FR2950341A1 - Porous structure useful as e.g. filter in automobiles, comprises ceramic material comprising oxide material corresponding to composition including aluminum trioxide, titanium oxide, magnesium oxide, iron oxide and zirconium oxide - Google Patents

Abstract

The porous structure comprises a ceramic material comprising an oxide material corresponding to a composition including aluminum trioxide (35-50 wt.%), titanium oxide (26-50 wt.%), less than 6 wt.% of magnesium oxide, 2-15 wt.% of iron oxide, 2-8 wt.% of zirconium oxide and more than 5% of silicon oxide. The material is obtained by reactive sintering of simple oxides or their precursors or by heat treatment of sintered grains. The material comprises a main phase including a solid solution comprising titanium, aluminum, zirconium-iron and magnesium. The porous structure comprises a ceramic material comprising an oxide material corresponding to a composition including aluminum trioxide (35-50 wt.%), titanium oxide (26-50 wt.%), less than 6 wt.% of magnesium oxide, 2-15 wt.% of iron oxide, 2-8 wt.% of zirconium oxide and more than 5% of silicon oxide. The material is obtained by reactive sintering of simple oxides or their precursors or by heat treatment of sintered grains. The material comprises a main phase including a solid solution comprising titanium, aluminum, zirconium-iron and magnesium, a phase including titanium oxide and/or zirconium oxide, and a silicate phase (0-45 wt.%). The molar percentage of the composition is calculated using an equation, a'-t+2m 1+m 2, where a is molar percent of aluminum oxide, s is molar percent of silicon oxide, a'=a-0.37x s, t is molar percent of titanium oxide, m 1is molar percent of magnesium and m 2is molar percent of iron. The silicate phase comprises silica and alumina, where the proportion of silica in the glass phase is greater than 34%. The ceramic material has a porosity of greater than 10%, where the size of the pores is 5-60 microns.

Description

1 POROUS STRUCTURE OF ALUMINA TITANATE TYPE

The invention relates to a porous structure such as a catalytic support or a particulate filter whose material constituting the filtering and / or active part is based on alumina titanate. The ceramic material at the base of the ceramic supports or filters according to the present invention consist mainly of oxides of the elements Al, Ti. The porous structures are most often honeycomb and in particular used in an exhaust line of a diesel-type internal combustion engine. In the remainder of the description, for convenience and in accordance with the habits in the field of ceramics, said oxides comprising the elements will be described with reference to the corresponding simple oxides, for example Al 2 O 3 or TiO 2. In particular, in the description which follows, unless otherwise stated, the proportions of the various elements constituting the oxides according to the invention are given with reference to the weight of the corresponding simple oxides, reported as a percentage by weight relative to all the oxides present in the compositions. described. In the remainder of the description, the application and advantages in the specific field of filters or catalytic supports allowing the elimination of pollutants contained in the exhaust gases resulting from a gasoline or diesel heat engine, the field to which reports the invention. At present, the exhaust gas depollution structures generally have a honeycomb structure.

In known manner, during use, a particulate filter is subjected to a succession of filtration (soot accumulation) and regeneration (soot elimination) phases. During the filtration phases, the soot particles emitted by the engine are retained and are deposited inside the filter. During the regeneration phases, the soot particles are burned inside the filter, in order to restore its filtration properties. It is thus conceivable that the mechanical strength properties at both low and high temperature of the constituent material of the filter are essential for such an application. Similarly, the material must have a sufficiently stable structure to withstand, especially throughout the life of the equipped vehicle, temperatures that can locally rise to values substantially greater than 1000 ° C, especially if certain regeneration phases are poorly controlled. At present, the filters are mainly made of porous ceramic material, most often made of silicon carbide or cordierite. Such silicon carbide catalytic filters are for example described in patent applications EP 816 065, EP 1 142 619, EP 1 455 923 or else WO 2004/090294 and WO 2004/065088. Such filters make it possible to obtain chemically inert filtering structures with excellent thermal conductivity and having porosity characteristics, in particular the average size and the pore size distribution, which are ideal for a filtering application of soot from a thermal motor. However, certain disadvantages peculiar to this material still remain: A first disadvantage is related to the slightly high thermal expansion coefficient of SiC, greater than 3.10-6 K-1, which does not allow the manufacture of monolithic filters of large size and in most cases, it is necessary to segment the filter into a plurality of honeycomb elements bonded by a cement, as described in application EP 1 455 923. A second disadvantage, of an economic nature, is related to the extremely firing temperature. high, typically greater than 2100 ° C, allowing sintering ensuring sufficient thermomechanical strength of honeycomb structures, especially during successive phases of regeneration of the filter. Such temperatures require the installation of special equipment that significantly increases the cost of the filter finally obtained. On the other hand, if the cordierite filters are known and used for a long time, because of their low cost, it is now known that problems can occur in such structures, especially during poorly controlled regeneration cycles, during which the filter can be subjected locally to temperatures above the melting temperature of cordierite. The consequences of these hot spots can range from a partial loss of efficiency of the filter to its total destruction in the most severe cases. In addition, cordierite does not have sufficient chemical inertness, with respect to the temperatures reached during successive cycles of regeneration and is therefore likely to react and be corroded by the species from residues of lubricant, fuel or other oils , accumulated in the structure during the filtration phases, this phenomenon can also be at the origin of the rapid deterioration of the properties of the structure.

For example, such disadvantages are described in the patent application WO 2004/011124 which proposes to remedy a filter based on aluminum titanate (60 to 90% by weight), reinforced by mullite (10 to 40% by weight). ), whose durability is improved. According to another embodiment, the application EP 1 559 696 proposes the use of powders for the manufacture of honeycomb filters obtained by reactive sintering of aluminum, titanium and magnesium oxides between 1000 and 1700 ° C. The material obtained after sintering is in the form of a mixture of two phases: a majority phase of structural type pseudo-brookite Al2TiO5 containing titanium, aluminum and magnesium and a minority feldspar phase, NayK1_yAlSi308 type.

However, the experiments carried out by the applicant have shown that it is difficult at the present time to guarantee the performance of a structure based on materials of the titanate alumina type, in particular to achieve values of thermal stability, thermal expansion coefficient e own for example to make them directly usable in a high temperature application of the type particulate filter. The object of the present invention is thus to provide a porous structure comprising an oxide material, having properties, as previously described, substantially improved, in particular so as to make it more advantageous for use in the manufacture of a porous filtering structure. and / or catalytic, typically honeycomb.

More specifically, the present invention relates to a porous structure comprising a ceramic material whose chemical composition comprises, in weight percentages on the basis of the oxides: - more than 15% and less than 55% of Al 2 O 3, - more than 25% and less than 60% of TiO2, less than 20%, in total, of at least one oxide of an M1 element selected from MgO, CoO, more than 0.7% and less than 25%, in total, at least one oxide of an element M2 selected from the group consisting of Fe 2 O 3, Cr 2 O 3, MnO 2, La 2 O 3, Y 2 O 3, Ga 2 O 3, - more than 0.7% and less than 25% in total, or even less than 20% at total, of at least one oxide of an element M3 selected from the group consisting of ZrO2, Ce203, HfO2, - less than 30% of SiO2, said material being obtained by reactive sintering of the corresponding simple oxides or from one of their precursors or by heat treatment of sintered grains corresponding to said composition. As already described above, the proportions of the various elements constituting the oxides of the material are given, in the preceding formulation, by reference to the weight of the corresponding simple oxides, as a percentage by weight relative to all the oxides present in said chemical compositions. It is however quite obvious that, in the sense of the present invention, if the elements M1, M2 or M3 are expressed in the preceding relation in the form of corresponding simple oxides, conventional in solid-state chemistry, they are most often present , at least for the most part, in another more complex form in the material according to the invention and may in particular be included in mixed oxides and in particular in phases of the aluminum titanate type. Preferably, the porous structure is constituted by said ceramic material. Said porous structure according to the invention also preferably corresponds to a composition, in molar percentage on the basis of all the oxides present in said composition, such that: a '- t + 2m1 + m2 is between -15 and 15 where: - a is the molar percentage of Al 2 O 3, - s is the molar percentage of SiO 2, - a '= a - 0.37 xs, - t is the molar percentage of TiO 2, - m 1 is the total molar percentage the oxide (s) of MI, m2 is the total molar percentage of the oxide (s) of M2. Preferably, in the above formulation, t + 2m + m2 is between -10 and 10, more preferably t + 2m + m2 is between -8 and 8 and very preferably - t + 2m1 + m2 is between -6 and 6. Preferably, Al2O3 represents more than 20% of the chemical composition, the percentages being given by weight on the basis of the oxides corresponding to the elements present. For example, especially for the application of the filter or catalytic support type, Al 2 O 3 may represent more than 25% and more preferably more than 30% of the chemical composition. Preferably Al 2 O 3 is less than 52%, even less than 51%, or even less than 50% of the chemical composition, the percentages being by weight based on the oxides. Preferably TiO 2 represents more than 26% of the chemical composition. Preferably TiO 2 is less than 55%, even less than 50%, or even less than 45%, of the chemical composition, the percentages being by weight based on the oxides. Preferably, if they are present, the oxide (s) of M1 represent (s) more than 0.7%, or even more than 1%, or even more than 1.5. % and very preferably more than 2% of the chemical composition. Preferably, the oxide (s) of M 1 represents (s) less than 10% and very preferably less than 6% of the chemical composition, the percentages being given by weight and on the basis of the oxides.

Preferably, M1 is Mg only. Preferably, the oxide (s) of M2 represent (s) more than 1%, even more than 1.5% and very preferably more than 2% of the chemical composition. Preferably, the oxide (s) of M2 represent (s) in total less than 20% and very preferably less than 15% of the chemical composition, the percentages being given by weight and on the basis of the oxides. Preferably, M2 is Fe only. In such an embodiment, Fe 2 O 3 represents more than 0.7% or even more than 1% and very preferably more than 1.5% of the chemical composition. Preferably, Fe 2 O 3 represents less than 20% and very preferably less than 18% or even less than 15% of the chemical composition, the percentages being given by weight on the basis of the oxides.

In one embodiment, the composition comprises iron and magnesium. The corresponding oxides Fe 2 O 3 and MgO then represent, by weight and in total, more than 1% or even more than 1.5% and very preferably more than 2% of the chemical composition of the chemical composition. Preferably Fe 2 O 3 and MgO together represent less than 18% and very preferably less than 15% of the chemical composition, the percentages being given by weight on the basis of the oxides. Preferably, the oxide (s) of M3 represent (s) in total more than 0.8% and very preferably more than 1% of the chemical composition, the percentages being given by weight and based on oxides. Preferably, the (or) oxide (s) of M3 represent (s) in total less than 10% and very preferably less than 8% of the chemical composition. Preferably, M3 is Zr only. It is understood that within the meaning of the present description, it is possible that the composition nevertheless comprises other compounds in the form of unavoidable impurities. In particular, even when only a zirconium-containing reagent is initially introduced into the process for producing a structure according to the invention, it is known that said reagents most often comprise a small amount of Hafnium, in the form of an impurity. inevitable, which can sometimes be up to 1% or 2% molar of the total amount of Zirconium introduced. The material may, for example, have the following chemical composition, in weight percent based on the oxides: greater than 35% and less than 50% Al 2 O 3, greater than 26% and less than 50% TiO 2, less than 6% MgO, more than 2% and less than 15% Fe2O3, more than 2% and less than 8% ZrO2, more than 0.5% and less than 15% SiO2.

Relative to the weight percentage of all the oxides present, the structures according to the invention may further comprise other minority elements. In particular, the structures may comprise silicon in an amount of from 0.1 to 20% by weight based on the corresponding oxide SiO 2. For example, SiO 2 represents more than 0.1%, especially more than 0.5% or even more than 1% or even more than 2%, or even more than 3% or even more than 5% of the chemical composition. For example, SiO 2 represents less than 18%, especially less than 15%, or even less than 12%, or even less than 10% of the chemical composition, the percentages being given by weight on the basis of the oxides. The porous structure may further comprise other elements such as boron, alkalis or alkaline earths of Ca, Sr, Na, K, Ba type, the total summed amount of said elements present being preferably less than 10% by weight. , for example less than 5%, even 4%, or even 3% by weight based on the corresponding oxides B2O3, CaO, SrO, Na2O, K2O, BaO relative to the weight percentage of all the oxides corresponding to the elements present in said porous structure . The percentage of each minority element, on the basis of the weight of the oxide corresponds, is for example less than 4%, even 3%, or even 1%. For example, according to one possible embodiment of the invention, the porous structure according to the invention has the following chemical composition, in weight percentage on the basis of the oxides: more than 35% and less than 51% of Al 2 O 3, for example between 38 and 50% of Al 2 O 3. - more than 25% and less than 45% of TiO2, - more than 0,7% and less than 20% of Fe203, - possibly more than 0,1% and less than 20% of SiO2, - less than 2% of MgO, or even less than 1% MgO. more than 0.7% and less than 10% of ZrO 2, optionally more than 2% and less than 13%, in total, of at least one oxide selected from the group consisting of B 2 O 3, CaO, Na 2 O, K 2 O , SrO, BaO. Such a chemical composition preferably has a weight percentage based on the oxides: between 1 and 18% of Fe 2 O 3, between 3 and 18% of SiO 2, and between 1 and 8% of ZrO 2. In order not to unnecessarily burden the present description, all the possible combinations according to the invention between the different preferred modes of the compositions of the materials according to the invention, as just described above, are not reported. It is understood, however, that all possible combinations of the initial and / or preferred domains and values previously described are contemplated and must be considered as described by the applicant in the context of this disclosure (in particular of two, three or more combinations) . The porous structure according to the invention may further comprise mainly or consist of a solid solution type oxide phase comprising titanium, aluminum, at least one element chosen from M2, at least one element selected from M3 and optionally a element selected from M1, and at least one phase consisting essentially of titanium oxide TiO2 and / or zirconium oxide ZrO2 and / or cerium oxide CeO2 and / or hafnium oxide HfO2 and optionally at least a silicate phase. Preferably, the porous structure according to the invention may comprise mainly or consist of a solid solution type oxide phase comprising titanium, aluminum, zirconium iron and optionally magnesium and at least one phase consisting essentially of titanium oxide TiO 2 and / or zirconium oxide ZrO 2 and optionally at least one silicate phase.

Said silicate phase may be present in proportions ranging from 0 to 45% of the total weight of the material. Typically, said silicate phase consists mainly of silica and alumina, the mass proportion of silica in the silicate phase being greater than 34%. According to possible alternative embodiments: Al 2 O 3 can represent between 48 and 54% by weight, TiO 2 can represent between 35 and 48% by weight, for example between 38 and 45% by weight, Fe 2 O 3 can represent between 1 and 8% by weight, for example between 2 and 6% by weight, - SiO 2 is present in proportions of less than 1% by weight, or even less than 0.5% by weight, - ZrO 2 is less than 3% by weight, MgO may represent between 1 and 8% by weight, for example between 2 and 6% by weight. The material constituting the porous structure according to the invention can be obtained according to any technique usually used in the field.

According to a first variant, the material constituting the structure can be obtained directly, in a conventional manner, by simply mixing the initial reactants in the appropriate proportions to obtain the desired composition and then by heating and reaction in the solid state (reactive sintering). Said reagents may be simple oxides, for example Al 2 O 3, TiO 2 and optionally other oxides of elements that may enter the structure, for example in the form of a solid solution. It is also possible according to the invention to use any precursor of said oxides, for example in the form of carbonates, hydroxides or other organometallic elements of the preceding elements. By precursors, is meant a material which decomposes into the simple oxide corresponding to an often early stage of the heat treatment, that is to say at a heating temperature typically below 1000 ° C, or even below 8000 or even at 500 ° C. According to another method of manufacturing the structure according to the invention, said reagents are sintered grains corresponding to the chemical composition described above and are obtained from said simple oxides. The mixture of the initial reactants is previously sintered, that is to say that it is heated to a temperature allowing the reaction of simple oxides to form sintered grains comprising at least one main phase of structure of the aluminum titanate type. It is also possible according to this mode to use the precursors of said oxides mentioned above. As before, the mixture of precursors is sintered, that is to say that it is heated to a temperature allowing reaction of the precursors to form sintered grains comprising at least a majority of a phase of structure of the aluminum titanate type .

A method of manufacturing such a structure according to the invention is generally as follows: Initially, the initial reactants are mixed in the appropriate proportions to obtain the desired composition. As is well known in the art, the manufacturing method typically comprises a step of mixing the initial mixture of reagents with an organic binder of the methylcellulose type and a porogen, for example of the starch, graphite, polyethylene, PMMA, etc. type. and gradually adding water until the necessary plasticity is obtained to allow the extrusion step of the honeycomb structure. For example, during the first step, the initial mixture is kneaded with from 1 to 30% by weight of at least one pore-forming agent selected according to the desired pore size, and then at least one organic plasticizer and / or or an organic binder and water. The kneading results in a homogeneous product in the form of a paste. The extrusion step of this product through a suitably shaped die makes it possible, according to well-known techniques, to obtain monoliths in the form of a honeycomb. The process may for example comprise a drying step of the monoliths obtained. During the drying step, the green ceramic monoliths obtained are typically dried by microwave or at a temperature and for a time sufficient to bring the water content not chemically bound to less than 1% by weight. In the case where it is desired to obtain a particulate filter, the method 30 may further comprise a plugging step of every other channel at each end of the monolith. The firing step of the monoliths whose filtering portion is based on aluminum titanate is in principle carried out at a temperature above 1300 ° C. but not exceeding 1800 ° C., preferably not exceeding 1750 ° C. The temperature is in particular adjusted according to the other phases and / or oxides present in the porous material. Most often, during the firing step, the monolithic structure is brought to a temperature of between 1300 ° C. and 1600 ° C. under an atmosphere containing oxygen or a neutral gas. Although one of the advantages of the invention lies in the possibility of obtaining monolithic structures whose size can be greatly increased without the need for segmentation, in contrast to the SiC filters (as previously described), according to a mode which however, it is not preferred, the process may optionally comprise a step of assembling the monoliths in an assembled filtration structure according to well-known techniques, for example described in application EP 816 065. The filtering structure or porous ceramic material according to the invention. The invention is preferably of the honeycomb type. It has a suitable porosity greater than 10%, generally between 20 and 70%, or even between 30 and 60%, the average pore size being ideally between 5 and 60 microns, especially between 10 and 20 microns. Such filtering structures typically have a central portion comprising a set of adjacent ducts or channels of axes parallel to each other separated by walls constituted by the porous material. In a particulate filter, the ducts are closed off by plugs at one or the other of their ends to delimit inlet chambers opening along a gas intake face and exit chambers opening following a gas evacuation face, so that the gas passes through the porous walls. The present invention also relates to a filter or a catalytic support obtained from a structure as previously described and by deposition, preferably by impregnation, of at least one supported or preferably unsupported active catalytic phase, typically comprising at least one precious metal such as Pt and / or Rh and / or Pd and optionally an oxide such as Ce02r ZrO2, Ce02-Zr02. The catalytic supports also have a honeycomb structure, but the conduits are not plugged and the catalyst is deposited in the pores of the channels.

The invention and its advantages will be better understood on reading the following nonlimiting examples. In the examples, unless otherwise indicated, all percentages are given by weight.

Examples: In the examples, the samples were prepared from the following raw materials: Alumina Almatis CL4400FG containing 99.8% Al 2 O 3 and having a median diameter of about 5.2 microns, TRONOX titanium oxide TR having 99.5% TiO 2 and having a diameter of the order of 0.3 μm, SiO 2 ElKem Microsilicia Grade 971U with a purity level of 99.7%, Fe 2 O 3 with a purity level greater than 98%, - Lime comprising approximately 97% of CaO, with more than 80% of particles having a diameter of less than 80 μm, - Strontium carbonate containing more than 98.5% of SrCO3r marketed by the Company of Chemicals Harbonnières, - Zirconia with a rate of with a purity of greater than 98.5% and a median diameter d 50 = 3.5 μm, marketed under the reference CC10 by the company Saint-Gobain ZirPro.

The samples according to the invention and comparative, were obtained from the above reagents, mixed in the appropriate proportions. Specifically, the initial reagent mixtures were mixed and then squeezed into cylinders which were then sintered at the temperature shown in Table 1 for 4 hours in air. The prepared samples are then analyzed. The results of the analyzes performed on each of the samples of the examples are summarized in Table 1.

In Table 1: 1 °) The chemical composition, indicated in weight percentages on the basis of the oxides, was determined by X-ray fluorescence. 2 °) The crystalline phases present in the refractory products were characterized by X-ray diffraction and microprobe analysis. In Table 1, AT indicates a solid solution of oxides (main phase) of the aluminum titanate type, PS indicates the presence of a silicate phase, other (s) phase (s) indicates the presence of at least one other minority phase P2, "-" means that the phase is present in the form of traces. 3 °) The stability of the crystalline phases present is evaluated by a test consisting of comparing by diffraction of the X-rays the crystalline phases present initially to those present after a heat treatment of 100 hours at 1100 ° C. The product is considered stable if the maximum intensity of the main peak reflecting the appearance of Al 2 O 3 corundum after this treatment remains less than 50% of the mean of the maximum intensities of the 3 main peaks of the AT phase. 4 °) The compressive strength (R) was measured at room temperature, on an LLOYD press equipped with a 10 kN sensor, by compression with a speed of 1 mm / min of the prepared samples. 5 °) the density was measured by the classical Archimedes method techniques. The porosity reported in Table 1 corresponds to the difference, given in percentages, between the theoretical density (expected maximum density of the material in the absence of any porosity and measured by helium picnometry on the ground product) and the measured density.

Comparative Example 1 (Invention) Al 2 O 3 38.67 40.7 TiO 2 37.23 39.19 Fe 2 O 3 12.07 12.7 SiO 2 3.84 4.04 SrO 2.27 2.39 CaO 0.36 0.38 MgO 0 0 Na2O 0.08 0.08 K20 0 0 ZrO2 5.48 0.52 to 36.6 38.1 to 34.3 35.7 t 44.9 46.8 ml 0 0 m2 7.3 7, 6 a '- t + 2ml + m2 -3,3 -3,5 Phases AT (main phase) yes yes PS yes yes Other phase (s) :( P2) yes Stability 100 hours yes yes Temp. sintering 4 h (° C) 1450 1450 Density 2,79 2,70 Porosity 27,6 28,5 R (MPa) 60,0 52,6 Table 1 Table 1 shows an improvement in the combined characteristics of porosity and mechanical strength: For an identical sintering temperature, it can be seen that the porosity of the example according to the invention is comparable to those of the comparative example. At the same time, as shown in Table 1, the example according to the invention has a resistance R significantly greater than that of the comparative example.

Thus the products of the invention make it possible, depending on the need: either to obtain better properties associated with a desired composition of the material, at an imposed sintering (cooking) temperature, or even to adjust a high level of porosity of the material (in particular by adding a porogen to the initial reagents) while maintaining a good mechanical strength.

Claims (10)

REVENDICATIONS1. A porous structure comprising a ceramic material comprising mainly or consisting of an oxide material having the following composition, in weight percent based on the oxides: - more than 15% and less than 55% Al 2 O 3, - more than 25% and less than 60% of TiO 2, less than 20%, in total, of at least one oxide of an element M 1 chosen from MgO, CoO, more than 0.7% and less than 20%, in total, of at least one oxide of an element M2 selected from the group consisting of Fe 2 O 3, Cr 2 O 3, MnO 2, La 2 O 3, Y 2 O 3, Ga 2 O 3, more than 0.7% and less than 25% in total, of at least one oxide of an element M3 selected from the group consisting of ZrO2, Ce203, Hf02, less than 30% SiO2, said material being obtained by reactive sintering of the corresponding simple oxides or a precursor thereof or by heat treatment of sintered grains corresponding to said composition. 2. The porous structure according to claim 1 further comprising a composition, in molar percentage on the basis of all the oxides present in said composition, such that: a 't + 2m1 + m2 is between -15 and 15, especially between -6 and 6, wherein: a is the molar percentage of Al 2 O 3, s is the molar percentage of SiO 2, a = 0.37 xs, t is the molar percentage of TiO 2, - m 1 is the total molar percentage of the oxide (s) of MI, m2 is the total molar percentage of the oxide (s) of M2. 3. Porous structure according to one of the preceding claims, wherein M1 is Mg, M2 is Fe and M3 is Zr. 10 4. Porous structure according to one of the preceding claims, wherein said material has the following chemical composition, in weight percent based on the oxides: - more than 25% and less than 52% of Al 2 O 3, 15 - more than 26 % and less than 55% of TiO2, - less than 10% of MgO, - more than 1% and less than 20% of Fe203, - more than 1% and less than 10% of ZrO2, - less than 20% of SiO2 . 20 5. Porous structure according to the preceding claim, wherein said material has the following chemical composition, weight percent based on the oxides. - more than 35% and less than 50% Al203, - more than 26% and less than 50% TiO2, - less than 6% MgO, - more than 2% and less than 15% Fe203, - more of 2% and less than 8% of ZrO2, - more than 0.5% and less than 15% of SiO2. 6. The porous structure according to one of the preceding claims, comprising more than 1% SiO 2, preferably comprising more than 3% SiO 2, preferably comprising more than 5% SiO 2. 7. Porous structure according to one of the preceding claims wherein said material comprises a main phase consisting of the solid solution type phase comprising titanium, aluminum, zirconium iron and optionally magnesium, at least one phase consisting of essentially titanium oxide TiO2 and / or zirconium oxide ZrO2 and optionally at least one silicate phase. 8. Porous structure according to claim 7 wherein the or silicate phase (s) are in proportions ranging from 0 to 45% of the total weight of the material. 9. The porous structure according to claim 8 wherein said silicate phase consists mainly of silica and alumina, the mass proportion of silica in the silicate phase being greater than 34%. 10. Porous structure according to one of the preceding claims, having a structure of the honeycomb type, in particular catalytic support or filter for automotive application, the ceramic material constituting said structure having a porosity greater than 10% and a size of pores centered between 5 and 60 microns.30