient (x10-6K-1) at from room temperature to 800°C, the thermal shocK resistance (°C) by an in- water dropping method, the softening temperature (°C) and the compression strength (MPa) were measured, and the 15 results are shown in Table 1-1. Here, the porosity was measured by a method in accordance with JIS R1634, the thermal expansion coefficient by a method in accordance with JIS R1618, the thermal shock resistance by a method in accordance with JIS R1648, the softening temperature 20 by a method in accordance with JIS R2209, and the compression strength by a method in accordance with JIS R1608, Further, with respect to the compression strength, from each honeycomb sintered product* a square test specimen having cross-sectionally 5x5 cells and a length 25 of 15 mm, was cut out, and tnis specimen was measured from three directions i.e. (A) in the lengthwise axial direction (axial), (B) in the vertical direction 34 (tangential) and (C) in the direction inclined by 45° from the lengthwise axis (diagonal). TABLE 1-1 Porosity(%) Thermalexpansioncoefficient(10-6K-1) Thermalshockresistance Softeningtemperature Compression strength(MPa) (A) (B) (C) Example 1-1 34 1.0 850 1580 >14 >3 >2 ComparativeExample 1-1 35 0.2 860 1600 >9 >1.5 >0.2 ComparativeExample 1-2 35 0.6 650 1320 >10 >1.3 >0.2 36 THERMAL DECOMPOSITION RESISTANCE TEST From the honeycomb carrier in Example 1-1, a test specimen of 10 mm x 10 mm x 10 mm was cut out and held in a high temperature atmosphere of 1,100°C, whereby the. 5 change with time of the remaining ratio α (%) of aluminum magnesium titanate was investigated to carry out a thermal decomposition resistance test. Here, the remaining ratio of aluminum magnesium titanate was obtained by the following method from the 10 spectrum of the X-ray diffraction measurement (XRD) , Firstly, as MgAl2O4 (spinel) and TiO2 (rutile) are formed when aluminum magnesium titanate undergoes thermal decomposition, by using the integrated intensity (IT102(110)) of the diffraction peak at the (110) face of is rutile and the integrated intensity (IMAT(023)) of the diffraction peak at the (023) face of aluminum magnesium ticanate, the intensity ratio R of aluminum magriesium titanate to rutile was obtained by the following formula: R= IMAT(023) / ( IMAT(023) + ( IT102 (110) ) 20 Further, also with respect to the sintered product before carrying out the thermal treatment at l,l00°c, the intensity Ratio R0 of aluminum magnesium titanate to rutile was obtained in the same manner. Then, using R and R0 obtained as described above, the remaining ratio α 25 (%) of aluminum magnesium titanate was obtained by the following formula; α=(R/R0) x 100 37 With respect to the respective sintered products in Example 1-1 and Comparative Example 1-1, the changes with time of the remaining ratio a of aluminum magnesium titanate are shown by a graph in Fig. 1. AS is evident 5 from Fig. 1, the sintered product in Example 1-1 is superior in the thermal decomposition resistance, as the remaining ratio α of aluminum magnesium titanate is maintained at a high level over a long time, as compared with the sintered product in Comparative Example 1-1. 10 ALKALI RESISTANCE TEST WITH RESPECT TO HONEYCOMB BODIES The following test was carried out to examine the corrosion resistance of the honeycomb bodies against a potassium-containing catalyst which is a catalyst for removal of NOx in an exhaust gas of an automobile. A 15 honeycomb carrier against an exhaust gas of an automobile is used at a temperature of from room temperature to 850°C, and the potassium concentration of the potassium- Containing catalyse is not so high. However, in this test, an accelerated test under severe conditions was 20 carried out, which comprises dipping a test specimen in an aqueous potassium nitrate solution at a concentration of 1 mol/liter, drying it and holding it in a furnace maintained at a temperature of 900°C for a long period of time. 25 TEST METHOD From each of the honeycomb bodies in Example 1-1 and 38 Comparative Example 1-2, a test specimen with, a 30 mm square cross section and a length of 50 mm was cut out, and the test specimen was dipped in an aqueous potassium nitrate solution at a concentration of 1 mol/liter at 5 room temperature for l hour, and then dried at 70°C for 1 hour- The dried honeycomb body was inserted into a tubular furnace with, an inner diameter of 5 cm and a length of 42 cm and held for a predetermined time under the following conditions while supplying the air 10 containing 10% of moisture to the tubular furnace at 25 cc/min. Then, the honeycomb body taken out from the tubular furnace was subjected to XRD measurement to examine degeneration of the honeycomb body material. The air containing 10% of moisture to be supplied to the 15 tubular furnace was prepared by making the air pass through a water tank controlled at 60°C. The results of the test are shown, in Table 1-2, Holding conditions: Temperature in the furnace: 900°C, temperature- 20 raising and lowering rate of the furnace: l00oC/hr, holding time: 50 hours, 100 hours, 150 hours or 200 hours 39 TABLE 1-2 Holding time 50 hours 100 hours 150 hours 200 hours Honeycombbody inExample 1-1 No change No change No change No change Honeycombbody inComparativeEXample 1-2 No change Peak ofKAlSiO4observedin thevicinityOf **29-28° Peak ofKAlSiO4 Peak ofKAlSiO4improved As is evident from the results shown in Table 1-2, the honeycomb body in Example 1-1 has a great corrosion 5 resistance to potassium, as compared with the honeycomb body in Camparative Example 1-2. EXAMPLE 2-1 To 100 parts fey mass of a mixture comprising 56,1 mass% (50 mol%} of easily sinterable α-alumina and 43.9 10 mass% (50 mol%) of anatase-type ticanium oxide, 4 parts by mass of an alkali feldspar represented by (Na0.6K0.4)AlSi3O2 as an additive, 0.25 part by mass of polyvinyl alcohol as a binder, 1 part by mass of diethylamine as a peptizer, 0.5 part by mass of 15 polypropylene glycol as a defeaming agent, and 35 parts by mass of activated carbon having a particle size of from 50 to 80 µm as a pore-forming agent, were added and mixed for 3 hours in a ball mill and then dried in a dryer at 120°C for at least 12 hours to obtain a raw 20 material povder. 40 The obtained raw material powder was pulverised to an average particle. size of about 5 µm and extruded by a vacuum extruder (manufactured by Miyazaki Iran. Works CO., Ltd.) to obtatin a cylindrical honeycomb body having a 5 diameter of 12 9 mm and a length of 150 mm, and having cross-sectionally square cells with a wall thickness of 0.1 mm and a cell density of 93 cells/cm2. This honeycomb body was dried and then fired in the atmosphere at l,400°c for. 4 hours and then left to cool, to obtain a 10 honeycomb body. COMPARATIVE EXAMPLE 2-1 A honeycomb carrier made of an aluminum titanate sintered product was obtained in the same manner as in Example 2-1 except that no alkali feldspar was used. 15 COMPARATIVE EXAMPLE 2-2 A honeycomb carrier having the same shape as that in Example 2-1 was prepared by using a cordierite powder (2MgO-2Al2O3-5SiO2) by a known method, EXAMPLE 2-2 20 To 100 parts by mass of a mixture comprising 56.1 mass% (50 mol%) of easily sinterable α-alumina and 43.9 mass% (50 mol%) of anatage-type titanium oxide, 4 parts by mass of an alkali feldspar represented by (Na0.6K0.4) AlSi3O8 and 6 parts by mass of a spinel compound 25 represented by the formula MgAl2O4 as additives, 0.25 part by mass of polyvinyl alcohol as a binder, 1 part by mass of diethylamine as a peptizer, 0.5 part by mass of 41 polypropylene glycol as a defoaming agent, and 35 parts by mass of activated carbon having a particle size of from 30 to 80 µm as a pore-forming agent, were added and mixed for 3 hours in a ball wil1 and then dried in a 5 drier at 120°c for at least 12 hours to obtain a raw material powder. Using the obtained raw material powder, pulverization, extrusion molding, drying and firing were carried out in the same manner as in Example 2-1 to 10 obtain a honeycomb carrier. EXAMPLE 2-1 To 100 parts by mass of a mixture comprising 56.1 mass% (50 mol%} of easily sinterable α-alumina and 43.9 mass* (50 mol%) of anatase-type titanium oxide, 6 parts 15 by mass of a spinel compound represented by the formula MgAl2O4 as an additive, 0.25 part by mass of polyvinyl alcohol as a binder, l part by mass of diethylamine as a peptizer, 0.5 part by mass of polypropylene glycol as a defoaming agent, and 35 parts by mass of activated carbon 20 having a particle size of from 5O to 80 µm as a pore- forming agent, were added and mixed for 3 hours in a ball mill and then dried in a drier at 120°C for at least 12 hours to obtain a raw material powder. Using the obtained raw material powder, 35 pulverization, extrusion molding, drying and firing were carried out in the same manner as in Example 2-1 to obtain a honeycomb carrier. 42 PROPERTY TESTS WITH RESPECT TO HONEYCOMB SINTERED PRODUCTS With respect to the honeycomb sintered products obtained in the above Examples 2-1, 2-2 and 2-3 and 5 Comparative Examples 2-1 and 2-3, the porosity (%), the thermal expansion coefficient (X 10-6K-1) at from room temperature to 800°C, the thermal shock resistance (°C) by an in-water dropping method, the softening temperature (°C) and the compression strength (MPa) were measured, 10 and the results are shown in Table 2-1. Here, the porosity was measured by a method in accordance with JIS Rl634, the thermal expansion coefficient by a method in accordance with JIS R1618, the thermal shock resistance by a method in accordance with JIS R1648, the softening 15 temperature by a method in accordance with JIS R2209, and the compression strength by a method in accordance with JIS R1608. Further, with respect to the compression strength, from each honeycomb sintered product, a square test apecimen having cross-sectionally 5x5 cells and a 20 length of 15 mm, was cut out, and this specimen was measured from three directions i.e. (A) in the lengthwise axial direction (axial), (B) in the vertical direction (tangential) and (C) in the direction inclined by 45° from the lengthwise axis {diagonal). 44 As is evident from Table 2-1, each of the honeycomb carriers in Examples 2-1, 2-2 and 2-3 has a compression strength sufficient for practical use. The honeycomb carrier in Comparative Example 2-1 has low strength 5 insufficient for practical use, and the honeycomb carrier in Comparative Example 2-2 has a low softening temperature and is thereby poor in heat resistance. THERRMAL DECOMPOSITION RESISTANCE TEST From each of the honeycomb carriers in Examples 2-1 10 and 2-2 and Comparative Example 2-1, a test specimen of 10 mm x lo mm x 10 mm was cut out and held in a high temperature atmosphere of 1,000°C whereby the change with time of the remaining ratio β(%) of aluminum titanate was investigated to carry out a thermal AS decomposition resistance test. Here, the remaining ratio of aluminum titan-ate was obtained by the following method from the specturm of the X-ray diffraction measurement (XRD). Firstly, as Al2O3 (corundum] and TiO2 {rutile} are 20 formed when alutninum titanate undergoes thermal decomposition ueirng the integrated intensity (IT120 (110)) of the diffraction peak at the (110) face of rutile and the integrated intensity (IAT(023)) of the diffraction peak at the (023) face of aluminum titanate, the intensity 25 ratio r of aluiminum titanate to rutile was obtained by the following formula: 45 Further, also with respect to the sintered product before carrying out the thermal treatment at 1,000°C, the intensity ratio r0 of aluminum, titanate to rutile was obtained in the same manner. Then, using r and rc 5 obtained as described above, the remaining ratio β(%) of aluminum titanate was obtained by the following formula: β= (r/ro) x 100 With respect to the respective honeycomb shape sintered products in Examples 2-1 and 2-2 and Comparative 10 Example 2-1, the changes with time of the remaining ratio β of aluminum titanate are shown by a graph in Fig, 2, As is evident from. Fig, 2, Examples 2-1 and 2-2 are supperior in the thermal decomposition resistance, as the remaining ratio is maintained at a high level over a long is time, as compared with Comparative Example 2-1. Further, it is evident that while the remaining ratio in Example 2-1 after expiration of 100 hours in Fig. 2 is slightly- low, the remaining ratio in Example 2-2 is still remained at a high level and thus shown that the thermal 20 decomposition resistance is further excellent over Example 2-1. ALKALI RESISTANCE TEST WITH RESPECT TO HONEYCOME BODIES The following test was carried out to examine the corrosion resistance of the honeycomb bodies against a 25 potassium-containing catalyst which is a catalyst for removal of NOx in an exhaust gas of an automobile. A honeycomb carrier against an exhaust gas of an automobile 45 is used at a temperature of from room temperature to 850oC, and the potassium concentration of the potaseium- containing catalyst is not so high. However, in this test, an accelerated test under severe conditions was 5 carried out, which comprises dipping a test specimen in an aqueous potassium nitrate solution at a concentration of 1 mol/liter, drying it and holding it in a furnace maintained at a temperature of 900°C for a long period of time, 10 TEST METHOD From each of the honeycomb bodies in Examples 2-1 and 2-2 and Comparative Example 2-2, a test specimen with a 30 mm sguare cross section and a length of 5 0 mm was cut out, and the test specimen was dipped in an aqueous 15 potassium nitrate solution, at a concentration of 1 mol/liter at room temperature for 1 hour, and then dried at 70°c for 1 hour. The dried honeycomb body was inserted into a tubular furnace with an inner diameter of 5 cm and a length of 42 cm and held for a predetermined 20 time under the following conditions while supplying the air containing 10% of moisture to the tubular furnace at 25 cc/min. Then, the honeycomb body taken out from the tubular furnace was subjected to XRD measurement to examine degeneration of the honeycomb body material. The 25 air containing 10% of moisture to be supplied to the tubular furnace was prepared by making the air pass through a water tank controlled at 60°C. The results of 47 the teat are shown in Table 2-2. Holding conditions: Temperature in the furnace: 900°C, teraperature- raising and lowering rate of the furnace: 100°C/hr, 5 holding time; 50 hours, 100 hours, 150 hours or 200 hours TABLE 3-2 Honeycombbody Holding time 50 hours 100 hours 150 hours 200 hours Example 2-1 No change No change No change No change Example 2-2 No change No change No change No change ComparativeExample 2-2 No change Peak ofKAlSiO4observedin. thevicinityof **2^=28° Peak ofKAlSiO4improved Peak ofKAlSiO4improved As is evident- from results shown in Table 2-2, each of the honeycomb carriers in Examples 2-1 and 2-2 is 10 excellent in corrosion resiacance to an alkali. 48 CLAIMS: 1. A honeycomb carrier for an exhaust: gas-cleaning catalyst which is a honeycomb carrier to support a catalyst to clean an exhaust gas, characterised in that 5 the material for the honeycomb carrier is an aluminum magnesium titanate sintered product obtained by firing at from 1,000 to l,700°C a mixture comprising 100 parts by mass, as calculated as oxides, of a mixture comprising a Mg-containing compound, an Al-containing compound and a 10 Ti-containing compound in the same metal component ratio as the metal component ratio of Mg, Al and Ti in an aluminum magnesium titanate represented by the empirical formula MgxAl2(1-x)Ti(1-x)O5 (wherein 0 15 empirical formula (Nayk1-y)AlSi3O8 (wherein XXX). 2 . A honeycomb carrier for an exhaust gas-cleaning catalyst which is a honeycomb carrier to support a catalyst to clean an exhaust gas, characterized in that the material for the honeycomb carrier is an aluminum 20 titanate sintered product obtained by firing at from 1,250 to 1,700°C a raw material mixture comprising 100 parts by mass of a mixture (hereinafter referred to as component X) comprising TiO2 and Al2O3 in a molar ratio of the former/the latter being 40 to 60/60 to 40, and from 1 25 to 10 parts by mass of an alkali feldspar represented by the empirical formula. (NayK1-y)AlSi3O8 (wherein XXX), an oxide of a spinel structure containing Mg, or MgO or a 49 Mg-containing compound which can be converted to MgO by firing (hereinafter referred to as component Y). 3. The honeycomb carrier for an exhaust gas-cleaning catalyst according to Claim 2, wherein the component Y is 5 a mixture comprising an alkali feldpar represented by (Nayk1-y) Alsi3O8 (wherein XXX) , and an oxide of a spinel structure containing Mg and/or MgO or a Mg-containing compound which can be converted to MgO by firing. 4, The honeycomb carrier for an exhaust gas-cleaning 10 catalyst according to any one of Claims 1 to 3 , which has a wall thickness of from 0.05 to 0.6 mm, a cell density of from 15 to 124 cells/ cm2, a porosity of the partition wall of from 20 to 50%, and a thermal expansion coefficient of at most 3.0x10-6K-1. 15 5. The honeycomb carrier for an exhaust gas-cleaning catalyst according to any one of Claims 1 to 4, wherein the catalyst contains an alkali metal or alkaline earth metal component to remove NOx in the exhaust gas_ 6, The honeycomb carrier for an exhaust gas-cleaning 20 catalyst according to any one of Claims 1 to 5, wherein the exhaust gas is an exhaust gas of an automobile of a system wherein a fuel is directly jetted, into an engine or of a system wherein a fuel is diluted and burned. 7. A process for producing honeycomb carrier for an as exhaust gas-cleaning catalyst, characterized by preparing a raw material mixture comprising 100 parts by mass, as calculated as oxides, of a mixture comprising a Mg- 50 containing compound, an Al-containing compound and a Ti- containing compound in the same metal component ratio as the metal component ratio of Kg, Al and Ti in an aluminum magnesium titanate represented by the empirical formula 5 MgxAl2(1-x)Ti(1-x)O5 (Wherein 0 empirical formula (NayK1-y)Alsi3O9 (wherein XXX), adding a molding assistant to the raw material mixture, followed by kneading to plasticize the raw materia1 mixture to 10 make it extrusion-processable, and then extrusion processing it into a honeycomb body, followed by firing at from 1,000 to 1,700°C. 8. A process for producing a honeycomb carrier for an exhaust gas-cleaning catalyst, characterized by preparing 15 a mixture comprising 100 parts by mass of a mixture (hereinafter referred to as component X) comprising TiO2 and Al2O3 in a molar ratio of the former/the latter being 40 to 60/60 to 40, and from 1 to 10 parts by mass of an alkali feldspar represented by the empirical formula 20 (NayK1-y)AlSi3O8 (where in XXX), an oxide of a spinel stmacture containing Mg, or MgO or a Mg-containing compound which can be converted to MgO by firing (hereinafter referred to as component Y) , adding a molding assistant to the mixture, followed by kneading to 25 plasticize the mixture to make it extrusion-processable, and extrusion processing it into a honeycomb body, followed by firing at from 1,250 to 1,700°C. 51 9. The process for producing a honeycomb carrier for an exhaust gas-cleaning catalyst according to Claim 7 or 8, wherein the average particle size of each component contained in the raw material mixture is at most 10 µm. 5 10 . A method for cleaning an exhaust gas, which comprises contacting the exhaust gas to a honeycomb carrier supporting a catalyst to clean an exhaust gas, characterized in that the material for the honeycomb carrier is an aluminum magnesium titanate sintered 10 product obtained by firing at from 1,000 to l,700°C a mixture comprising 100 parts by mass, as calculated as oxides, of a mixture comprising a Mg-containing compound, an Al-containing compound and a Ti-containing compound in the same metal component ratio as the metal component is ratio of Mg, Al and Ti in an aluminum magnesium titanate represented by the empirical formula MgxAl2(3-x)Ti(1+x)O5 (wherein 0 (NayK1-y)AlSi308 (wherein XXX). 20 11. A method for cleaning an exhaust gas, which comprises contacting the exhaust gas to a honeycomb carrier supporting a catalyst to clean an exhaust gas, characterized in that the material for the honeycomb carrier is an aluminum titanate sintered product obtained 25 by firing at from 1,250 to l,700°C a raw material mixture comprising 100 parts by mass of a mixture (hereinafter referred to as component X) comprising TiO2 and A12O3 in a 52 molar ratio of the former/the latter being 40 to 60/60 to 40, and from 1 to 10 parts by mass of an alkali feldspar represented by the empirical formula (NayK1-y)AlSi3O8 (wherein XXX) , an oxide of a spinel structure 5 containing Mg, ox MgO or a Mg-containing conpound which can be converted to MgO by firing (hereinafter referred to as component Y). to provide a honeycomb carrier to support a catalyst to clean e.g. an exhaust gas of an automobile particularly containing NOx, which is excellent in heat 5 resistance, thermal shock, resiatance, mechanica1 strength and thermal decomposition resistance and has a great corrosion resistance to a catalyst, and is thus capable of being used with stability for a long period of time, and a procege for its production. 10 The material for the honeycojnb carrier is an aluminum magnesium titanate sintered product obtained by firing at from 1,000 to l,700°C a molded product formed from a raw material mixcture eomprising 100 parts by mass, as calculated as oxides, of a mixture comprising a Mg- 15 containing compound, an Al-containing compound and a Ti- containing compound in the same metal component ratio as the metal component ratio ot Mg, Al and Ti in an aluminium magnesium titanate represented by the empirical formula MgxAl2(1+x)Ti(1+x)O5 fwherein 0 empirical formula (NayK1-y)AlSi3O8 (wherein XXX) . |
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| Patent Number | 224197 | ||||||||||||||||||
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| Indian Patent Application Number | 00217/KOLNP/2006 | ||||||||||||||||||
| PG Journal Number | 41/2008 | ||||||||||||||||||
| Publication Date | 10-Oct-2008 | ||||||||||||||||||
| Grant Date | 03-Oct-2008 | ||||||||||||||||||
| Date of Filing | 30-Jan-2006 | ||||||||||||||||||
| Name of Patentee | OHCERA CO., LTD | ||||||||||||||||||
| Applicant Address | 1-19, UCHIHONMACHI 2-CHOME, CHUOU-KU, OSAKA-SHI, OSAKA | ||||||||||||||||||
Inventors:
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| PCT International Classification Number | C04B 35/478 | ||||||||||||||||||
| PCT International Application Number | PCT/JP2004/011203 | ||||||||||||||||||
| PCT International Filing date | 2004-07-29 | ||||||||||||||||||
PCT Conventions:
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