Solid shaped body and use of the solid shaped body

Abstract

A solid shaped body in the shape of a cylinder with a first bottom surface, a second bottom surface and a lateral surface, wherein the solid shaped body comprises in the lateral surface a first number of grooves, each groove extending from the first bottom surface to the second bottom surface, and a second number of openings, each opening extending from the first bottom surface to the second bottom surface. The invention also relates to a process comprising contacting a reactant mixture with the solid shaped body, and the use of the solid shaped body as a catalyst.

Description

[0001] This invention relates to a cylindrical solid molded body having a first bottom surface, a second bottom surface, and side surfaces, wherein the solid molded body includes a first number of grooves in the side surfaces, each groove extending from the first bottom surface to the second bottom surface; and a second number of openings, each opening extending from the first bottom surface to the second bottom surface. The invention also relates to a method comprising contacting a reactant mixture with the solid molded body, and the use of the solid molded body as a catalyst.

[0002] The performance of solid molded bodies (especially when used as catalysts) depends largely on their shape and therefore on their geometry. Mechanical strength, pressure drop, packed bed density, and bed mass diffusion coefficient are examples of performance parameters. Other important parameters are the weight of a single solid molded body, its specific surface area, and its heat and mass transfer properties.

[0003] Solid molded bodies are used, for example, in hydrocarbon reforming to syngas, where oxide-based catalysts containing Ni or Co can be used.

[0004] US 2005 / 212153 A1 relates to a ceramic packing element suitable for use as a bed limiter, the packing element having a substantially uniform cross section in the length direction, having a basic bow-tie shape, and having a plurality of through channels parallel to the length dimension.

[0005] WO 2010 / 029324 A1 relates to a catalyst unit comprising a cylinder having five holes arranged in a pentagonal pattern and five riffles.

[0006] WO 2010 / 029323 A1 relates to a catalyst unit in the form of a cylinder having a length of C and a diameter of D, having one or more pores extending therethrough, wherein the cylinder has domed ends of lengths A and B, such that (A + B + C) / D is in the range of 0.50 to 2.00, and (A + B) / C is in the range of 0.40 to 5.00.

[0007] US 2006 / 0204414 A1 relates to a system for processing one or more flowing materials. The system includes a housing and a support bed within the housing, the support bed comprising a plurality of support elements.

[0008] WO 2006 / 114320 A1 relates to a cylindrical catalyst component, wherein embossings are provided on the circumferential surface of the catalyst component.

[0009] WO 2022 / 023194 A1 relates to a cylindrical solid molded body having a first bottom surface, a second bottom surface, and a side surface, wherein the solid molded body includes a first number of grooves in the side surface, each groove extending from the first bottom surface to the second bottom surface, and a second number of openings, each opening extending from the first bottom surface to the second bottom surface, wherein the second number of openings is in the range of 2 to 8, the second number of openings is larger than the first number of grooves, and wherein the ratio of the first radius of at least one groove to the second radius of at least one opening is at least 1.15.

[0010] SU957948 relates to catalyst supports for hydrocarbon conversion and can be used in the catalytic conversion of hydrocarbons in the chemical, petrochemical, food, construction and metallurgical industries.

[0011] The geometry of a molded body affects its performance metrics. Typically, the geometry of catalytic solid molded bodies is optimized for only a single performance metric, such as better pressure drop or larger surface area, while other key performance indicators (KPIs), such as mechanical strength and packed bed density, are often neglected. One object of this invention is to provide a solid molded body that provides improvements in at least two KPIs, such as high mechanical strength and low reactor pressure drop, while achieving satisfactory performance in the remaining KPIs, such as large surface area and packed bed density. Therefore, the solid molded body should provide a targeted trade-off among various KPIs.

[0012] This objective is achieved by a cylindrical solid molded body (1) having a first maximum radius (1R) and having a first bottom surface (3), a second bottom surface (5) and a side surface (7). The solid molded body (1) includes a first number of grooves (9) on the side surface (7), each groove extending from the first bottom surface (3) to the second bottom surface (5), and A second number of openings (11), each opening extending from the first bottom surface (3) to the second bottom surface (5), and The second number of openings (11) is larger than the first number of grooves (9). At least one of the grooves (9) has a second maximum radius (9R), and at least one opening (11) has a third maximum radius (11R), wherein the ratio of the second maximum radius (9R) to the third maximum radius (11R) is less than 1.

[0013] A novel geometry has been discovered that offers a good trade-off between the following key performance indicators (1), (2), (3), and (4), with at least (1) and (2) being improved compared to existing technologies: (1) Mechanical strength (2) Pressure drop (3) Packed bed density (4) Specific surface area of ​​the packed bed in the reactor.

[0014] Since a groove is not necessarily a segment of a circle, and an opening is not necessarily circular, the term "maximum radius" is used to specify which radius of the geometry forming the groove and the geometry forming the opening. In the case where the groove is a segment of a circle and / or the opening is circular, the "maximum radius" is the radius of the corresponding circle.

[0015] Preferably, the cross-section of the groove (9) is in the form of a portion of a circle.

[0016] Since the groove in the solid molded body of the present invention exists not in the form of a complete circle or a complete ellipse, but in the form of a part of a circle or a part of an ellipse, the groove has an imaginary center (9C) and an imaginary radius (9R) of its cross-sectional area. The imaginary center of the groove may be located inside or outside the outer wall (outer edge) of the solid molded body, or exactly on the outer wall.

[0017] The solid molded body has a basic cylindrical shape with a first maximum radius (1R), wherein the first bottom surface and the second bottom surface are preferably arranged parallel to each other, especially in the case of a planar bottom surface; and / or are arranged in a mirror image, especially in the case of a curved or dome-shaped bottom surface. The first bottom surface and the second bottom surface are preferably connected by a side surface. The side surface includes a first number of grooves (9) such that the perimeter of the cross-section of the molded body is divided by the grooves, which may also be referred to as corrugated grooves or embossed structures. The grooves preferably have rounded edges.

[0018] The solid molded body further includes a second number of openings (11), which may also be referred to as holes and extend through the solid molded body from the first bottom surface to the second bottom surface. The first number refers to grooves, and the second number refers to openings. In a cross-sectional view, the circumference of the openings is completely surrounded by the molded body, while in contrast, the grooves are located only on the outer circumference of the solid molded body and are concave portions of the circumference of the solid molded body.

[0019] The terms “extending from the first bottom surface (3) to the second bottom surface (5)”, “extending through the solid molded body from the first bottom surface to the second bottom surface”, and “extending from the first bottom surface 3 to the second bottom surface 5 of the solid molded body 1” cover solid molded bodies 1 with and without domes. It should be understood that the opening 11 and the groove 9 extend through the entire solid molded body, from top to bottom.

[0020] The solid molded body of the present invention has a cylindrical shape.

[0021] Therefore, the solid molded body is a cylinder composed of two congruent circles in parallel planes (first and second bottom surfaces (without a dome)).

[0022] The first maximum radius is the radius of each base. The height (altitude) is the perpendicular line segment from the plane of one base to the plane of another base, and the height of the cylinder without a dome is the length of this height.

[0023] The central axis (1C) is a line segment that includes the centers of the two bases. The central axis is perpendicular to the plane of the two bases.

[0024] Preferably, the longitudinal axes of the solid molded body, the groove, and / or the opening, more preferably the central axis, are arranged parallel to each other. The term "parallel" is understood to mean that the included angle formed by the longitudinal axes (more preferably the central axis) of the solid molded body, the groove, and / or the opening is less than 20°, preferably less than 10°, more preferably less than 5°, and most preferably less than 2°.

[0025] The solid molded body includes more openings than grooves. In particular, the difference between the second number of openings and the first number of grooves is exactly 1, so the solid molded body preferably includes one more opening than grooves.

[0026] Preferably, the solid molded body includes at least 5 grooves (9), more preferably 5, 6, 7, 8 or 9 grooves, and more preferably 5 or 6 grooves. The grooves are preferably equidistant from adjacent grooves and from the central axis of the solid molded body.

[0027] The preferred number of openings in the solid molded body is at least 6, preferably 6, 7, 8, 9 or 10, more preferably 6 or 7.

[0028] The ratio between the second maximum radius of the at least one groove and the third maximum radius of the at least one opening is less than 1, preferably 0.25 to 0.99, more preferably 0.40 to 0.95.

[0029] Each opening preferably has a circular or elliptical cross-section, preferably a circular cross-section (i.e., in a circular form). The third maximum radius can be the radius of the circular cross-section or the maximum radius of the elliptical cross-section. An elliptical cross-section is characterized by having a minimum radius and a maximum radius, respectively denoted as the radial (minimum) radius and the tangential (maximum) radius relative to the center of the solid molded body. The third maximum radius of the at least one opening refers to the tangential radius (maximum radius) of the elliptical cross-section.

[0030] The smaller radius of the ellipse may extend in the radial or tangential direction of the reference solid molded body. The ratio between the tangential radius and the radial radius of the elliptical cross-section of at least one peripheral opening is preferably in the range of 0.2 to 1.7, more preferably in the range of 0.3 to 1.6.

[0031] The third maximum radius of the at least one opening is preferably in the range of 0.5 mm to 2.5 mm, more preferably in the range of 0.8 mm to 2 mm.

[0032] The maximum radius (sixth maximum radius) of at least one peripheral opening is preferably in the range of 0.5 mm to 2.5 mm, more preferably in the range of 0.8 mm to 2.0 mm. Most preferably, all peripheral openings have the same sixth maximum radius, and even more preferably, all peripheral openings have a circular cross-section, and the maximum radius is the radius of that circle.

[0033] The central opening has a seventh maximum radius, which is preferably equal to or greater than at least one sixth maximum radius of the at least one peripheral opening. More preferably, the seventh maximum radius is equal to or greater than all sixth maximum radii of all peripheral openings. The maximum radius of the central opening (seventh maximum radius) is preferably in the range of 0.5 mm to 2.5 mm, more preferably in the range of 0.8 mm to 2.0 mm, provided that the seventh maximum radius is preferably equal to or greater than at least one sixth maximum radius of the at least one peripheral opening.

[0034] The central opening preferably has a circular cross-section. The at least one peripheral opening preferably has a circular cross-section.

[0035] Preferably, the second number of openings (11) includes a central opening (21) and at least one peripheral opening (23). The central opening (21) preferably has a circular cross-section, and / or the at least one peripheral opening (23) preferably has a circular cross-section.

[0036] Preferably, the at least one peripheral opening (23) has a sixth maximum radius (23R), and the sixth maximum radius (23R) of all such peripheral openings (23) is equal, and the central opening (21) has a seventh maximum radius (21R), and the seventh maximum radius (21R) is preferably equal to or greater than the sixth maximum radius (23R) of the at least one peripheral opening (23).

[0037] Each groove preferably has a cross-section that is part of an ellipse or a circle, more preferably a circle. The second maximum radius can be the radius of a circular cross-section or the maximum radius of an elliptical cross-section. The second maximum radius of the at least one opening refers to the tangential radius (maximum radius) of the elliptical cross-section. Preferably, at least one groove, more preferably, all grooves have a cross-section that is part of a circle.

[0038] The second maximum radius of the at least one groove is preferably in the range of 0.4 mm to 2.8 mm, more preferably in the range of 0.5 mm to 2.5 mm.

[0039] Preferably, the second number of openings includes a central opening and at least one peripheral opening. In this case, the second number of openings is the sum of the number of peripheral openings and the central opening. The circumference of the at least one peripheral opening is still completely contained within and surrounded by the solid molded body. The central opening includes a first center and preferably extends along the central axis of the solid molded body. In particular, the first center is located on the central axis of the solid molded body. The center should be understood as the geometric center. The potential offset between the first center of the central opening and the central axis of the solid molded body is less than the offset between the second center of the peripheral opening and the central axis of the solid molded body.

[0040] Preferably, with reference to the centers of the central opening and the peripheral openings, the peripheral openings are equidistant from adjacent peripheral openings and equidistant from the central opening.

[0041] Preferably, the central opening has a circular cross-section. More preferably, the at least one peripheral opening has a circular cross-section. More preferably, all openings have a circular cross-section.

[0042] Preferably, the first number of grooves equals the third number of peripheral openings. More preferably, each at least one peripheral opening is disposed between two grooves. Accordingly, the peripheral openings and grooves are each preferably disposed in separate sections of the circular cross-section of the solid molded body. A section with peripheral openings but no grooves may also be referred to as a lobe. Preferably, one lobe is disposed between two grooves, and one groove is disposed between two lobes. Thus, the grooves and lobes are preferably disposed alternately on the circumference of the solid molded body, and therefore on its sides.

[0043] Preferably, the solid molded body includes a fourth number of lobes on its side surface, each lobe extending from a first bottom surface of the solid molded body to a second bottom surface and disposed between two grooves, wherein the at least one lobe having a cross-section in the form of a portion of a circle has a fourth radius, wherein the fourth radius is equal to the first maximum radius of the solid molded body.

[0044] The at least one leaflet preferably has two rounded corners, wherein the two rounded corners preferably have a cross-section in the form of a portion of a circle with a fifth radius, and the ratio between the second maximum radius of at least one groove and the fifth radius of at least one rounded corner is preferably greater than 0.2, more preferably greater than 0.25, and most preferably greater than 0.3.

[0045] The solid molded body preferably has a maximum diameter and a maximum height, and the ratio between the maximum diameter and the maximum height is preferably 0.4 to 3.0, more preferably 0.5 to 2.8, and more preferably 0.6 to 2.6.

[0046] Since the height of a solid molded body is not necessarily uniform (it can be, for example, dome-shaped), the term "maximum height" (1Hmax) is used to specify which height of the solid molded body it refers to.

[0047] As understood in this application, the “height” (1H) of a solid molded body refers to the distance between the first bottom surface (3) and the second bottom surface (5) without a dome (flat bottom surface). In the absence of a dome, the “maximum height” is the same as the height of the solid molded body. However, in the case where the solid molded body is domed (i.e., the solid molded body includes one or two domes), the “maximum height” of the solid molded body is the height of the solid molded body with a dome (i.e., the solid molded body containing one or two domes).

[0048] Furthermore, in the solid molded body, the ratio between the second maximum radius of at least one groove and the maximum diameter of the solid molded body is preferably 0.02 to 0.7, more preferably 0.03 to 0.6, and even more preferably 0.04 to 0.5. Preferably, all grooves have the same maximum radius, referred to as the second maximum radius.

[0049] Preferably, the solid molded body according to the invention is symmetrical.

[0050] An object is symmetrical in the sense of this invention if it can be transformed into a position indistinguishable from its initial position through geometric operations, namely symmetry operations (covering operations).

[0051] In a preferred embodiment, the central axis of the solid molded body is a 3, 4, 5, 6, 7, 8 or 9-fold rotation axis, preferably a 4, 5 or 6-fold rotation axis.

[0052] If n coincidences are achieved during a 360° rotation, or if the minimum rotation angle required to achieve coincidence is 360° / n, then this is an axis with a count of n (an n-fold rotation axis).

[0053] In another preferred embodiment, the solid molded body includes 3, 4, 5, 6, 7, 8 or 9 mirror planes containing a central axis, preferably including 4, 5 or 6 mirror planes containing a central axis.

[0054] A mirror plane divides an object in two, making it appear like an image and its reflection.

[0055] In a further preferred embodiment, the central axis of the solid molded body is a 4- or 6-axis rotation and includes 4 or 6 mirror planes containing the central axis.

[0056] In another preferred embodiment, the solid molded body includes a mirror plane parallel to the first bottom surface and the second bottom surface (i.e., perpendicular to the central axis).

[0057] Preferably, the ratio between (the first distance from the first center of the central opening (i.e., the central axis (1C) of the solid molded body) to the second center (23C) of at least one peripheral opening) and (the maximum diameter of the solid molded body) is in the range of 0.10 to 0.50, more preferably 0.15 to 0.45, and most preferably 0.20 to 0.40.

[0058] The first distance from the first center of the central opening (particularly from the central axis of the solid molded body) to the second center of the at least one peripheral opening is preferably in the range of 1.5 to 10.0 mm, more preferably in the range of 2.5 to 8.0 mm, and most preferably in the range of 3.0 to 6.0 mm.

[0059] The maximum diameter of the solid molded body is preferably in the range of 6 to 22 mm, more preferably in the range of 7 to 20 mm, and most preferably in the range of 8 to 18 mm.

[0060] In a preferred embodiment, the solid molded body has an outer edge, and the openings are separated from each other by walls with a thickness of at least 0.8 mm (preferably 0.8 to 4 mm, more preferably 1 to 3 mm) and separated from the outer edge of the solid molded body; and the grooves and openings are separated from each other by walls with a thickness of at least 0.8 mm (preferably 0.8 to 4 mm, more preferably 1 to 3 mm).

[0061] Preferably, in the solid molded article of the present invention, The following ratios: The ratio of (the distance from the first center (1C) of the central opening to the second center (23C) of the peripheral openings) to (the sum of the maximum radius (21R) of the central opening and the maximum radius (23R) of the peripheral openings). Greater than 1 (wall 1 (1W)); and The following ratios: The ratio of (the first maximum radius (1R) of the solid molded body) to (the sum of the distance from the first center (1C) of the central opening to the second center (23C) of the peripheral opening and the second maximum radius of the peripheral opening) Greater than 1 (wall 4 (4W)); and The following ratios: The ratio of (the distance from the second center (23C) of the peripheral opening to the center (9C) of the adjacent groove) to (the sum of the maximum radii of the groove and the peripheral opening). Greater than 1 (wall 3 (3W)).

[0062] More preferably, in the solid molded article of the present invention, The following ratios: The ratio of (the distance from the second center (23C) of the peripheral opening to the second center (23C) of the adjacent peripheral opening) to (the sum of the maximum radii of the two peripheral openings). Greater than 1 (wall 2 (2W)).

[0063] In the description of the walls between the openings in the solid molded body according to the invention, different distances are mentioned: Distance 1 (D1): The distance from the first center (1C) of the central opening to the second center (23C) of the peripheral openings.

[0064] Distance 2 (D2): The distance from the second center (23C) of the peripheral opening to the second center (23C) of the adjacent peripheral opening.

[0065] Distance 3 (D3): The distance from the second center (23C) of the peripheral opening to the center (9C) of the adjacent groove.

[0066] Distance 4 (D4): The distance from the first center (1C) of the central opening to the second center (23C) of the peripheral opening is the sum of the second maximum radius of the peripheral opening (i.e., D1 plus the second maximum radius of the peripheral opening).

[0067] Preferably, the ratio between the maximum diameter of the solid molded body and the height of the solid molded body (1H, without a dome) is in the range of 0.4 to 3, more preferably in the range of 0.5 to 2.8, and most preferably in the range of 0.6 to 2.6.

[0068] Preferably, the height (1H, without dome) of the solid molded body is in the range of 4 to 16 mm, more preferably in the range of 5 to 14 mm.

[0069] Furthermore, the side of the solid molded body can be divided into a straight part and two inclined parts, wherein the straight part (e.g., in the form of a ring) is preferably located between the two inclined parts. The surface of the straight part is more preferably oriented parallel to the central axis of the solid molded body.

[0070] The flat portion of the side surface (also referred to as a slit) has a slit length. In this embodiment, the ratio between the slit length and the maximum height of the solid molded body is preferably up to 1. More preferably, the slit length is in the range of 4 mm to 16 mm, and even more preferably in the range of 5 mm to 14 mm. In particular, the flat portion of the side surface represents the maximum diameter of the solid molded body.

[0071] When there is an inclined portion on the side, the inclined portion of the side is preferably inclined from the flat portion toward the central axis of the solid molded body. Preferably, the inclined portion is inclined at a certain angle, which may also be called the pitch angle, and is in the range of 0.1° to 5.0°, more preferably in the range of 1.0° to 4.0°.

[0072] The first and / or second bottom surfaces of the solid molded article are dome-shaped or dome-less, preferably dome-shaped. More preferably, the first and second bottom surfaces are dome-shaped.

[0073] Specifically, the ratio between the maximum total height of the two domes and the height (1H) of the solid molded body (1) (without domes) is in the range of 0.05 to < 0.40.

[0074] Furthermore, the ratio between the maximum height of a dome and the height (1H) of the solid molded body (1) (without a dome) is in the range of 0.01 to 0.195.

[0075] Preferably, the maximum height of each dome is independently within the range of 0.01 to 3 mm, more preferably within the range of 0.1 to 2 mm. More preferably, the maximum height of the two domes is the same.

[0076] The dome is understood as the top and bottom portions of a solid molded body, the surfaces of which are curved in two directions. Accordingly, the height of the dome, and thus the dome height, ends at a position where the sides are curved in only one direction (referring to the radial direction of the solid molded body).

[0077] The solid molded body according to the invention provides a good trade-off between key performance indicators such as mechanical strength (1), pressure drop (2), packed bed density (3) and packed bed specific surface area (4) in the reactor, wherein at least (1) and (2) are improved compared with the prior art.

[0078] The solid molded article according to the invention is preferably characterized in that its minimum side crushing strength is at least 60 N, preferably at least 80 N, as determined in Reference Example 1 of WO 2020 / 157202 A1.

[0079] The present invention also relates to the use of the solid molded body according to the invention as a catalyst, preferably for hydrotreating, hydrogenation, reforming, catalytic partial oxidation, water-gas shift reaction, methanation, hydrocarbon synthesis via Fischer-Tropsch reaction, methanol synthesis, ammonia synthesis, ammonia conversion (e.g., ammonia reforming to produce hydrogen and nitrogen), or ammonia oxidation and nitrous oxide decomposition reactions, or for the recovery of heavy metals (such as mercury and arsenic) from contaminated gaseous or liquid fluid streams, more preferably for reforming.

[0080] Furthermore, the present invention relates to a method comprising contacting a mixture of reactants with a solid molded body according to the invention, wherein the method is preferably selected from hydrogenation treatment, hydrogenation, reforming, catalytic partial oxidation, water-gas shift reaction, methanation, hydrocarbon synthesis via Fischer-Tropsch reaction, methanol synthesis, ammonia synthesis, ammonia oxidation and nitrous oxide decomposition reaction, and recovery of heavy metals (such as mercury and arsenic) from contaminated gaseous or liquid fluid streams, more preferably selected from reforming.

[0081] Reforming in the sense of this invention, particularly steam reforming of hydrocarbons, includes pre-reforming, catalytic steam reforming, autothermal reforming, and secondary reforming, ammonia reforming to N2 and H2, and hydrocarbon steam reforming with ammonia and / or carbon dioxide as co-feeds. Most preferably, hydrocarbons or hydrocarbon mixtures (e.g., natural gas, light gasoline, methanol, biogas, or biomass) are steam reformed to syngas containing hydrogen and carbon monoxide, preferably with ammonia and / or carbon dioxide as co-feeds; or ammonia is reformed to nitrogen and hydrogen. The hydrocarbons or hydrocarbon mixtures in the steam reforming preferably contain hydrocarbons selected from the group consisting of methane, ethane, propane, and butane, with methane being more preferably included in the hydrocarbons or hydrocarbon mixtures.

[0082] The water-gas shift reaction in this invention preferably includes isothermal shift, sulfur-containing shift, low-temperature shift, medium-temperature shift, and high-temperature shift reactions. It also includes a reverse reaction, where CO2 reacts with hydrogen to produce CO and water. This so-called reverse water-gas shift reaction can be carried out at temperatures ranging from a low to a high of 300°C to a high of 1000°C.

[0083] Hydrotreating in this invention refers to the reaction of oil fractions with hydrogen. Hydrotreating includes hydrotreating and hydrocracking.

[0084] Hydrorefining encompasses the removal of contaminants and the upgrading of oil fractions. The contaminants typically referred to are sulfur, nitrogen, oxygenated compounds, metals, and aromatics. For example, hydrorefining is used to produce low-sulfur fuels to reduce emissions, because removing sulfur (S) reduces SOx emissions during fuel combustion.

[0085] In hydrocracking, heavier oil fractions are converted into lighter oil fractions.

[0086] The above methods are known to those skilled in the art.

[0087] The solid molded article according to the invention preferably comprises at least one metal compound selected from at least one metal oxide, metal hydroxide, metal carbonate, metal hydroxycarbonate, and mixtures thereof; and / or at least one metal. Preferably, the solid molded article comprises at least one metal oxide, or at least one metal oxide and at least one metal. More preferably, the solid molded article comprises at least aluminum and oxygen, preferably aluminum, oxygen, and at least one further metal.

[0088] More preferably, the solid molded article comprises a mixed oxide. As understood in this application, a mixed oxide refers to an oxide comprising one or more metals, or an oxide comprising one or more oxidation states of a single element. Preferably, the mixed oxide comprises oxygen, aluminum, and at least one further metal. More preferably, the mixed oxide comprises oxygen, aluminum, and at least one alkaline earth metal (e.g., magnesium).

[0089] In another preferred embodiment, in addition to a mixed oxide comprising oxygen, aluminum and at least one alkaline earth metal (such as magnesium), the solid molded body also comprises at least one of nickel and ruthenium and an alkali metal (such as potassium).

[0090] In another preferred embodiment, the solid molded body according to the invention comprises a mixed oxide, wherein the mixed oxide comprises oxygen, aluminum, cobalt and at least one element selected from rare earth metals (such as lanthanum) and optionally alkaline earth metals (such as strontium or barium).

[0091] Preferably, the solid molded article comprises a mixed oxide from 50 wt% to 100 wt%, more preferably from 60 wt% to 100 wt%, even more preferably from 70 wt% to 100 wt%, further preferably from 80 wt% to 100 wt%, particularly from 90 wt% to 100 wt%, especially preferably from 95 wt% to 100 wt%, and most preferably from 99 wt% to 100 wt%, and optionally comprises at least one suitable binder. Even more preferably, the solid molded article comprises a mixed oxide from 99.5 wt% to 100 wt%, and most preferably from 99.9 wt% to 100 wt%. In a further preferred embodiment, the solid molded article is composed of a mixed oxide. Suitable and preferred mixed oxides are mentioned above and below.

[0092] When the mixed oxide contains nickel, it preferably comprises at least a nickel-magnesium mixed oxide and magnesium spinel, and aluminum is preferably in the form of aluminum hydroxide. The nickel-magnesium mixed oxide preferably has an average crystallite size of ≤ 100 nm, more preferably ≤ 70 nm, and even more preferably ≤ 50 nm. The magnesium spinel phase preferably has an average crystallite size of ≤ 100 nm, more preferably ≤ 70 nm, and even more preferably ≤ 50 nm. The proportion of nickel in the mixed oxide is preferably around 30 mol-%, more preferably in the range of 6 mol-% to 30 mol-%, the proportion of magnesium is preferably in the range of 8 mol-% to 38 mol-%, more preferably 23 mol-% to 35 mol-%, and the proportion of aluminum is preferably in the range of 50 mol-% to 70 mol-%.

[0093] The solid molded body can be prepared, for example, as described in WO 2013 / 068905, especially when the solid molded body contains a nickel-containing mixed oxide.

[0094] When the mixed oxide contains cobalt, the weight ratio of cobalt to aluminum in the mixed oxide, calculated by element, is preferably at least 0.17:1.

[0095] There are no specific restrictions on the content of cobalt, rare earth metals (such as lanthanum), and aluminum in the mixed oxides contained in solid molded articles.

[0096] This solid molded body can generally be produced by any method known in the art, such as that described in WO 2022 / 023194.

[0097] Preferably, the solid molded body is a calcined solid molded body, wherein the calcination is carried out in a gaseous atmosphere, the temperature of which is typically in the range of 600°C to 1400°C, more preferably in the range of 700°C to 1300°C, wherein the gaseous atmosphere preferably contains oxygen, such as one or more of oxygen, air, or air-lean. Preferably, the calcination is carried out for 2 hours to 20 hours. Attached Figure Description

[0098] The present invention is described in more detail in the accompanying drawings, wherein: Figure 1 A top view of a preferred embodiment of a solid molded body having a cylindrical shape and including seven openings and six grooves is shown.

[0099] Figure 2 A longitudinal section of a solid molded body with a cylindrical shape is shown.

[0100] Figure 3A side view of a solid molded body according to a first embodiment of a solid molded body having a cylindrical shape and including four grooves and five openings is shown.

[0101] Figure 1 A top view of a preferred embodiment of a solid molded body 1 having a cylindrical shape and comprising six grooves 9 and seven openings 11 is shown. The grooves 9 are located on the side surface 7 of the solid molded body 1. Furthermore, the grooves 9 and the openings 11 extend from a first bottom surface 3 of the solid molded body 1 to a second bottom surface 5. In the preferred embodiment shown herein, the grooves 9 are equidistant from each other and have a second maximum radius 9R, which is smaller than the third maximum radius 11R of at least one opening 11.

[0102] These seven openings 11 include a central opening 21 and six peripheral openings 23. In the preferred embodiment shown herein, each peripheral opening 23 is disposed between two recesses 9, and vice versa. Two adjacent recesses 9 are separated from each other by lobes 37. Therefore, according to Figure 1 The solid molded body 1 of the preferred embodiment shown includes six leaflets 37.

[0103] exist Figure 1 In the preferred embodiment shown, each peripheral opening 23 is located within one of the leaflets 37. The peripheral opening 23 has a circular cross-section, therefore the sixth maximum radius 23R is the radius of the opening.

[0104] The center opening 21 has a seventh maximum radius 21R. Figure 1 In the preferred embodiment shown, the central opening 21 has a circular cross-section, therefore the seventh maximum radius 21R is the radius of the opening. Furthermore, the central opening 21 has a first center 1C located on the central axis 1C of the solid molded body 1, and the peripheral openings 23 have a second center 23C. Figure 1 In the preferred embodiment shown, the first distance between the first center 1C of the solid molded body 1 and the second center 23C of the peripheral opening 23 is represented by the radius of a circle, on which the second center 23C of the peripheral opening 23 is located.

[0105] In addition, Figure 1 In the preferred embodiment shown, the first maximum diameter 1D of the solid molded body is represented by the radius of a circle on which the third center 9C of the groove 9 is located. Each third center 9C refers to an imaginary circle, an arc segment of which forms one of the grooves 9.

[0106] Figure 2 A longitudinal section of a preferred cylindrical solid molded body 1 is shown. The solid molded body 1 includes a first bottom surface 3 and a second bottom surface 5, which are connected by a side surface 7. The side surface 7 includes a slit 6 and an angle 8. Figure 1In an exemplary embodiment, the first bottom surface 3 and the second bottom surface 5 are dome-shaped, with a dome height 36. The solid molded body 1 has a maximum height 1Hmax including the two domes, a height 1H without the two domes, and a diameter 1D.

[0107] Figure 3 A side view of a preferred solid molded body 1 is shown, which is cylindrical and includes six grooves 9 and seven openings 11. The grooves 9 are located on the side surface 7 of the solid molded body 1. Furthermore, the grooves 9 and openings 11 extend from a first bottom surface 3 to a second bottom surface 5 of the solid molded body 1. Figure 3 In an exemplary embodiment, the first bottom surface 3 and the second bottom surface 5 are dome-shaped, with a dome height of 36. The solid molded body 1 has a maximum height 1Hmax including the two domes and a height 1H without the two domes.

[0108] Examples and Comparisons

[0109] The given reference numbers refer to respectively Figure 1 , 2 And 3.

[0110] Description of geometric structure

[0111] All parametric geometries described herein were created using computer-aided design (CAD) or an automated 3D finite element mesh generator. Table 1 shows parametric examples of the present invention (B) and comparative examples (A).

[0112] Table 1 - Examples of parametric geometries, dimensions in mm.

[0113]

[0114] Comparison of geometric structural characteristics

[0115] experiment: (a) CFD simulation: Pressure drop simulation The correlation between pressure drop and catalyst shape was calculated using numerical flow simulation, which fully analyzes the flow within the catalyst bed. The procedure comprises three consecutive steps. First, the bed geometry is created. For this, a CAD (computer-aided design) model of the individual shaped catalyst body is created using any CAD program. This determines the catalyst shape (e.g., cylindrical, annular, trilobal, etc.). A tube with an internal diameter typical of industrial reactors (approximately 100 mm) serves as the external container for the bulk material. Both the digital container geometry and the digital catalyst geometry are input into the simulation program, which uses Newton's equations of motion to calculate the setup when the shaped catalyst body is filled into the container. Pressure drop calculations are performed using air at ambient temperature and varying gas hourly space velocities (GHSV). The thermodynamic and transport properties of the gas are derived from air data obtained from scientific literature at a constant operating pressure of 1 bar and a temperature of 20°C. The calculated pressure drop characteristics can be transferred to actual operating conditions using dimensionless numbers.

[0116] Simulation of geometric surface area and geometric volume

[0117] Create a CAD (computer-aided design) model of a single molded catalyst body using any CAD program to calculate the geometric surface area and geometric volume.

[0118] Simulation of lateral pressure intensity

[0119] Create a CAD (Computer-Aided Design) model of a single molded catalyst body using any CAD program to calculate the lateral compressive strength of that body. Use numerical methods (such as finite element analysis) to simulate the lateral compressive strength test.

[0120] Table 2 shows the calculated values ​​for Example B of the present invention and Comparative Example A.

[0121] Table 2

[0122] Compared to the comparative solid molded body A, the solid molded body (B) of the present invention exhibits improved minimum compressive strength and improved pressure drop, while other parameters such as packed bed density and specific surface area are comparable.

[0123] Comparison Examples

[0124] Catalysts containing cobalt were prepared by following the methods for preparing extrudates and pellets as described in Example 2 of PCT / EP2023 / 068006 and Example 1 of WO 2020 / 157202, respectively.

[0125] 30.7 kg of aqueous AlOOH (Disperal; Sasol; containing 77.9 wt% Al, calculated as Al2O3), 5.5 kg of cobalt(II) carbonate hydrate (containing 46 wt% Co; Umicore, Todini)), and 16.1 kg of lanthanum(III) carbonate hydrate (containing 39.3 wt% La; Inner Mongolia Baogang Rare Earth International Trade Co., Ltd.) were premixed in a kneader for several minutes. Then, 23 kg of aqueous formic acid (containing 37 wt% formic acid; based on 98-100 wt% formic acid, BASF SE) was added under mixing and a uniform pink dough-like mass was formed.

[0126] The kneaded agglomerates were then shaped into 6 mm ropes. The ropes were dried at 95°C–120°C for 10 h, followed by calcination at 400°C–440°C for 4 h. The calcined extrudate was then ground. The material was then sieved using a 1 mm mesh. The sieved powder (83 wt% (0.3–1 mm fraction) + 17 wt% (< 0.3 mm fraction)) was then mixed with 3 wt% graphite (Asbury Graphite 3160) and 3 wt% microcrystalline cellulose (Vivapur SCG102). The resulting mixture was compressed into tablets having a four-hole cross-section as shown in WO 2020 / 157202.

[0127] For firing, the molded part is heated to 700°C over 3 hours and held at that temperature for 1 hour. The molded part is then further heated to a temperature in the range of 1170°C to 1200°C and held within this range for 4 hours. Firing is carried out in an annealing furnace.

[0128] The calcined molded parts contained 7.2 wt% cobalt, 18.6 wt% lanthanum, and 36 wt% aluminum, respectively, calculated elementally. The minimum compressive strength was characterized for the 10 molded part samples finally calcined in Example 1. The results are listed below. In addition, the diameter, height, and mass of each sample are also listed.

[0129] Examples of the present invention

[0130] The cobalt-containing catalyst was prepared according to the method described in the comparative example, but with a novel six-lobed geometry.

[0131] The detailed tableting steps of the catalyst tableting process in the examples and comparative examples of this invention were performed on a Korsch E150+ tablet press. For two different geometries, tableting was performed at a constant tool main compression / cross-sectional area of ​​0.32 kN / mm². 2The following will proceed.

[0132] result: Table 3. Physical properties of particles calcined at 1200°C

[0133] The minimum lateral compressive strength of the final molded body was determined experimentally using a commercial material testing machine (model BZ2.5 / TS1S) manufactured by Zwick, which allows for the testing of mechanical properties according to DIN EN ISO 7500-1:2018-06. Ten independent solid molded bodies were studied for each type. The analytical methods applied included a preload of 0.5 N and a preload speed of 10 mm / min. The analysis speed was 1.6 mm / min.

[0134] The diameter and height of a single solid molded object are measured using calipers. The weight of the solid molded object is measured using an analytical balance. Typically, 10 molded objects are analyzed and their average value is considered.

[0135] Pressure drop was measured in a flow reactor at ambient temperature and pressure. Air was used as the gas mixture. Catalyst particles were packed to a height of 400 mm in a 100 mm inner diameter tube. The air flow rate was gradually varied between 0 and 150 Nm³ / h.

[0136] Compared to existing technologies, the shape of this invention exhibits improved minimum lateral pressure strength and improved pressure drop. The packed bed density is comparable.

[0137] Reference number

[0138] 1 Solid molded body

[0139] 1R is the first maximum radius of the solid molded body.

[0140] 3 First bottom surface

[0141] 5 Second bottom surface

[0142] 7. Side view

[0143] 9 grooves

[0144] 11. Opening

[0145] The second maximum radius of the 9R groove

[0146] The second largest diameter of the 9D groove

[0147] The third maximum radius of the 11R opening

[0148] The third largest diameter of the 11D aperture

[0149] 21 Center opening

[0150] 23 Peripheral openings

[0151] 1C Central axis = First center of the central opening

[0152] 37 leaf petals

[0153] The fourth radius of the 37R leaflet

[0154] 38 Rounded corners

[0155] 38R is the fifth radius of the fillet.

[0156] The first maximum diameter of a 1D solid molded body

[0157] 1Hmax is the maximum height of the solid molded body.

[0158] The sixth maximum radius of the 23R peripheral opening

[0159] The sixth largest diameter of the 23D peripheral opening

[0160] The seventh maximum radius of the center opening of 21R

[0161] The seventh largest diameter of the 21D center opening

[0162] 35. Maximum height of the two domes

[0163] 36. The maximum height of a dome

[0164] 1H is the height of the solid molded body without a dome.

[0165] The second center of the 23C peripheral opening

[0166] The third center of the 9C groove

[0167] 6. Slit

[0168] 8 Inclination

[0169] 1W wall 1

[0170] 2W wall 2

[0171] 3W wall 3

[0172] 4W wall 4.

Claims

1. A cylindrical solid molded body (1) having a first maximum radius (1R) and having a first bottom surface (3), a second bottom surface (5) and a side surface (7). The solid molded body (1) includes a first number of grooves (9) on the side surface (7), each groove extending from the first bottom surface (3) to the second bottom surface (5), and A second number of openings (11), each opening extending from the first bottom surface (3) to the second bottom surface (5), and The second number of openings (11) is larger than the first number of grooves (9). At least one of the grooves (9) has a second maximum radius (9R), and at least one opening (11) has a third maximum radius (11R), wherein the ratio of the second maximum radius (9R) to the third maximum radius (11R) is less than 1.

2. The solid molded body (1) according to claim 1, wherein, These grooves (9) have a cross-section that is part of a circle.

3. The solid molded body (1) according to claim 1 or 2, wherein, The second number of openings (11) includes a central opening (21) and at least one peripheral opening (23). The central opening (21) preferably has a circular cross-section, and / or the at least one peripheral opening (23) preferably has a circular cross-section.

4. The solid molded article (1) according to any one of claims 1 to 3, wherein, The solid molded body is symmetrical. Preferably, the solid molded body (1) includes a central axis (1C), wherein the central axis of the solid molded body is a 3, 4, 5, 6, 7, 8 or 9 rotation axis.

5. The solid molded article (1) according to any one of claims 1 to 4, wherein, The solid molded body (1) includes a fourth number of lobes (37) on the side (7), each lobe extending from the first bottom surface (3) of the solid molded body to the second bottom surface (5) and disposed between two grooves, wherein at least one lobe (37) having a cross section in the form of a partial circle has a fourth radius (37R), wherein the fourth radius (37R) is equal to the first radius (1R) of the solid molded body (1).

6. The solid molded body (1) according to claim 5, wherein at least one leaflet (37) has two rounded corners (38), wherein the two rounded corners (38) preferably have a cross section in the form of a portion of a circle having a fifth radius (38R), and the ratio of the second maximum radius (9R) of the at least one groove (9) to the fifth radius (38R) of the at least one rounded corner (38) is greater than 0.

2.

7. The solid molded article (1) according to any one of claims 1 to 6, wherein, The solid molded body (1) includes at least 5 grooves (9), preferably 5, 6, 7, 8 or 9 grooves (9), more preferably 5 or 6 grooves (9).

8. The solid molded article (1) according to any one of claims 1 to 7, wherein, The solid molded body has a maximum diameter (1D) and a maximum height (1Hmax), and the ratio of the maximum diameter (1D) to the maximum height (1Hmax) is between 0.4 and 3.

0.

9. The solid molded article (1) according to any one of claims 3 to 8, wherein, The at least one peripheral opening (23) has a sixth maximum radius (23R), and the sixth maximum radius (23R) of all such peripheral openings (23) is equal, and the central opening (21) has a seventh maximum radius (21R), and the seventh maximum radius (21R) is preferably equal to or greater than the sixth maximum radius (23R) of the at least one peripheral opening (23).

10. The solid molded article (1) according to any one of claims 3 to 9, wherein, The first number of grooves (9) is equal to the third number of peripheral openings (23).

11. The solid molded article (1) according to any one of claims 3 to 10, wherein, Each of the at least one peripheral opening (23) is disposed between the two grooves (9).

12. The solid molded article (1) according to any one of claims 1 to 11, wherein, The first bottom surface (3) and / or the second bottom surface (5) are dome-shaped.

13. The solid molded body (1) according to claim 12, wherein it is dome-shaped at the first bottom surface (3) and the second bottom surface (5), wherein, The ratio of the sum of the maximum heights (35) of the two domes to the height (1H) of the solid molded body (1) without domes is in the range of 0.05 to < 0.

40.

14. The solid molded article (1) according to any one of claims 1 to 13, wherein, The solid molded body (1) comprises at least one metal compound selected from at least one metal oxide, metal hydroxide, metal carbonate, metal hydroxy carbonate and mixtures thereof; and / or at least one metal.

15. A method comprising contacting a mixture of reactants with a solid molded body (1) according to any one of claims 1 to 14, wherein, The method is preferably selected from hydrotreating, hydrogenation, reforming, catalytic partial oxidation, water-gas shift reaction, methanation, hydrocarbon synthesis via Fischer-Tropsch reaction, methanol synthesis, ammonia synthesis, ammonia conversion, or ammonia oxidation and nitrous oxide decomposition reaction, as well as the recovery of heavy metals such as mercury and arsenic from contaminated gaseous or liquid fluid streams, and more preferably from reforming.

16. Use of the solid molded body (1) according to any one of claims 1 to 14 as a catalyst, preferably for hydrogenation, hydrogenation, reforming, catalytic partial oxidation, water-gas shift reaction, methanation, hydrocarbon synthesis via Fischer-Tropsch reaction, methanol synthesis, ammonia conversion, or ammonia synthesis, ammonia oxidation and nitrous oxide decomposition reaction, or recovery of heavy metals such as mercury and arsenic from contaminated gaseous or liquid fluid streams, more preferably for reforming.

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