Porous molded article comprising spinel

Abstract

The present invention relates to a novel molded article with fine-tuned porosity. In particular, the invention relates to a novel molded article comprising a mixed metal oxide having the empirical formula M1M2O4, in which M1 comprises one or more divalent elements M1, in which M2 comprises one or more trivalent elements M2, in which the mixed metal oxide comprises a crystalline phase having a spinel structure, and wherein the molded article has a total pore volume in the range of 0.10 to 0.90 ml / g. Further, the invention relates to a method for producing novel molded bodies, in particular said novel molded bodies, and to molded bodies obtained or obtainable by said method. Yet further, the invention relates to the use of the molded body as a catalyst or catalyst support.

Description

Technical Field

[0001] This invention relates to a molded article comprising having empirical formula M 1 M 2 Mixed metal oxides of 2O4, wherein M 1 Contains one or more divalent elements M 1 M 2 Contains one or more trivalent elements M 2 The mixed metal oxide comprises a crystalline phase having a spinel structure, and the molding article has a total pore volume in the range of 0.10 to 0.90 ml / g. Further, the present invention relates to a method for preparing novel molding articles, molding articles obtainable or acquired by said method, and the use of the novel molding articles of the present invention. Background Technology

[0002] Typically, a catalyst comprises a support material and a catalytic material loaded thereon. The support material used is usually in the form of a molded article, which can have a specific shape. This loading can be carried out by known methods, particularly by impregnation, and more specifically by initial wet impregnation (e.g., using a molten metal). The wetting behavior of the support material is crucial for achieving a uniform loading distribution of the catalytic material.

[0003] Uniform impregnation of molded articles with molten metal can be challenging due to the non-uniform distribution of the molten metal within them. Such non-uniformity can lead to undesirable core-shell structures, where a higher metal density is observed in the shell. When used in catalytic processes, this can result in stronger sintering of these metal centers.

[0004] CA 1189052 relates to a method for producing a catalyst or catalyst support having both high surface area and large pore size, wherein the method specifically includes mixing a metal oxide with water and an acid to form a rare metal gel composed of a loose three-dimensional oxide network containing a large amount of water uniformly dispersed throughout the network.

[0005] US 4558031 relates to a high-porosity catalyst and discloses a method for producing a catalyst or catalyst support having both high surface area and large pore size, the method specifically comprising mixing alumina with water and nitric acid to form an alumina gel consisting of a loose three-dimensional network, the acid being present in an amount of at least 250 parts of 70% HNO3 per 100 parts of alumina.

[0006] EP 0210681 A1 relates to a catalyst suitable for use in reduction and oxidation reactions, the catalyst comprising a combination of magnesium aluminum spinel with copper, cobalt, a compound of copper or cobalt, or a mixture thereof, wherein the spinel-based support optionally comprises an oxide of another divalent metal.

[0007] WO 94 / 16798 A1 relates to a method for catalytically decomposing nitrous oxide contained in pure or gaseous mixtures at 200°C to 900°C and pressures of 0.1 and 20 bar, the method using a catalyst prepared by combining CuAl2O4 with tin, lead, or elements of Group II or subgroup II of the periodic table as oxides or salts or in elemental form, and calcining at 300°C to 1300°C and pressures of 0.1 to 200 bar.

[0008] GB 1377191 A relates to a catalyst comprising metallic cobalt or cobalt oxide or both supported on a mixed oxide material having a predominantly spinel structure and substantially free of unbonded oxides capable of forming spinel with cobalt oxide, i.e. containing less than 5% wt. of any divalent or tetravalent oxide capable of forming such spinel or less than 1% wt. of any trivalent oxide capable of forming such spinel.

[0009] Therefore, there is a need to provide a molding article with finely tuned porosity, and preferably a molding article with increased porosity. Furthermore, an object of the present invention is to provide a method for preparing a molding article with finely tuned porosity, preferably for preparing a molding article with increased porosity, and more preferably for preparing a molding article that allows for uniform distribution of metal ions therein. Detailed Implementation

[0010] Therefore, an object of the present invention is to provide a novel molding article comprising a mixed metal oxide having a spinel structure, wherein the molding article has finely tuned porosity. In particular, an object of the present invention is to provide a novel molding article with increased porosity, which particularly allows for uniform impregnation with a molten metal. Further, an object of the present invention is to provide a method for preparing the novel molding article, wherein the method includes a pre-calcination step, an acid treatment, and a final calcination step.

[0011] It has been unexpectedly found that the method, including the steps of calcining the molded article and subsequently treating it with acid, results in a molded article that allows for a significant improvement in the distribution of molten metal throughout the article. In particular, it has been found that the porosity, especially the total pore volume, of the molded article can be adjusted and fine-tuned, and especially increased, when the corresponding treatment is performed. Therefore, it has been found that treating the pre-calcined molded article with acid significantly improves its wetting properties. This treatment particularly allows for the impregnation of molded articles with desired shapes. Specifically, molded articles with a low surface-to-volume ratio can be uniformly impregnated.

[0012] The effect is Figure 3 As shown in the figure, two sample molds were immersed in molten metal, calcined, and then cut in half. Figure 3 The sample mold shown in A was not processed according to the present invention, but Figure 3 The sample molded article shown in section B was treated according to the invention prior to impregnation. (See section B for details.) Figure 3 A and Figure 3 As can be seen from B, the sample molded articles not treated with an aqueous solution containing acid according to the present invention are not uniformly impregnated, which is indicated by different coloring. In contrast, Figure 3 The uniform coloring of the sample mold shown in B indicates uniform impregnation.

[0013] Therefore, the present invention relates to a molded article comprising having empirical formula M 1 M 2 Mixed metal oxides of 2O4, wherein M 1 Contains one or more divalent elements M 1 M 2 Contains one or more trivalent elements M 2 The mixed metal oxide comprises a crystalline phase having a spinel structure, wherein the crystalline phase having a spinel structure is preferably determined according to Reference Example 1.2, wherein the molded article has a total pore volume in the range of 0.10 to 0.90 ml / g, wherein the total pore volume is preferably determined according to Reference Example 1.4.

[0014] Preferably, M 1 Elements selected from Groups 2, 10, 11, and 12 of the periodic table, where M... 1 More preferably, it is selected from the group consisting of Mg, Ni, Cu, Zn, Mn, Co, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of Mg, Ni, Cu, Zn, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of Mg, Zn, Cu, and mixtures thereof; more preferably, it is selected from the group consisting of Mg, Zn, and mixtures thereof, wherein M 1 More preferably, it is Mg.

[0015] Preferably, M 2 Elements selected from Groups 5, 6, 7, 8, and 13 of the periodic table, where M... 2 More preferably, it is selected from the group consisting of Al, Cr, Fe, V, Mn, Co, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, Fe, V, Mn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, V, Mn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, and mixtures of two or more thereof, wherein M... 2 More preferably, it is Al.

[0016] Preferably, the molded article comprises one or more divalent elements M contained in the molded article. 1 With M 1 The total weight calculated by O is 10% or less by weight, more preferably 5% or less by weight, more preferably 1.0% or less by weight, more preferably 0.1% or less by weight, and more preferably 0.01% or less by weight. 1 O, which is preferably determined according to reference example 1.2, wherein the one or more divalent elements M in the molded article 1 With M 1 The total weight calculated by O is preferably determined according to Reference Example 1.6.

[0017] Preferably, the molded article comprises one or more trivalent elements M contained in the molded article. 2 With M 2 The total weight of 2O3 calculated is 10 wt% or less, more preferably 5 wt% or less, more preferably 1 wt% or less, more preferably 0.1 wt% or less, more preferably 0.01 wt% or less of M. 2 2O3, preferably as determined according to Reference Example 1.2, wherein the molded article contains one or more divalent elements M. 2 With M 2 The total weight calculated from 2O3 is preferably determined according to reference example 1.6.

[0018] Preferably, the mixed metal oxide has a crystallinity in the range of 50% to 100%, more preferably 60% to 100%, more preferably 70% to 95%, and more preferably 80% to 90%, wherein the crystallinity is determined according to Reference Example 1.2.

[0019] When the mixed metal oxide has a crystallinity in the range of 50% to 100%, it is preferred that 50% to 100%, more preferably 70% to 100%, and even more preferably 95% to 100% of the crystalline phase has a spinel structure as determined by XRD, preferably as determined according to Reference Example 1.2.

[0020] Preferably, the X-ray diffraction pattern exhibited by the molded article includes at least the following reflections:

[0021]

[0022] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0023] More preferably, it includes at least the following reflections:

[0024]

[0025] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0026] More preferably, it includes at least the following reflections:

[0027]

[0028] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0029] Where M 1 More preferably Mg and wherein M 2 More preferably, it is Al.

[0030] Preferably, the molded article has a median pore size in the range of 0.001 to 0.1 µm, more preferably in the range of 0.005 to 0.05 µm, more preferably in the range of 0.02 to 0.04 µm, more preferably in the range of 0.027 to 0.035 µm, and more preferably in the range of 0.028 to 0.034 µm, wherein the pore size distribution is preferably determined according to Reference Example 1.5.

[0031] Preferably, the molded article has a water adsorption amount in the range of 10 to 80 wt%, more preferably in the range of 30 to 60 wt%, more preferably in the range of 40 to 50 wt%, and even more preferably in the range of 43 to 47 wt%, wherein the water adsorption amount is preferably determined according to Reference Example 1.1.

[0032] Preferably, the molded article has a diameter of 20.0 to 150.0 m. 2 Within the range of / g, more preferably from 30.0 to 90.0 m 2 Within the range of / g, more preferably from 40.0 to 65.0 m 2 Within the range of / g, more preferably from 47.0 to 49.0 m 2 The BET specific surface area in the range of / g, wherein the BET specific surface area is preferably determined according to Reference Example 1.3.

[0033] Preferably, the molded article has a total pore volume in the range of 0.18 to 0.75 ml / g, more preferably in the range of 0.25 to 0.60 ml / g, more preferably in the range of 0.33 to 0.53 ml / g, more preferably in the range of 0.37 to 0.49 ml / g, and more preferably in the range of 0.40 to 0.46 ml / g, wherein the total pore volume is preferably determined according to Reference Example 1.4.

[0034] Preferably, the molded article further comprises one or more metals M 3 M 3 The metal is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Mo, Sn, and mixtures of two or more thereof, more preferably from the group consisting of Fe, Ru, and mixtures of two or more thereof, wherein the one or more metals M 3 More preferably, it is loaded onto a mixed metal oxide.

[0035] The molded article further comprises one or more metals M 3 M 3 When the composition is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Mo, Sn, and mixtures of two or more thereof, it is preferred that the molded article contains a component based on one or more of the divalent element M. 1 With M 1 The weight calculated by O and the weight of one or more trivalent elements M. 2 With M 2 The sum of the weights of the one or more metals M calculated as elemental is 20 wt% or less, more preferably 10 wt% or less, more preferably 5 wt% or less. 3 The molded article contains one or more divalent elements M. 1 With M 1 The weight calculated by O and the weight of one or more trivalent elements M. 2 With M 2 The sum of weights calculated from 2O3 is preferably determined according to reference example 1.6.

[0036] Furthermore, the molded article further comprises one or more metals M 3 M 3 When the selection is made from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Mo, Sn, and mixtures thereof, it is preferred that one or more of the metals M are present. 3 Distribute evenly throughout the molded part.

[0037] Preferably, 85 to 100% by weight, more preferably 90 to 100% by weight, even more preferably 95 to 100% by weight, even more preferably 98 to 100% by weight, even more preferably 99 to 100% by weight, even more preferably 99.9 to 100% by weight of the molded article is made from M 1 M 2 O, H and one or more optional metals M 3 composition.

[0038] Preferably, the molded article is composed of a mixed metal oxide and one or more of the optional metal M, at a weight percentage of 85 to 100%, more preferably 90 to 100%, more preferably 95 to 100%, more preferably 98 to 100%, more preferably 99 to 100%, and more preferably 99.9 to 100% by weight. 3 composition.

[0039] Preferably, the molded article is an extrusion, tablet, or granule.

[0040] When the molded article is an extrusion, tablet, or granule, it is preferred that the extrusion or tablet has a cross-section, wherein the cross-section is circular, hexagonal, rectangular, square, triangular, elliptical, star-shaped polygon, or clover-shaped, more preferably circular, hexagonal, rectangular, square, triangular, elliptical, star-shaped polygon with 3, 4, 5, 6, 7, or 8 apexes, clover-shaped, four-leaf-shaped, or hexalobed, more preferably circular, hexagonal, rectangular, square, triangular, elliptical, star-shaped polygon with 3 or 4 apexes, clover-shaped, four-leaf-shaped, or hexalobed.

[0041] Preferably, the molded article is a tablet with a cross section, wherein the cross section is four-leaf shaped.

[0042] When the molded article is a tablet with a cross section, wherein the cross section is tetralobed, it is preferable that the tablet has a thickness, wherein the thickness is in the range of 2.0 to 13.0 mm, more preferably in the range of 5.0 to 10.0 mm, and even more preferably in the range of 6.5 to 9.0 mm.

[0043] Furthermore, when the molded article is a tablet with a cross section, it is preferable that the tablet has a diameter D in the range of 5 to 20 mm, more preferably in the range of 7 to 17 mm, and even more preferably in the range of 9 to 15 mm.

[0044] Preferably, the molded article is a tablet with a cross section, wherein the cross section is hexagonal.

[0045] When the molded article is a tablet with a cross-section, wherein the cross-section is hexagonal, it is preferable that the tablet has a thickness, wherein the thickness is in the range of 2.0 to 15.0 mm, more preferably in the range of 5.0 to 12.0 mm, and even more preferably in the range of 8.0 to 9.0 mm.

[0046] Furthermore, when the molded article is a tablet with a cross-section, wherein the cross-section is hexagonal, it is preferable that the tablet has a diameter D in the range of 5 to 25 mm, more preferably in the range of 12 to 19 mm, and even more preferably in the range of 14 to 17 mm.

[0047] Furthermore, the present invention relates to a method for preparing a molded article, preferably for preparing a molded article according to any one of the specific and preferred embodiments disclosed herein, the method comprising:

[0048] (i) Provide M 1 O and M 2 One or more sources of 2O3, wherein M 1 Represents one or more divalent elements and M 2 Represents one or more trivalent elements;

[0049] (ii) Molding the one or more sources obtained from (i);

[0050] (iii) Calcination of the molded product obtained by (ii) in a gaseous atmosphere;

[0051] (iv) Treat the molded article obtained from (iii) with acid;

[0052] (v) Calcine the molded product obtained by (iv) in a gaseous atmosphere.

[0053] Preferably, M 1 Elements selected from Groups 2, 10, 11, and 12 of the periodic table, where M... 1More preferably, it is selected from the group consisting of Mg, Ni, Cu, Zn, Mn, Co, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of Mg, Ni, Cu, Zn, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of Mg, Zn, Cu, and mixtures thereof; more preferably, it is selected from the group consisting of Mg, Zn, and mixtures thereof, wherein M 1 More preferably, it is Mg.

[0054] Preferably, M 2 Elements selected from Groups 5, 6, 7, 8, and 13 of the periodic table, where M... 2 More preferably, it is selected from the group consisting of Al, Cr, Fe, V, Mn, Co, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, Fe, V, Mn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, V, Mn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, and mixtures of two or more thereof, wherein M... 2 More preferably, it is Al.

[0055] Preferably, M 1 O and M 2 The one or more sources of 2O3 comprise one or more compounds selected from the group consisting of, preferably, one or more compounds selected from the group consisting of: M 1 oxides, M 1 hydroxide, M 1 carbonates, M 1 Bicarbonate, M 1 Hydroxycarbonate, M 2 oxides, M 2 hydroxide, M 2 carbonates, M 2 Bicarbonate, M 2 Hydroxycarbonate, M 1 and M 2 Mixed metal oxides, M 1 and M 2 Mixed metal hydroxy carbonates, and mixtures of two or more thereof.

[0056] Preferably, M 1 O and M 2 The one or more sources of 2O3 comprise one or more compounds selected from the group consisting of, preferably, one or more compounds selected from the group consisting of: M 1 and M 2 Mixed metal oxides, M 1 and M 2Mixed metal hydroxy carbonates and their mixtures.

[0057] Preferably, M 1 O and M 2 The one or more sources of 2O3 have an M ratio in the range of 1:5 to 5:1.0, more preferably in the range of 1:2.5 to 2.5:1, more preferably in the range of 1:2 to 2:1, and more preferably in the range of 1:2.1 to 1:1.9. 1 With M 2 The molar ratio.

[0058] Preferably, M 1 O and M 2 The one or more sources of 2O3 contain based on M 1 O and M 2 M in one or more sources of 2O3 1 With M 1 The weight calculated by O and M 2 With M 2 The sum of the weights of 2O3 calculated is 22 to 34 wt%, more preferably 25 to 31 wt%, and even more preferably 27 to 29 wt%, in M 1 O calculation of M 1 .

[0059] Preferably, M 1 O and M 2 The one or more sources of 2O3 contain based on M 1 O and M 2 M in one or more sources of 2O3 1 With M 1 The weight calculated by O and M 2 With M 2 The sum of the weights of 2O3 calculated is 66 to 78% by weight, more preferably 69 to 75% by weight, and even more preferably 71 to 73% by weight, in M 2 M calculated from 2O3 2 .

[0060] Preferably, molding the mixture according to (ii) includes tableting or extrusion.

[0061] Preferably, the calcination according to (iii) is carried out at a temperature in the range of 300°C to 1200°C, more preferably in the range of 700°C to 1100°C, and even more preferably in the range of 900°C to 1000°C.

[0062] Preferably, the calcination according to (iii) is carried out for a period of time ranging from 0.1 to 48 h, more preferably from 0.5 to 24 h, and even more preferably from 1 to 5 h.

[0063] Preferably, the gas atmosphere according to (iii) comprises, preferably consists of, one or more of oxygen and nitrogen, more preferably air.

[0064] Preferably, the X-ray diffraction pattern of the molded article obtained by (iii) includes at least the following reflections:

[0065]

[0066] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0067] More preferably, it includes at least the following reflections:

[0068]

[0069] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0070] More preferably, it includes at least the following reflections:

[0071]

[0072] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0073] Where M 1 More preferably Mg and wherein M 2 More preferably, it is Al.

[0074] Preferably, the molded article obtained by (iii) has a water adsorption amount in the range of 25 to 50 wt%, more preferably in the range of 37 to 47 wt%, and even more preferably in the range of 40 to 44 wt%, wherein the water adsorption amount is preferably determined according to Reference Example 1.1.

[0075] Preferably, the molded article obtained by (iii) has a thickness of 40.0 to 60.0 m. 2 Within the range of / g, more preferably from 47.0 to 53.0 m 2 Within the range of / g, more preferably from 49.0 to 51.0 m 2 The BET specific surface area in the range of / g, wherein the BET specific surface area is preferably determined according to Reference Example 1.3.

[0076] Preferably, the molded article obtained by (iii) has a total pore volume in the range of 0.20 to 0.55 ml / g, more preferably in the range of 0.30 to 0.42 ml / g, and even more preferably in the range of 0.33 to 0.39 ml / g, wherein the total pore volume is preferably determined according to Reference Example 1.4.

[0077] Preferably, the treatment according to (iv) includes immersing the molded article in acid.

[0078] Preferably, the treatment according to (iv) is carried out for a period of time ranging from 20 to 100 minutes, more preferably from 45 to 75 minutes, and even more preferably from 55 to 65 minutes.

[0079] Preferably, the treatment according to (iv) is carried out at a temperature in the range of 0°C to 50°C, more preferably in the range of 10°C to 40°C, and even more preferably in the range of 15°C to 35°C.

[0080] Preferably, the acid according to (iv) is an aqueous solution of an acid.

[0081] When the acid according to (iv) is an aqueous solution of the acid, it is preferred that the aqueous solution of the acid has a weight ratio of acid to water in the range of 1:1 to 1:10, more preferably in the range of 1:3 to 1:5, and even more preferably in the range of 1:3.9 to 1:4.1.

[0082] Furthermore, when the acid according to (iv) is an aqueous solution of an acid, it is preferable that the aqueous solution of the acid has a concentration of acid in water in the range of 2.5 to 4.5 mol / L, more preferably in the range of 3.2 to 3.7 mol / L, and even more preferably in the range of 3.3 to 3.6 mol / L.

[0083] Preferably, the acid according to (iv) comprises, and preferably consists of, one or more of inorganic and organic acids, more preferably one or more of HNO3, HCl, H2SO4, H3PO4, formic acid, oxalic acid, and acetic acid, more preferably HNO3.

[0084] Preferably, the method further includes, after (iv) and before (v), the following steps:

[0085] (w) Wash the molded product obtained from (iv) with deionized water.

[0086] Preferably, the method further includes, after (iv) and before (v), and preferably after (w) and before (v), the following steps:

[0087] (d) Dry the molded articles obtained by (iv) or (w) in a gaseous atmosphere.

[0088] In cases where the method further includes drying according to (d), it is preferred that the drying is carried out at a temperature in the range of 80°C to 160°C, more preferably in the range of 100°C to 140°C, and even more preferably in the range of 110°C to 130°C.

[0089] Furthermore, in cases where the method further includes drying according to (d), it is preferred that the drying according to (d) be carried out for a period of time ranging from 0.5 to 16 hours, more preferably from 2 to 12 hours, and even more preferably from 3 to 8 hours.

[0090] Furthermore, in cases where the method further includes drying according to (d), it is preferred that the gaseous atmosphere according to (d) comprises, preferably, one or more of oxygen and nitrogen, more preferably air.

[0091] Preferably, the calcination according to (v) is carried out at a temperature in the range of 400°C to 1000°C, more preferably in the range of 600°C to 950°C, and even more preferably in the range of 825°C to 875°C.

[0092] Preferably, the calcination of (v) is carried out for a period of time ranging from 0.1 to 1.5 h, more preferably from 0.3 to 0.7 h, and more preferably from 0.4 to 0.6 h.

[0093] Preferably, the gas atmosphere according to (v) comprises, preferably, one or more of oxygen and nitrogen, more preferably air.

[0094] Preferably, the method further includes (v) after which...

[0095] (vi) To mix one or more metals M 3 The load is applied to the molded part obtained by (v).

[0096] The loading is more preferably carried out by impregnation, more preferably by wet impregnation, and even more preferably by initial wet impregnation.

[0097] Where M 3 The sample is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Pd, Pt, and mixtures of two or more thereof, and more preferably from the group consisting of Fe, Ru, and mixtures of two or more thereof.

[0098] Furthermore, the present invention relates to a molding article, preferably a molding article according to any one of the specific and preferred embodiments disclosed herein, wherein the molding article is obtainable or acquired by a method according to any one of the specific and preferred embodiments disclosed herein.

[0099] Furthermore, the present invention relates to the use of a molded article as a catalyst or catalyst support according to any one of the specific and preferred embodiments disclosed herein.

[0100] The invention is further illustrated by the following set of embodiments and combinations of embodiments derived from the dependent relationships and references shown. In particular, it should be noted that in each instance of reference to a series of embodiments, such as in the context of the term "molded article as described in any one of embodiments 1 to 4," each embodiment in this series is intended to clearly disclose to a person skilled in the art that the wording of this term should be understood by a person skilled in the art to be synonymous with "molded article as described in any one of embodiments 1, 2, 3, and 4." Furthermore, it is explicitly stated that the following set of embodiments is not a set of claims defining the scope of protection, but rather represents a suitable structural portion of this specification relating to the general and preferred aspects of the invention.

[0101] 1. A molded article comprising an empirical formula M 1 M 2 Mixed metal oxides of 2O4, wherein M 1 Contains one or more divalent elements M 1 M 2 Contains one or more trivalent elements M 2 The mixed metal oxide comprises a crystalline phase having a spinel structure, wherein the crystalline phase having a spinel structure is preferably determined according to Reference Example 1.2, wherein the molded article has a total pore volume in the range of 0.10 to 0.90 ml / g, wherein the total pore volume is preferably determined according to Reference Example 1.4.

[0102] 2. The molded article as described in Example 1, wherein M 1 Elements selected from Groups 2, 10, 11, and 12 of the periodic table, where M... 1 Preferably, it is selected from the group consisting of Mg, Ni, Cu, Zn, Mn, Co, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of Mg, Ni, Cu, Zn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Mg, Zn, Cu, and mixtures thereof; even more preferably, it is selected from the group consisting of Mg, Zn, and mixtures thereof, wherein M... 1 More preferably, it is Mg.

[0103] 3. The molded article as described in Example 1 or 2, wherein M 2Elements selected from Groups 5, 6, 7, 8, and 13 of the periodic table, where M... 2 Preferably, it is selected from the group consisting of Al, Cr, Fe, V, Mn, Co, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of Al, Cr, Fe, V, Mn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, V, Mn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, and mixtures of two or more thereof, wherein M... 2 More preferably, it is Al.

[0104] 4. The molding article as described in any one of Examples 1 to 3, wherein the molding article comprises based on the one or more divalent elements M contained in the molding article. 1 With M 1 The total weight calculated by O is 10% or less by weight, preferably 5% or less by weight, more preferably 1.0% or less by weight, more preferably 0.1% or less by weight, and more preferably 0.01% or less by weight. 1 O, which is preferably determined according to reference example 1.2, wherein the one or more divalent elements M in the molded article 1 With M 1 The total weight calculated by O is preferably determined according to Reference Example 1.6.

[0105] 5. The molding article as described in any one of Examples 1 to 4, wherein the molding article comprises based on the one or more trivalent elements M contained in the molding article. 2 With M 2 The total weight of M calculated from 2O3 is 10 wt% or less, preferably 5 wt% or less, more preferably 1 wt% or less, more preferably 0.1 wt% or less, and more preferably 0.01 wt% or less. 2 2O3, preferably as determined according to Reference Example 1.2, wherein the molded article contains one or more divalent elements M. 2 With M 2 The total weight calculated from 2O3 is preferably determined according to reference example 1.6.

[0106] 6. The molded article as described in any one of Examples 1 to 5, wherein the mixed metal oxide has a crystallinity in the range of 50% to 100%, preferably 60% to 100%, more preferably 70% to 95%, and even more preferably 80% to 90%, wherein the crystallinity was determined according to Reference Example 1.2.

[0107] 7. The molded article as described in Example 6, wherein 50% to 100%, preferably 70% to 100%, more preferably 95% to 100% of the crystalline phase has a spinel structure as determined by XRD, preferably as determined according to Reference Example 1.2.

[0108] 8. The molded article as described in any one of Examples 1 to 7, wherein the X-ray diffraction pattern exhibited by the molded article includes at least the following reflections:

[0109]

[0110] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0111] Preferably, it includes at least the following reflections:

[0112]

[0113] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0114] More preferably, it includes at least the following reflections:

[0115]

[0116] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0117] Where M 1 More preferably Mg and wherein M 2 More preferably, it is Al.

[0118] 9. A molded article as described in any one of Examples 1 to 8, the molded article having a median pore size in the range of 0.001 to 0.1 µm, preferably in the range of 0.005 to 0.05 µm, more preferably in the range of 0.02 to 0.04 µm, more preferably in the range of 0.027 to 0.035 µm, and more preferably in the range of 0.028 to 0.034 µm, wherein the pore size distribution is preferably determined according to Reference Example 1.5.

[0119] 10. The molded article as described in any one of Examples 1 to 9, wherein the molded article has a water adsorption amount in the range of 10 to 80 wt%, preferably in the range of 30 to 60 wt%, more preferably in the range of 40 to 50 wt%, and even more preferably in the range of 43 to 47 wt%, wherein the water adsorption amount is preferably determined according to Reference Example 1.1.

[0120] 11. The molded article as described in any one of Examples 1 to 10, wherein the molded article has a diameter of 20.0 to 150.0 m. 2 Within the range of / g, preferably from 30.0 to 90.0 m 2 Within the range of / g, more preferably from 40.0 to 65.0 m 2 Within the range of / g, more preferably from 47.0 to 49.0 m 2 The BET specific surface area in the range of / g, wherein the BET specific surface area is preferably determined according to Reference Example 1.3.

[0121] 12. The molding article as described in any one of Examples 1 to 11, wherein the molding article has a total pore volume in the range of 0.18 to 0.75 ml / g, preferably in the range of 0.25 to 0.60 ml / g, more preferably in the range of 0.33 to 0.53 ml / g, more preferably in the range of 0.37 to 0.49 ml / g, and even more preferably in the range of 0.40 to 0.46 ml / g, wherein the total pore volume is preferably determined according to Reference Example 1.4.

[0122] 13. The molding article as described in any one of Examples 1 to 12, further comprising one or more metals M 3 M 3 The metal is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Mo, Sn, and mixtures of two or more thereof, preferably from the group consisting of Fe, Ru, and mixtures of two or more thereof, wherein the one or more metals M 3 More preferably, it is loaded onto a mixed metal oxide.

[0123] 14. The molding article as described in Example 13, the molding article comprising based on the one or more divalent elements M 1 With M 1 The weight calculated by O and the weight of one or more trivalent elements M. 2 With M 2 The sum of the weights of the one or more metals M, calculated as elemental, is 20 wt% or less, preferably 10 wt% or less, more preferably 5 wt% or less. 3 The molded article contains one or more divalent elements M. 1 With M 1 The weight calculated by O and the weight of one or more trivalent elements M. 2 With M 2 The sum of weights calculated from 2O3 is preferably determined according to reference example 1.6.

[0124] 15. The molded article as described in Example 13 or 14, wherein the one or more metals M 3 Distribute evenly throughout the molded part.

[0125] 16. The molded article as described in any one of Examples 1 to 15, wherein 85 to 100% by weight, preferably 90 to 100% by weight, more preferably 95 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, and more preferably 99.9 to 100% by weight of the molded article is made from M 1 M 2 O, H and one or more optional metals M 3 composition.

[0126] 17. The molded article as described in any one of Examples 1 to 16, wherein 85 to 100 wt%, preferably 90 to 100 wt%, more preferably 95 to 100 wt%, more preferably 98 to 100 wt%, more preferably 99 to 100 wt%, and more preferably 99.9 to 100 wt%, of the molded article is composed of a mixed metal oxide and one or more of the optional metal M. 3 composition.

[0127] 18. The molded article as described in any one of Examples 1 to 17, wherein the molded article is an extrusion, tablet or granule.

[0128] 19. The molded article as described in Example 18, wherein the extrudate or the tablet has a cross section, wherein the cross section is circular, hexagonal, rectangular, square, triangular, elliptical, star-shaped polygon, or clover-shaped, preferably circular, hexagonal, rectangular, square, triangular, elliptical, star-shaped polygon with 3, 4, 5, 6, 7, or 8 apexes, clover-shaped, four-leaf-shaped, or hexagonal, more preferably circular, hexagonal, rectangular, square, triangular, elliptical, star-shaped polygon with 3 or 4 apexes, clover-shaped, four-leaf-shaped, or hexagonal.

[0129] 20. The molded article as described in any one of Examples 1 to 19, wherein the molded article is a tablet having a cross section, wherein the cross section is tetralobed.

[0130] 21. The molded article as described in Example 20, wherein the tablet has a thickness, wherein the thickness is in the range of 2.0 to 13.0 mm, preferably in the range of 5.0 to 10.0 mm, and more preferably in the range of 6.5 to 9.0 mm.

[0131] 22. The molded article as described in Example 20 or 21, wherein the tablet has a diameter D in the range of 5 to 20 mm, preferably in the range of 7 to 17 mm, and more preferably in the range of 9 to 15 mm.

[0132] 23. The molded article as described in any one of Examples 1 to 19, wherein the molded article is a tablet having a cross section, wherein the cross section is hexagonal.

[0133] 24. The molded article as described in Example 23, wherein the tablet has a thickness, wherein the thickness is in the range of 2.0 to 15.0 mm, preferably in the range of 5.0 to 12.0 mm, and more preferably in the range of 8.0 to 9.0 mm.

[0134] 25. A molded article as described in Example 23 or 24, wherein the tablet has a diameter D in the range of 5 to 25 mm, preferably in the range of 12 to 19 mm, and more preferably in the range of 14 to 17 mm.

[0135] 26. A method for preparing a molded article, preferably for preparing a molded article according to any one of Examples 1 to 25, the method comprising:

[0136] (i) Provide M 1 O and M 2 One or more sources of 2O3, wherein M 1 Represents one or more divalent elements and M 2 Represents one or more trivalent elements;

[0137] (ii) Molding the one or more sources obtained from (i);

[0138] (iii) Calcination of the molded product obtained by (ii) in a gaseous atmosphere;

[0139] (iv) Treat the molded article obtained from (iii) with acid;

[0140] (v) Calcine the molded product obtained by (iv) in a gaseous atmosphere.

[0141] 27. The method as described in Example 26, wherein M 1 Elements selected from Groups 2, 10, 11, and 12 of the periodic table, where M... 1 Preferably, it is selected from the group consisting of Mg, Ni, Cu, Zn, Mn, Co, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of Mg, Ni, Cu, Zn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Mg, Zn, Cu, and mixtures thereof; even more preferably, it is selected from the group consisting of Mg, Zn, and mixtures thereof, wherein M... 1 More preferably, it is Mg.

[0142] 28. The method as described in Example 26 or 27, wherein M 2Elements selected from Groups 5, 6, 7, 8, and 13 of the periodic table, where M... 2 Preferably, it is selected from the group consisting of Al, Cr, Fe, V, Mn, Co, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of Al, Cr, Fe, V, Mn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, V, Mn, and mixtures of two or more thereof; even more preferably, it is selected from the group consisting of Al, Cr, and mixtures of two or more thereof, wherein M... 2 More preferably, it is Al.

[0143] 29. The method as described in any one of Examples 26 to 28, wherein M 1 O and M 2 The one or more sources of 2O3 comprise one or more compounds selected from the group consisting of, preferably, one or more compounds selected from the group consisting of: M 1 oxides, M 1 hydroxide, M 1 carbonates, M 1 Bicarbonate, M 1 Hydroxycarbonate, M 2 oxides, M 2 hydroxide, M 2 carbonates, M 2 Bicarbonate, M 2 Hydroxycarbonate, M 1 and M 2 Mixed metal oxides, M 1 and M 2 Mixed metal hydroxy carbonates, and mixtures of two or more thereof.

[0144] 30. The method as described in any one of Examples 26 to 29, wherein M 1 O and M 2 The one or more sources of 2O3 comprise one or more compounds selected from the group consisting of, preferably, one or more compounds selected from the group consisting of: M 1 and M 2 Mixed metal oxides, M 1 and M 2 Mixed metal hydroxy carbonates and their mixtures.

[0145] 31. The method as described in any one of Examples 1 to 30, wherein M 1 O and M 2The one or more sources of 2O3 have an M ratio in the range of 1:5 to 5:1.0, preferably in the range of 1:2.5 to 2.5:1, more preferably in the range of 1:2 to 2:1, and even more preferably in the range of 1:2.1 to 1:1.9. 1 With M 2 The molar ratio.

[0146] 32. The method as described in any one of Examples 1 to 31, wherein M 1 O and M 2 The one or more sources of 2O3 contain based on M 1 O and M 2 M in one or more sources of 2O3 1 With M 1 The weight calculated by O and M 2 With M 2 The sum of the weights of 2O3 calculated is 22 to 34 wt%, preferably 25 to 31 wt%, more preferably 27 to 29 wt%, in M 1 O calculation of M 1 .

[0147] 33. The method as described in any one of Examples 1 to 32, wherein M 1 O and M 2 The one or more sources of 2O3 contain based on M 1 O and M 2 M in one or more sources of 2O3 1 With M 1 The weight calculated by O and M 2 With M 2 The total weight of 2O3 calculated is 66 to 78% by weight, preferably 69 to 75% by weight, more preferably 71 to 73% by weight, in M 2 M calculated from 2O3 2 .

[0148] 34. The method of any one of Examples 26 to 33, wherein molding the mixture according to (ii) includes tableting or extrusion.

[0149] 35. The method as described in any one of Examples 26 to 34, wherein the calcination according to (iii) is carried out at a temperature in the range of 300°C to 1200°C, preferably in the range of 700°C to 1100°C, and more preferably in the range of 900°C to 1000°C.

[0150] 36. The method as described in any one of Examples 26 to 35, wherein the calcination according to (iii) is carried out for a period of time ranging from 0.1 to 48 h, preferably from 0.5 to 24 h, and more preferably from 1 to 5 h.

[0151] 37. The method as described in any one of Examples 26 to 36, wherein the gas atmosphere according to (iii) comprises, preferably, one or more of oxygen and nitrogen, preferably air.

[0152] 38. The method of any one of Examples 26 to 37, wherein the X-ray diffraction pattern of the molded article obtained by (iii) includes at least the following reflections:

[0153]

[0154] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0155] Preferably, it includes at least the following reflections:

[0156]

[0157] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0158] More preferably, it includes at least the following reflections:

[0159]

[0160] This involves 100% the intensity of the maximum peak in the X-ray powder diffraction pattern, which is preferably determined according to reference example 1.2.

[0161] Where M 1 More preferably Mg and wherein M 2 More preferably, it is Al.

[0162] 39. The method of any one of Examples 26 to 38, wherein the molded article obtained by (iii) has a water adsorption amount in the range of 25 to 50 wt%, preferably in the range of 37 to 47 wt%, more preferably in the range of 40 to 44 wt%, wherein the water adsorption amount is preferably determined according to Reference Example 1.1.

[0163] 40. The method as described in any one of Examples 26 to 39, wherein the molded article obtained by (iii) has a thickness of 40.0 to 60.0 m. 2Within the range of / g, preferably between 47.0 and 53.0 m 2 Within the range of / g, more preferably from 49.0 to 51.0 m 2 The BET specific surface area in the range of / g, wherein the BET specific surface area is preferably determined according to Reference Example 1.3.

[0164] 41. The method of any one of Examples 26 to 40, wherein the molded article obtained by (iii) has a total pore volume in the range of 0.20 to 0.55 ml / g, preferably in the range of 0.30 to 0.42 ml / g, more preferably in the range of 0.33 to 0.39 ml / g, wherein the total pore volume is preferably determined according to Reference Example 1.4.

[0165] 42. The method as described in any one of Examples 26 to 41, wherein the treatment according to (iv) includes immersing the molded article in acid.

[0166] 43. The method as described in any one of Examples 26 to 42, wherein the treatment according to (iv) is carried out for a period of time ranging from 20 to 100 minutes, preferably from 45 to 75 minutes, and more preferably from 55 to 65 minutes.

[0167] 44. The method as described in any one of Examples 26 to 43, wherein the treatment according to (iv) is carried out at a temperature in the range of 0°C to 50°C, preferably in the range of 10°C to 40°C, and more preferably in the range of 15°C to 35°C.

[0168] 45. The method as described in any one of Examples 26 to 44, wherein the acid according to (iv) is an aqueous solution of an acid.

[0169] 46. ​​The method as described in Example 45, wherein the aqueous solution of the acid has an acid-to-water weight ratio in the range of 1:1 to 1:10, preferably in the range of 1:3 to 1:5, and more preferably in the range of 1:3.9 to 1:4.1.

[0170] 47. The method as described in Examples 45 or 46, wherein the aqueous solution of the acid has an acid concentration in water in the range of 2.5 to 4.5 mol / L, preferably in the range of 3.2 to 3.7 mol / L, and more preferably in the range of 3.3 to 3.6 mol / L.

[0171] 48. The method as described in any one of Examples 26 to 47, wherein the acid according to (iv) comprises, preferably consists of, one or more of an inorganic acid and an organic acid, preferably one or more of HNO3, HCl, H2SO4, H3PO4, formic acid, oxalic acid, and acetic acid, more preferably HNO3.

[0172] 49. The method as described in any one of Examples 26 to 48, wherein the method further comprises, after (iv) and before (v),

[0173] (w) Wash the molded product obtained from (iv) with deionized water.

[0174] 50. The method as described in any one of Examples 26 to 49, wherein the method further comprises, after (iv) and before (v), preferably after (w) and before (v), the method further comprising

[0175] (d) Dry the molded articles obtained by (iv) or (w) in a gaseous atmosphere.

[0176] 51. The method as described in Example 50, wherein the drying according to (d) is carried out at a temperature in the range of 80°C to 160°C, preferably in the range of 100°C to 140°C, and more preferably in the range of 110°C to 130°C.

[0177] 52. The method as described in Example 50 or 51, wherein the drying of (d) is carried out for a period of time ranging from 0.5 to 16 h, preferably from 2 to 12 h, and more preferably from 3 to 8 h.

[0178] 53. The method as described in any one of Examples 50 to 52, wherein the gas atmosphere according to (d) comprises, preferably, one or more of oxygen and nitrogen, preferably air.

[0179] 54. The method as described in any one of Examples 26 to 53, wherein the calcination according to (v) is carried out at a temperature in the range of 400°C to 1000°C, preferably in the range of 600°C to 950°C, and more preferably in the range of 825°C to 875°C.

[0180] 55. The method as described in any one of Examples 26 to 54, wherein the calcination according to (v) is carried out for a period of time ranging from 0.1 to 1.5 h, preferably from 0.3 to 0.7 h, and more preferably from 0.4 to 0.6 h.

[0181] 56. The method as described in any one of Examples 26 to 55, wherein the gas atmosphere according to (v) comprises, preferably, one or more of oxygen and nitrogen, preferably air.

[0182] 57. The method as described in any one of Examples 26 to 56, wherein the method further comprises, after (v),

[0183] (vi) To mix one or more metals M 3 The load is applied to the molded part obtained by (v).

[0184] The loading is preferably carried out by impregnation, more preferably by wet impregnation, and even more preferably by initial wet impregnation.

[0185] Where M 3 The group consisting of Fe, Ru, Os, Co, Rh, Ir, Pd, Pt, Cu, Ag, Mo, Sn, and mixtures of two or more thereof is selected, preferably the group consisting of Fe, Ru, and mixtures of two or more thereof.

[0186] 58. A molded article, preferably according to any one of Examples 1 to 57, wherein the molded article is obtainable or acquired by the method according to any one of Examples 26 to 57.

[0187] 59. Use of the molded article according to any one of Examples 1 to 25 and 58 as a catalyst or catalyst support.

[0188] The invention is further illustrated by the following examples, comparative examples, and reference examples. Example

[0189] Reference Example 1: Measurement Method

[0190] Reference Example 1.1: Determination of Water Adsorption Capacity

[0191] Place the dried molded product in water until it is completely submerged. Leave the molded product in the water for 60 minutes. Afterward, allow the outer surface of the molded product to dry and measure its weight. The water absorption rate (in weight %) is calculated according to Formula I:

[0192] Water absorption rate = (Weight of wet molded product - Weight of dry molded product) / Weight of dry molded product (I).

[0193] Reference Example 1.2: Determination of X-ray Powder Diffraction and Crystallinity

[0194] Powder X-ray diffraction (PXRD) data were collected using a diffractometer (D8 Advance II series, Bruker AXS GmbH) equipped with a LYNXEYE detector that operates with a copper anode X-ray tube at 40 kV and 40 mA. The geometry was Bragg-Brentano, and an air scattering shield was used to reduce air scattering.

[0195] Crystallinity calculation: The crystallinity of the sample was determined using the software DIFFRAC.EVA provided by Bruker AXS in Karlsruhe, according to the method described on page 121 of the user manual. Default parameters were used for the calculations.

[0196] Phase composition was calculated using the modeling software DIFFRAC.TOPAS (DIFFRAC.TOPAS version 6, 2017 user manual, BRUSH AXS, Karlsruhe) provided by BRUSH AXS. The diffraction pattern was simulated using the crystal structure of the determined phases, instrument parameters, and grain size of individual phases. In addition to a function modeling the background intensity, it was fitted to the data.

[0197] Data Collection: Samples were homogenized in a mortar and then pressed into a standard flat sample holder provided by Bruker AXS for geometric data collection in the Bragg-Brentano region. A flat surface was achieved by compressing and flattening the sample powder using a glass plate. Data were collected in 0.02° 2θ steps from an angle range of 2° to 70° 2θ, with the variable divergence slit set at an angle of 0.1°. Crystal content describes the ratio of the intensity of the crystal signal to the total scattered intensity.

[0198] Reference Example 1.3: Determination of BET specific surface area

[0199] The BET surface area was determined by nitrogen physisorption at 77 K according to the method disclosed in DIN 66131.

[0200] Refer to Example 1.4: Determination of Total Pore Volume

[0201] Total pore volume was determined according to DIN 66133 by mercury porosimetry. For this purpose, a MicroActiveAutoPore V 9600 was used.

[0202] Reference Example 1.5: Determination of Pore Size Distribution

[0203] Pore ​​size distribution was determined according to DIN 66133 by mercury porosimetry. For this purpose, a MicroActiveAutoPore V 9600 was used.

[0204] Reference Example 1.6: Elemental Analysis

[0205] Elemental analysis was performed according to ICP-OES and DIN ISO 17025.

[0206] Example 1: Preparation of a molded article according to the present invention

[0207] Pural Mg 30 (containing Mg calculated as MgO and Al calculated as Al2O3 in a weight ratio of 30:70) tetralobes were calcined in air at 950°C for 3 h. The calcined tetralobes were then treated with nitric acid as follows. The calcined tetralobes were placed in a glass beaker, which was then filled with an aqueous solution containing HNO3 (20 wt.-% concentration, corresponding to 3.3 mol / L). All tablets were completely covered by the acidic solution. After 60 minutes, the acidic solution was removed, and the obtained tetralobes were washed with demineralized water. The tetralobes were dried at 120°C for 4 h (heating rate 5°C / min). Following the drying step, a calcination step was performed at 850°C for 0.5 h (heating rate 5°C / min) to remove residual nitrates. The characteristics of the molded product before and after acid treatment are recorded in Table 1 below.

[0208] Table 1

[0209] Characteristics of Pural Mg 30 four-leaf shaped parts before and after treatment with an aqueous solution containing HNO3.

[0210] Attached Figure Description

[0211] Figure 1 The image shows a sample of the molded article according to Example 1 before acid treatment, with powder XRD. It shows the presence of the MgO periclase phase in addition to the MgAl₂O₄ spinel phase.

[0212] Figure 2 The image shows a powder XRD pattern of a sample of the molded article according to Example 1 after acid treatment. It shows the presence of the MgAl₂O₄ spinel phase, but the absence of the MgO periclase phase.

[0213] Figure 3 :exist Figure 3 Figure A shows a cross-section of an impregnated sample molded article that has not been treated according to the present invention, and... Figure 3 Figure B shows a cross-section of a sample molded article processed according to the present invention.

[0214] Figure 4 The diagram illustrates the pore size distribution of a molded article according to Example 1 of the present invention before and after HNO3 treatment. The pore diameter is given on the horizontal axis in µm on a logarithmic scale, and the relative differential indentation volume is given on the vertical axis. References

[0215] -CA 1189052

[0216] -US 4558031

[0217] -EP 0210681 A1

[0218] -WO 94 / 16798 A1

[0219] -GB 1377191 A.

Claims

1. A molded article comprising an empirical formula M 1 M 2 Mixed metal oxides of 2O4, wherein M 1 Contains one or more divalent elements M 1 M 2 Contains one or more trivalent elements M 2 The mixed metal oxide comprises a crystalline phase having a spinel structure, and the molded article has a total pore volume in the range of 0.10 to 0.90 ml / g.

2. The molded article as claimed in claim 1, wherein, M 1 Elements are selected from Groups 2, 10, 11, and 12 of the periodic table.

3. The molded article as described in claim 1 or 2, wherein, M 2 Elements are selected from groups 5, 6, 7, 8, and 13 of the periodic table.

4. The molded article as described in any one of claims 1 to 3, comprising based on the one or more divalent elements M contained in the molded article. 1 With M 1 The total weight calculated by O is 1.0% of the weight or less of M. 1 O.

5. The molded article as described in any one of claims 1 to 4, comprising based on the one or more trivalent elements M contained in the molded article. 2 With M 2 The total weight calculated from 2O3 is 1 wt% or less of M. 2 2O3.

6. The molded article according to any one of claims 1 to 5, having a median pore size in the range of 0.001 to 0.1 µm.

7. The molded article according to any one of claims 1 to 6, having a water adsorption amount in the range of 10 to 80% by weight.

8. The molded article according to any one of claims 1 to 7, optionally further comprising one or more metals M 3 And has a range of 20.0 to 150.0 m 2 BET specific surface area within the range of / g.

9. The molded article as claimed in any one of claims 1 to 8, wherein, 85 to 100% by weight of this molded part is made of M 1 M 2 O, H, and one or more optional metals M 3 composition.

10. The molded article as claimed in any one of claims 1 to 9, wherein the molded article is an extrusion, tablet, or granule.

11. The molded article as claimed in claim 10, wherein, The extrudate or the tablet has a cross section, wherein the cross section is circular, hexagonal, rectangular, square, triangular, elliptical, star-shaped polygon, or clover-shaped.

12. A method for preparing a molded article, the method comprising: (i) Provide M 1 O and M 2 One or more sources of 2O3, wherein M 1 Represents one or more divalent elements and M 2 Represents one or more trivalent elements; (ii) Molding the one or more sources obtained from (i); (iii) Calcination of the molded product obtained by (ii) in a gaseous atmosphere; (iv) Treat the molded article obtained from (iii) with acid; (v) Calcine the molded product obtained by (iv) in a gaseous atmosphere.

13. The method of claim 12, wherein, M 1 O and M 2 The one or more sources of 2O3 comprise one or more compounds selected from the group consisting of: M 1 oxides, M 1 hydroxide, M 1 carbonates, M 1 Bicarbonate, M 1 Hydroxycarbonate, M 2 oxides, M 2 hydroxide, M 2 carbonates, M 2 Bicarbonate, M 2 Hydroxycarbonate, M 1 and M 2 Mixed metal oxides, M 1 and M 2 Mixed metal hydroxy carbonates, and mixtures of two or more thereof.

14. A molded article, wherein the molded article is obtainable or acquired by the method according to claim 12 or 13.

15. Use of the molded article as a catalyst or catalyst support as claimed in any one of claims 1 to 11 and 14.

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