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WO2025027150A1 - Moulage poreux comprenant un spinelle - Google Patents

Moulage poreux comprenant un spinelle Download PDF

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Publication number
WO2025027150A1
WO2025027150A1 PCT/EP2024/071861 EP2024071861W WO2025027150A1 WO 2025027150 A1 WO2025027150 A1 WO 2025027150A1 EP 2024071861 W EP2024071861 W EP 2024071861W WO 2025027150 A1 WO2025027150 A1 WO 2025027150A1
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WO
WIPO (PCT)
Prior art keywords
molding
range
weight
elements
preferred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/071861
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English (en)
Inventor
Elias Christopher FREI
Lukasz KARWACKI
Adelheid Schulz
Nils Bottke
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BASF SE
Original Assignee
BASF SE
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Publication of WO2025027150A1 publication Critical patent/WO2025027150A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing

Definitions

  • a porous molding comprising a spinel
  • the present invention relates to a molding comprising a mixed metal oxide having the empirical formula M 1 M 2 2O4, wherein M 1 comprises one or more divalent elements M 1 , wherein M 2 comprises one or more trivalent elements M 2 , wherein the mixed metal oxide comprises a crystalline phase having a spinel structure, and wherein the molding has a total pore volume in the range of from 0.10 to 0.90 ml/g. Further, the present invention relates to a process for preparing a novel molding, the molding obtainable or obtained by said process, as well as use of the novel molding of the present invention.
  • a catalyst comprises a support material and a catalytic material loaded thereon.
  • the support materials used are usually in form of a molding, which may have a specific shape.
  • the loading can be conducted with known methods, in particular by impregnation, and more specifically by incipient wet impregnation, e.g. using a metal solution.
  • the soaking behavior of a support material is crucial.
  • CA 1189052 relates to a method of producing catalysts or catalyst supports having both high surface area and large pore sizes, wherein said method particularly comprises mixing a metal oxide with water and an acid to form a dilute metal gel consisting of a loose three dimensional network of oxide containing a large amount of water evenly dispersed throughout.
  • US 4558031 relates to a high porosity catalyst and discloses a method of producing catalysts or catalyst supports having both high surface area and large pore sizes which particularly comprises mixing an 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.
  • EP 0210681 A1 relates to a catalyst suitable for reduction and oxidation reactions, the catalyst comprising a magnesium-aluminate spinel in combination with copper, cobalt, compounds of copper or cobalt or mixture thereof, wherein the spinel-based carrier optionally comprises an oxide of a secondary bivalent metal.
  • WO 94/16798 A1 relates to a process for catalytically decomposing nitrous oxide pure or contained in gaseous mixtures at 200 to 900 °C and pressures of 0.1 and 20 bar, by using a catalyst prepared by combining CUAI2O4 with tin, lead, an element of the II. main or subgroup of the periodic table of elements as oxide or salt or in the elementary form, and calcining at 300 to 1300 °C and at a pressure from 0.1 to 200 bars.
  • GB 1377191 A relates to a catalyst comprising metallic cobalt or cobalt oxide or both supported on a mixed oxide material having predominantly a spinel structure and being substantially free of uncombined oxide capable of forming a spinel with cobalt oxide, i.e. containing less than 5% wt. of any divalent or a tetravalent oxide capable of forming such a spinel or less than 1 % wt. of any trivalent oxide capable of forming such a spinel.
  • a molding having a fine-tuned porosity preferably for providing a molding having an increased porosity.
  • a process comprising the steps of calcining the molding and subsequent treatment thereof with an acid, leads to a molding allowing a significantly improved distribution of the metal solution throughout the whole molding. It was particularly found that the porosity, especially the total pore volume, of the molding can be adjusted and fine-tuned, and in particular increased, when treated accordingly. Thus, it was found that upon treating a pre-cal- cined molding with an acid improved significantly the soaking properties of the molding. This treatment particularly allows impregnating moldings with a demanding shape. In particular, moldings having a low surface to volume ratio can be impregnated homogeneously.
  • FIG 3 Two sample moldings were impregnated with a metal solution, calcined and then cut in half.
  • the sample molding shown in figure 3A was not treated according to the present invention, whereas the sample molding shown in figure 3B was treated in accordance with the present invention prior to the impregnation.
  • the sample molding which was not treated with an aqueous solution comprising an acid in accordance with the present invention is not homogeneously impregnated, indicated by a different coloring.
  • a uniform coloring for the sample molding shown in figure 3B indicates a homogeneous impregnation.
  • the present invention relates to a molding comprising a mixed metal oxide having the empirical formula M 1 M 2 2O4, wherein M 1 comprises one or more divalent elements M 1 , wherein M 2 comprises one or more trivalent elements M 2 , wherein 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 molding has a total pore volume in the range of from 0.10 to 0.90 ml/g, wherein the total pore volume is preferably determined according to Reference Example 1.4.
  • M 1 is selected from groups 2, 10, 11 and 12 of the periodic table of elements, wherein M 1 is more preferably selected from the group consisting of Mg, Ni, Cu, Zn, Mn, Co, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Ni, Cu, Zn, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Zn, Cu, and mixtures thereof, more preferably from the group consisting of Mg, Zn, and mixtures thereof, wherein M 1 more preferably is Mg.
  • M 2 is selected from groups 5, 6, 7, 8 and 13 of the periodic table of elements, wherein M 2 is more preferably selected from the group consisting of Al, Cr, Fe, V, Mn, Co, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, Fe, V, Mn, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, V, Mn, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, and mixtures of two or more thereof, wherein M 2 more preferably is Al.
  • the molding comprises 10 weight- % or less, more preferably 5 weight-% or less, more preferably 1 .0 weight-% or less, more preferably 0.1 weight-% or less, more preferably 0.01 weight-% or less of M 1 O, preferably determined according to Reference Example 1.2, based on the total weight of the one or more divalent elements M 1 , calculated as M 1 O, contained in the molding, wherein the total weight of the one or more divalent elements M 1 , calculated as M 1 O, in the molding is preferably determined according to Reference Example 1.6.
  • the molding comprises 10 weight-% or less, more preferably 5 weight-% or less, more preferably 1 weight-% or less, more preferably 0.1 weight-% or less, more preferably 0.01 weight-% or less, of M 2 2O3, preferably determined according to Reference Example 1.2, based on the total weight of the one or more trivalent elements M 2 , calculated as M 2 2O3, contained in the molding, wherein the total weight of the one or more divalent elements M 2 , calculated as M 2 20S, contained in the molding is preferably determined according to Reference Example 1 .6.
  • the mixed metal oxide has a crystallinity in the range of 50 to 100 %, more preferably of 60 to 100 %, more preferably of 70 to 95 %, more preferably of 80 to 90 %, wherein the crystallinity is determined according to Reference Example 1 .2.
  • the mixed metal oxide has a crystallinity in the range of 50 to 100 %
  • the molding exhibits an X-ray diffraction pattern comprising at least the following reflections: wherein 100 % relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, wherein the X-ray diffraction pattern is preferably determined according to Reference Example 1 .2, more preferably comprising at least the following reflections: wherein 100 % relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, wherein the X-ray diffraction pattern is preferably determined according to Reference Example 1 .2, more preferably comprising at least the following reflections: wherein 100 % relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, wherein the X-ray diffraction pattern is preferably determined according to Reference Example 1 .2, wherein M 1 is more preferably Mg and wherein M 2 is more preferably Al.
  • the molding has a water adsorption in the range of from 10 to 80 weight-%, more preferably in the range of from 30 to 60 weight-%, more preferably in the range of from 40 to 50 weight-%, more preferably in the range of from 43 to 47 weight-%, wherein the water adsorption is preferably determined according to Reference Example 1.1.
  • the molding has a BET specific surface area in the range of from 20.0 to 150.0 m 2 /g, more preferably in the range of from 30.0 to 90.0 m 2 /g, more preferably in the range of from 40.0 to 65.0 m 2 /g, more preferably in the range of from 47.0 to 49.0 m 2 /g, wherein the BET specific surface area is preferably determined according to Reference Example 1 .3.
  • the molding has a total pore volume in the range of from 0.18 to 0.75 ml/g, more preferably in the range of from 0.25 to 0.60 ml/g, more preferably in the range of from 0.33 to 0.53 ml/g, more preferably in the range of from 0.37 to 0.49 ml/g, more preferably in the range of from 0.40 to 0.46 ml/g, wherein the total pore volume is preferably determined according to Reference Example 1 .4.
  • the molding further comprises one or more metals M 3 , wherein M 3 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 are more preferably supported on the mixed metal oxide.
  • M 3 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 are more preferably supported on the mixed metal oxide.
  • the molding further comprises comprises one or more metals M 3 , wherein M 3 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 molding comprises 20 weight-% or less, more preferably 10 weight-% or less, more preferably 5 weight-% or less, of the one or more metals M 3 , calculated as elements, based on the sum of the weights of the one or more divalent elements M 1 , calculated as M 1 O, and the one or more trivalent elements M 2 , calculated as M 2 20S, wherein the sum of the weights of the one or more divalent elements M 1 , calculated as M 1 O, and the one or more trivalent elements M 2 , calculated as M 2 2O3, contained in the molding is preferably determined according to Reference Example 1 .6.
  • the molding further comprises one or more metals M 3 , wherein M 3 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 one or more metals M 3 are homogeneously dispersed throughout the molding.
  • the molding is an extrudate, a tablet, or a granule.
  • the extrudate or the tablet has a cross-section, wherein the cross-section is circular, hexagonal, rectangular, quadratic, triangular, oval, a star-shaped polygon, or cloverleaf-shaped, more preferably circular, hexagonal, rectangular, quadratic, triangular, oval, a star-shaped polygon having 3, 4, 5, 6, 7, or 8 tips, a trilobe, a quadrilobe or a hexalobe, more preferably circular, hexagonal, rectangular, quadratic, triangular, oval, a star-shaped polygon having 3 or 4 tips, a trilobe, a quadrilobe or a hexalobe.
  • the molding is a tablet having a cross-section, wherein the cross-section is a quadrilobe
  • the tablet has a thickness, wherein the thickness is in the range of from 2.0 to 13.0 mm, more preferably in the range of from 5.0 to 10.0 mm, more preferably in the range of from 6.5 to 9.0 mm.
  • the molding is a tablet having a cross-section
  • the tablet has a diameter D in the range of from 5 to 20 mm, more preferably in the range of from 7 to 17 mm, more preferably in the range of from 9 to 15 mm.
  • the molding is a tablet having a cross-section, wherein the cross-section is a hexalobe.
  • the molding is a tablet having a cross-section, wherein the cross-section is a hexalobe
  • the tablet has a thickness, wherein the thickness is in the range of from 2.0 to 15.0 mm, more preferably in the range of from 5.0 to 12.0 mm, more preferably in the range of from 8.0 to 9.0 mm.
  • the molding is a tablet having a cross-section, wherein the crosssection is a hexalobe
  • the tablet has a diameter D in the range of from 5 to 25 mm, more preferably in the range of from 12 to 19 mm, more preferably in the range of from 14 to 17 mm.
  • the present invention relates to a process for preparing a molding, preferably for preparing a molding according to any one of the particular and preferred embodiments disclosed herein, the process comprising
  • M 1 is selected from groups 2, 10, 11 and 12 of the periodic table of elements, wherein M 1 is more preferably selected from the group consisting of Mg, Ni, Cu, Zn, Mn, Co, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Ni, Cu, Zn, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Zn, Cu, and mixtures thereof, more preferably from the group consisting of Mg, Zn, and mixtures thereof, wherein M 1 more preferably is Mg.
  • M 2 is selected from groups 5, 6, 7, 8 and 13 of the periodic table of elements, wherein M 2 is more preferably selected from the group consisting of Al, Cr, Fe, V, Mn, Co, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, Fe, V, Mn, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, V, Mn, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, and mixtures of two or more thereof, wherein M 2 more preferably is Al.
  • the one or more sources for M 1 O and M 2 2O3 comprise, preferably consist of, one or more compounds selected from the group consisting of oxides of M 1 , hydroxides of M 1 , carbonates of M 1 , hydrogencarbonates of M 1 , hydroxy carbonates of M 1 , oxides of M 2 , hydroxides of M 2 , carbonates of M 2 , hydrogencarbonates of M 2 , hydroxy carbonates of M 2 , mixed metal oxides of M 1 and M 2 , mixed metal hydroxy carbonates of M 1 and M 2 , and mixtures of two or more thereof.
  • the one or more sources for M 1 O and M 2 2O3 comprise, preferably consist of, one or more compounds selected from the group consisting of mixed metal oxides of M 1 and M 2 , mixed metal hydroxy carbonates of M 1 and M 2 , and mixtures thereof.
  • the one or more sources for M 1 O and M 2 2O3 have a molar ratio of M 1 to M 2 in the range of from 1 :5 to 5:1.0, more preferably in the range of from 1 :2.5 to 2.5:1 , more preferably in the range of from 1 :2 to 2:1 , more preferably in the range of from 1 :2.1 to 1 :1 .9.
  • the one or more sources for M 1 O and M 2 2O3 comprise from 22 to 34 weight- %, more preferably from 25 to 31 weight-%, more preferably from 27 to 29 weight-%, of M 1 , calculated as M 1 O, based on the sum of the weights of M 1 , calculated as M 1 O, and M 2 , calculated as M 2 2C>3, comprised in the one or more sources for M 1 O and M 2 2O3.
  • the one or more sources for M 1 O and M 2 2O3 comprise from 66 to 78 weight- %, more preferably from 69 to 75 weight-%, more preferably from 71 to 73 weight-%, of M 2 , calculated as M 2 2C>3, based on the sum of the weights of M 1 , calculated as M 1 O, and M 2 , calculated as M 2 2C>3, comprised in the one or more sources for M 1 O and M 2 2O3.
  • molding the mixture according to (ii) comprises tableting or extruding.
  • calcining according to (iii) is conducted at a temperature in the range of from 300 to 1200 °C, more preferably in the range of from 700 to 1100 °C, more preferably in the range of from 900 to 1000 °C.
  • calcining according to (iii) is conducted for a period of time in the range of from 0.1 to 48 h, more preferably in the range of from 0.5 to 24 h, more preferably in the range of from 1 to 5 h.
  • the gas atmosphere according to (iii) comprises, preferably consists of, one or more of oxygen and nitrogen, more preferably air.
  • the molding obtained from (iii) exhibits an X-ray diffraction pattern comprising at least the following reflections: wherein 100 % relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, wherein the X-ray diffraction pattern is preferably determined according to Reference Example 1 .2, more preferably comprising at least the following reflections: wherein 100 % relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, wherein the X-ray diffraction pattern is preferably determined according to Reference Example 1 .2, more preferably comprising at least the following reflections: wherein 100 % relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, wherein the X-ray diffraction pattern is preferably determined according to Reference Example 1 .2, wherein M 1 is more preferably Mg and wherein M 2 is more preferably Al.
  • the molding obtained from (iii) has a water adsorption in the range of from 25 to 50 weight-%, more preferably in the range of from 37 to 47 weight-%, more preferably in the range of from 40 to 44 weight-%, wherein the water adsorption is preferably determined according to Reference Example 1.1.
  • the molding obtained from (iii) has a BET specific surface area in the range of from 40.0 to 60.0 m 2 /g, more preferably in the range of from 47.0 to 53.0 m 2 /g, more preferably in the range of from 49.0 to 51 .0 m 2 /g, wherein the BET specific surface area is preferably determined according to Reference Example 1 .3.
  • the molding obtained from (iii) has a total pore volume in the range of from 0.20 to 0.55 ml/g, more preferably in the range of from 0.30 to 0.42 ml/g, more preferably in the range of from 0.33 to 0.39 ml/g, wherein the total pore volume is preferably determined according to Reference Example 1 .4.
  • treating according to (iv) comprises immersing the molding in the acid.
  • treating according to (iv) is conducted for a period of time in the range of from 20 to 100 minutes, more preferably in the range of from 45 to 75 minutes, more preferably in the range of from 55 to 65 minutes.
  • treating according to (iv) is conducted at a temperature in the range of from 0 to 50 °C, more preferably in the range of from 10 to 40 °C, more preferably in the range of from 15 to 35 °C.
  • the acid according to (iv) is an aqueous acid.
  • the aqueous acid has a weight ratio of acid to water in the range of from 1 :1 to 1 :10, more preferably in the range of from 1 :3 to 1 :5, more preferably in the range of from 1 :3.9 to 1 :4.1. Further in the case wherein the acid according to (iv) is an aqueous acid, it is preferred that the aqueous acid has a concentration of acid in water in the range of from 2.5 to 4.5 mol/l, more preferably in the range of from 3.2 to 3.7 mol/l, more preferably in the range of from 3.3 to 3.6 mol/l.
  • the acid according to (iv) comprises, preferably consists of, one or more of an inorganic acid and an organic acid, more preferably one or more of HNO3, HCI, H2SO4, H3PO4, formic acid, oxalic acid, acetic acid, more preferably HNO3.
  • the process further comprises after (iv) and prior to (v), (w) washing the molding obtained from (iv) with de-ionized water.
  • the process further comprises after (iv) and prior to (v), preferably after (w) and prior to (v),
  • drying is conducted at a temperature in the range of from 80 to 160 °C, more preferably in the range of from 100 to 140 °C, more preferably in the range of from 110 to 130 °C.
  • drying according to (d) is conducted for a period of time in the range of from 0.5 to 16 h, more preferably in the range of from 2 to12 h, more preferably in the range of from 3 to 8 h.
  • the process further comprises drying according to (d)
  • the gas atmosphere according to (d) comprises, preferably consists of, one or more of oxygen and nitrogen, more preferably air.
  • calcining according to (v) is conducted at a temperature in the range of from 400 to 1000 °C, more preferably in the range of from 600 to 950 °C, more preferably in the range of from 825 to 875 °C.
  • calcining according to (v) is conducted for a period of time in the range of from 0.1 to 1.5 h, preferably in the range of from 0.3 to 0.7 h, more preferably in the range of from 0.4 to 0.6 h.
  • the gas atmosphere according to (v) comprises, preferably consists of, one or more of oxygen and nitrogen, more preferably air.
  • process further comprises after (v)
  • the present invention relates to a molding, preferably according to any one of the particular and preferred embodiments disclosed herein, wherein the molding is obtainable or obtained by the process according to any one of the particular and preferred embodiments disclosed herein.
  • the present invention relates to use of the molding according to any one of the particular and preferred embodiments disclosed herein, as a catalyst or catalyst support.
  • a molding comprising a mixed metal oxide having the empirical formula M 1 M 2 2O4, wherein M 1 comprises one or more divalent elements M 1 , wherein M 2 comprises one or more triva- lent elements M 2 , wherein 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 molding has a total pore volume in the range of from 0.10 to 0.90 ml/g, wherein the total pore volume is preferably determined according to Reference Example 1.4.
  • M 1 is selected from groups 2, 10, 11 and 12 of the periodic table of elements, wherein M 1 is preferably selected from the group consisting of Mg, Ni, Cu, Zn, Mn, Co, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Ni, Cu, Zn, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Zn, Cu, and mixtures thereof, more preferably from the group consisting of Mg, Zn, and mixtures thereof, wherein M 1 more preferably is Mg. 3.
  • M 2 is selected from groups 5, 6, 7, 8 and 13 of the periodic table of elements, wherein M 2 is preferably selected from the group consisting of Al, Cr, Fe, V, Mn, Co, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, Fe, V, Mn, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, V, Mn, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, and mixtures of two or more thereof, wherein M 2 more preferably is Al.
  • any one of embodiments 1 to 3, comprising 10 weight- % or less, preferably 5 weight-% or less, more preferably 1.0 weight-% or less, more preferably 0.1 weight- % or less, more preferably 0.01 weight-% or less of M 1 O, preferably determined according to Reference Example 1 .2, based on the total weight of the one or more divalent elements M 1 , calculated as M 1 O, contained in the molding, wherein the total weight of the one or more divalent elements M 1 , calculated as M 1 O, in the molding is preferably determined according to Reference Example 1 .6.
  • any one of embodiments 1 to 4 comprising 10 weight-% or less, preferably 5 weight-% or less, more preferably 1 weight-% or less, more preferably 0.1 weight-% or less, more preferably 0.01 weight-% or less, of M 2 2O3, preferably determined according to Reference Example 1 .2, based on the total weight of the one or more trivalent elements M 2 , calculated as M 2 2O3, contained in the molding, wherein the total weight of the one or more divalent elements M 2 , calculated as M 2 2O3, contained in the molding is preferably determined according to Reference Example 1.6.
  • any one of embodiments 1 to 8 having a median pore diameter in the range of from 0.001 to 0.1 pm, preferably in the range of from 0.005 to 0.05 pm, more preferably in the range of from 0.02 to 0.04 pm, more preferably in the range of from 0.027 to 0.035 pm, more preferably in the range of from 0.028 to 0.034 pm, wherein the pore size distribution is preferably determined according to Reference Example 1.5.
  • the molding of any one of embodiments 1 to 11 having a total pore volume in the range of from 0.18 to 0.75 ml/g, preferably in the range of from 0.25 to 0.60 ml/g, more preferably in the range of from 0.33 to 0.53 ml/g, more preferably in the range of from 0.37 to 0.49 ml/g, more preferably in the range of from 0.40 to 0.46 ml/g, wherein the total pore volume is preferably determined according to Reference Example 1.4.
  • M 3 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 are more preferably supported on the mixed metal oxide.
  • the molding of embodiment 13, comprising 20 weight-% or less, preferably 10 weight-% or less, more preferably 5 weight-% or less, of the one or more metals M 3 , calculated as elements, based on the sum of the weights of the one or more divalent elements M 1 , calculated as M 1 O, and the one or more trivalent elements M 2 , calculated as M 2 2O3, wherein the sum of the weights of the one or more divalent elements M 1 , calculated as M 1 O, and the one or more trivalent elements M 2 , calculated as M 2 2O3, contained in the molding is preferably determined according to Reference Example 1.6.
  • the tablet has a thickness, wherein the thickness is in the range of from 2.0 to 13.0 mm, preferably in the range of from 5.0 to 10.0 mm, more preferably in the range of from 6.5 to 9.0 mm.
  • a process for preparing a molding preferably for preparing a molding according to any one of embodiments 1 to 25, the process comprising
  • M 1 is selected from groups 2, 10, 11 and 12 of the periodic table of elements, wherein M 1 is preferably selected from the group consisting of Mg, Ni, Cu, Zn, Mn, Co, and mixtures of two or more thereof, more preferably selected from the group consisting of Mg, Ni, Cu, Zn, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Zn, Cu, and mixtures thereof, more preferably from the group consisting of Mg, Zn, and mixtures thereof, wherein M 1 more preferably is Mg.
  • M 2 is selected from groups 5, 6, 7, 8 and
  • M 2 is preferably selected from the group consisting of Al, Cr, Fe, V, Mn, Co, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, Fe, V, Mn, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, V, Mn, and mixtures of two or more thereof, more preferably selected from the group consisting of Al, Cr, and mixtures of two or more thereof, wherein M 2 more preferably is Al.
  • any one of embodiments 26 to 28, wherein the one or more sources for M 1 O and M 2 2O3 comprise, preferably consist of, one or more compounds selected from the group consisting of oxides of M 1 , hydroxides of M 1 , carbonates of M 1 , hydrogencarbonates of M 1 , hydroxy carbonates of M 1 , oxides of M 2 , hydroxides of M 2 , carbonates of M 2 , hydrogencarbonates of M 2 , hydroxy carbonates of M 2 , mixed metal oxides of M 1 and M 2 , mixed metal hydroxy carbonates of M 1 and M 2 , and mixtures of two or more thereof.
  • any one of embodiments 26 to 29, wherein the one or more sources for M 1 O and M 2 2O3 comprise, preferably consist of, one or more compounds selected from the group consisting of mixed metal oxides of M 1 and M 2 , mixed metal hydroxy carbonates of M 1 and M 2 , and mixtures thereof.
  • any one of embodiments 1 to 31 wherein the one or more sources for M 1 O and M 2 2O3 comprise from 22 to 34 weight-%, preferably from 25 to 31 weight-%, more preferably from 27 to 29 weight-%, of M 1 , calculated as M 1 O, based on the sum of the weights of M 1 , calculated as M 1 O, and M 2 , calculated as M 2 2O3, comprised in the one or more sources for M 1 O and M 2 2O3.
  • any one of embodiments 1 to 32 wherein the one or more sources for M 1 O and M 2 2O3 comprise from 66 to 78 weight-%, preferably from 69 to 75 weight-%, more preferably from 71 to 73 weight-%, of M 2 , calculated as M 2 2O3, based on the sum of the weights of M 1 , calculated as M 1 O, and M 2 , calculated as M 2 2O3, comprised in the one or more sources for M 1 O and M 2 2O3.
  • molding the mixture according to (ii) comprises tableting or extruding.
  • gas atmosphere according to (iii) comprises, preferably consists of, one or more of oxygen and nitrogen, preferably air.
  • treating according to (iv) comprises immersing the molding in the acid.
  • aqueous acid has a weight ratio of acid to water in the range of from 1 :1 to 1 : 10, preferably in the range of from 1 :3 to 1 :5, more preferably in the range of from 1 :3.9 to 1 :4.1.
  • drying according to (d) is conducted at a temperature in the range of from 80 to 160 °C, preferably in the range of from 100 to 140 °C, more preferably in the range of from 110 to 130 °C.
  • gas atmosphere according to (d) comprises, preferably consists of, one or more of oxygen and nitrogen, preferably air.
  • gas atmosphere according to (v) comprises, preferably consists of, one or more of oxygen and nitrogen, preferably air.
  • a molding preferably according to any one of embodiments 1 to 57, wherein the molding is obtainable or obtained by the process according to any one of embodiments 26 to 57. 59. Use of the molding according to any one of embodiments 1 to 25 and 58, as a catalyst or catalyst support.
  • the present invention is further illustrated by the following examples, comparative examples and reference examples.
  • water uptake (weight of wet molding - weight of dried molding) I weight of dried molding (I).
  • Powder X-ray diffraction (PXRD) data was collected using a diffractometer (D8 Advance Series II, Bruker AXS GmbH) equipped with a LYNXEYE detector operated with a Copper anode X-ray tube running at 40 kV and 40 mA.
  • the geometry was Bragg-Brentano, and air scattering was reduced using an air scatter shield.
  • Crystallinity of the samples was determined using the software DIF- FRAC.EVA provided by Bruker AXS GmbH, Düsseldorf, according to the method which is described on page 121 of the user manual. The default parameters for the calculation were used.
  • phase composition The phase composition was computed against the raw data using the modelling software DIFFRAC.TOPAS provided by Bruker AXS GmbH (User Manual for DI FFRAC. TOPAS Version 6, 2017, Bruker AXS GmbH, Düsseldorf). The crystal structures of the identified phases, instrumental parameters as well the crystallite size of the individual phases were used to simulate the diffraction pattern. This was fit against the data in addition to a function modelling the background intensities.
  • the BET specific surface area was determined via nitrogen physisorption at 77 K according to the method disclosed in DIN 66131.
  • the total pore volume was determined via intrusion mercury porosimetry according to DIN 66133. To this effect, a MicroActive AutoPore V 9600 was applied.
  • the pore size distribution was determined via intrusion mercury porosimetry according to DIN 66133. To this effect, a MicroActive AutoPore V 9600 was applied.
  • Example 1 Preparing a molding according to the present invention
  • Pural Mg 30 (comprising Mg, calculated as MgO, and Al, calculated as AI2O3, in a weight ratio of 30:70) quadrilobes were calcined at 950 °C for 3 h in air.
  • the calcined quadrilobes were treated with nitric acid as follows.
  • the calcined quadrilobes were placed in a glass beaker, which was then filled with an aqueous HNOs-containing solution (20 wt.-% concentration, corresponding to 3.3 mol/l). All tablets were fully covered by said acidic solution. After 60 minutes, the acidic solution was removed and the obtained quadrilobes washed with demineralized water.
  • the quadrilobes were dried at 120 °C for 4 h (heating rate of 5 °C/min). After the drying step, a calcination step for removing residual nitrates was conducted at 850 °C for 0.5 h (heating rate of 5 °C/min).
  • the characteristics of the molding before and after the acid treatment are noted in Table 1 below.
  • Figure 1 shows the powder XRD of a sample of the molding according to Example 1 before the acid treatment. It is shown that besides an MgAhC spinel phase also a MgO periclase phase is present.
  • Figure 3 shows in figure 3A the cross-section of an impregnated sample molding which was not treated according to the present invention, and in figure 3B the cross-section of a sample molding which was treated according to the present invention.
  • Figure 4 shows the pore size distribution of a molding according to Example 1 of the present invention before and after HNO3 treatment.
  • the pore size diameter is given in pm on the abscissa in a logarithmic scale, and the relative differential intrusion volume is given on the ordinate.

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Abstract

La présente invention concerne un nouveau moulage présentant une porosité ajustée finement. En particulier, la présente invention concerne un nouveau moulage comprenant un oxyde métallique mixte de formule empirique M1M2 2O4, dans laquelle M1 comprend un ou plusieurs éléments divalents M1, dans laquelle M2 comprend un ou plusieurs éléments trivalents M2, dans laquelle l'oxyde métallique mixte comprend une phase cristalline présentant une structure de spinelle, et dans laquelle le moulage présente un volume total des pores se situant dans la plage allant de 0,10 à 0,90 ml/g. En outre, la présente invention concerne un procédé de préparation d'un nouveau moulage, en particulier dudit nouveau moulage, et un moulage obtenu ou pouvant être obtenu par ledit procédé. En outre, la présente invention concerne l'utilisation dudit moulage en tant que catalyseur ou support de catalyseur.
PCT/EP2024/071861 2023-08-02 2024-08-01 Moulage poreux comprenant un spinelle Pending WO2025027150A1 (fr)

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EP23189163.1 2023-08-02

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1377191A (en) 1971-03-17 1974-12-11 Ici Ltd Catalyst and oxidation process
CA1189052A (fr) 1983-01-18 1985-06-18 Marten Ternan Catalyseur super-poreux
US4558031A (en) 1983-01-24 1985-12-10 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources Of Canada High porosity catalyst
EP0210681A1 (fr) 1985-07-31 1987-02-04 Shell Internationale Researchmaatschappij B.V. Catalyseur d'aluminate et de métal bivalent
WO1994016798A1 (fr) 1993-01-21 1994-08-04 Basf Aktiengesellschaft Procede de decomposition catalytique de l'oxyde azote pur ou contenu dans des melanges gazeux

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1377191A (en) 1971-03-17 1974-12-11 Ici Ltd Catalyst and oxidation process
CA1189052A (fr) 1983-01-18 1985-06-18 Marten Ternan Catalyseur super-poreux
US4558031A (en) 1983-01-24 1985-12-10 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources Of Canada High porosity catalyst
EP0210681A1 (fr) 1985-07-31 1987-02-04 Shell Internationale Researchmaatschappij B.V. Catalyseur d'aluminate et de métal bivalent
WO1994016798A1 (fr) 1993-01-21 1994-08-04 Basf Aktiengesellschaft Procede de decomposition catalytique de l'oxyde azote pur ou contenu dans des melanges gazeux

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