Catalyst materials and articles, processes for making them, and catalytic processes using them

Abstract

The present disclosure relates generally to catalyst articles, particularly to flexible catalyst articles, as well as to processes for making them and for using them in catalytic processes such as hydrogen production processes like LPG reforming and ammonia cracking. In one aspect, the disclosure provides a metallic catalytic component comprising: a metallic substrate; and disposed on the metallic substrate, a catalyst material comprising a refractory oxide support, the refractory oxide support. In various advantageous embodiments, the refractory oxide support comprises one or more of rare earth-stabilized alumina, rare earth-stabilized zirconia, silica- stabilized zirconia, rare earth-stabilized titania, and silica-stabilized titania.

Description

Clariant International Ltd 2024US702-WO-PCTCATALYST MATERIALS AND ARTICLES, PROCESSES FOR MAKING THEM, AND CATALYTIC PROCESSES USING THEMBACKGROUND OF THE DISCLOSURE1 . Field

[0001] The present disclosure relates generally to catalyst articles, particularly to flexible catalyst articles, as well as to processes for making them and for using them in catalytic processes such as hydrogen production processes like LPG reforming and ammonia cracking.2. Technical Background

[0002] In the realm of catalysis and emission control technologies, the use of structured catalysts has long been a subject of extensive research and development. Among these structured catalysts, the honeycomb monolith has garnered significant attention for its effectiveness in various applications, particularly in exhaust gas purification. However, recent advancements in reactor design and catalysis have introduced an innovation - the washcoated flexible metallic substrate.

[0003] The flexible metallic substrate represents a novel catalytic support system characterized by its adaptable and flexible nature. Unlike honeycomb monoliths, which are typically based on rigid, honeycomb-shaped structures, the flexible metallic substrate offers remarkable versatility in terms of its form and application. It is characterized by a metallic substrate that is both robust and malleable, allowing for diverse configurations and shapes to accommodate specific catalytic requirements ranging from automotive emissions control to industrial processes.

[0004] Catalysts based on metallic substrates are typically prepared using a technique called “washcoating,” in which a suspension of particulate catalyst material is applied to the metal substrate then dried and calcined to provide a refractory oxide coating, which can be impregnated to provide catalytic metal(s). There are numerous washcoat compositions used forClariant International Ltd 2024US702-WO-PCT rigid metal monoliths made from FeCr-Alloy. Certain common washcoat compositions are based on alumina and contain zirconia-stabilized ceria as an oxygen storage component. Metal monoliths are well suited for exhaust gas catalysis, as they can be directly welded into the exhaust pipe of a vehicle.

[0005] But metal monoliths cannot be easily integrated in existing tubular reactors for chemical processes. If one introduces them into a tubular reactor, there is either a small slit at the border, which can enable bypass, or the use of a ceramic fleece around the metal monolith, which can be a barrier to heat transfer. Accordingly, conventional metal monoliths, while potentially offering a high heat transfer for exothermal or endothermal reactions, cannot be conveniently used in tubular reactors.

[0006] Thus, there is a need for new structured catalyst material, especially flexible substrate materials that are effective at thermal transfer.SUMMARY OF THE DISCLOSURE

[0007] In one aspect, the disclosure provides a metallic catalytic component comprising: a metallic substrate; and disposed on the metallic substrate, a catalyst material comprising a refractory oxide support, the refractory oxide support.

[0008] In another aspect, the disclosure provides a process for preparing a metallic catalytic component as described herein, the method comprising: providing a metallic substrate; providing a suspension of refractory oxide components in a first aqueous liquid; coating the metallic substrate with the suspension to provide a wet coating on the substrate; and drying and calcining the wet-coated substrate to provide a refractory oxide coating on the substrate.Clariant International Ltd 2024US702-WO-PCT

[0009] In another aspect, the disclosure provides a process for installing a metallic catalytic component as described herein in an enclosure, the process comprising flexing the metallic catalytic component to fit through an aperture of the enclosure.

[0010] In another aspect, the disclosure provides a process for reacting a feedstock to provide hydrogen, the process comprising: providing a metallic catalytic component of any of claims 1 -18 and comprising one or more catalytic metals, wherein at least 10 atom% of the catalytic metal(s) is in a metallic form; contacting the metallic catalytic component with a feed stream comprising one or more of C1-C4 alkanes and ammonia and, optionally, water and / or carbon dioxide, at a reaction temperature of at least 500 °C to provide a stream comprising hydrogen.

[0011] Other aspects of the disclosure will be apparent to the person of ordinary skill in the art in view of the discussion herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The accompanying drawings are included to provide a further understanding of the compositions and processes of the disclosure, and are incorporated in and constitute a part of this specification. The drawings are not necessarily to scale, and sizes of various elements may be distorted for clarity. The drawings illustrate one or more embodiment(s) of the disclosure and, together with the description, serve to explain the principles and operation of the disclosure.

[0013] FIG. 1 provides a picture of a holder for setting the shape of a flexible metallic substrate during the coating process.

[0014] FIG. 2 provides a picture of an attrition testing apparatus and method.

[0015] FIG. 3 is a graph that demonstrates the relationship between reaction temperature and methane conversion for an example catalyst material under steam methane reformingClariant International Ltd 2024US702-WO-PCT conditions. In this graph the line lacking data points represents the equilibrium conversion vs. temperatureDETAILED DESCRIPTION

[0016] Reforming and cracking processes, such as steam methane reforming, dry methane reforming, LPG reforming and ammonia cracking, are highly endothermic chemical processes. A considerable amount of heat (e.g., reactor temperature of 700-900 °C) is required to drive such equilibrium processes towards hydrogen production. Heat transfer is problematic when conducting steam methane reforming in conventional packed bed reactors with ceramic pellet catalysts, as the relatively low thermal conductivity of such ceramic materials leads to low heat transfer rate in the reactor. A variety of solutions towards improving heat transfer in reactors have been proposed, including changes to the bed configuration or the heating source.

[0017] The present inventors have noted the use of flexible metal substrates in such systems. One possible implementation of a metallic catalytic component based on a flexible metal substrate is the introduction directly into the tube of a corrugated foil coated with catalyst material. If one folds the corrugated foil, so that it fits into the tube and then unfolds the corrugated foil, so that it is attached to the wall of the tube has a perfect thermal contact to the catalyst coated metal foil.

[0018] But the present inventors have noted that, while such bending of a coated flexible metal substrate can be convenient for installation, it poses an issue with respect to the catalyst material itself: The catalyst material need not only strongly adhere to the substrate to sufficiently to resist breakage or delamination due to thermal expansion during use, it must also be tough enough to resist the much greater, albeit occasional, movement of the folding and unfolding of the corrugated foil during installation.

[0019] Most conventional reforming and cracking catalyst materials are low surface area and highly thermally-stabilized ceramic materials, such as CC-AI2O3 and CaAli2Oig (hibonite). ButClariant International Ltd 2024US702-WO-PCT it can be difficult to coat these ceramic materials on metallic substrates such that they have acceptable and durable adhesion at high temperature reforming and cracking conditions. Therefore, it is desirable to develop new catalyst materials which can be easily coated on metallic substrates, especially flexible metal substrates, to have durable adhesion property in high temperature processes like the endothermal hydrogen production processes described here.

[0020] The present inventors provide here a catalyst composition that can be especially useful in providing metallic catalytic components for use in high-temperature processes and with flexible metal substrates that may be bent, folded, rolled or unrolled, or otherwise significantly deformed during installation. The catalyst compositions described herein can be provided on a variety of substrates, as described in more detail below, including substrates like metal substrates that can have especially high thermal conductivity.

[0021] Accordingly, one aspect of the disclosure provides a catalyst material that comprises a refractory oxide support. In various embodiments, the refractory oxide support comprises one or more of rare earth-stabilized alumina, rare earth-stabilized zirconia, rare earth-stabilized titania, silica-stabilized zirconia and silica-stabilized titania.

[0022] As the person of ordinary skill in the art will appreciate, refractory oxide support will be provided in substantially oxidic form. A small portion of the refractory oxide support can be in other than oxidic form, but the metal atoms of the support will generally be at least 95 atom% oxidic, e.g., at least 99 atom% oxidic.

[0023] Calculations of amounts of components of the refractory oxide support are provided on an oxide basis, i.e., in which all components of the refractory oxide are in their most stable oxide form (e.g., AI2O3, ZrC>2, TiC>2, SiC>2, CeO2, La2Os, Y2O3).

[0024] Aluminum oxide can be a desirable support material. Thus, in various embodiments as described herein, the refractory oxide comprises rare-earth-stabilized alumina. In various embodiments, the refractory oxide support comprises aluminum in an amount of 60-98 wt%,Clariant International Ltd 2024US702-WO-PCT e.g., 65-98 wt%, or 70-98 wt%, or 75-98 wt%, or 80-98 wt%, calculated on an oxide basis. In various embodiments, the refractory oxide support comprises aluminum in an amount of 60-95 wt%, e.g., 65-95 wt%, or 70-95 wt%, or 75-95 wt%, or 80-95 wt%, calculated on an oxide basis. In various embodiments, the refractory oxide support comprises aluminum in an amount of 60- 90 wt%, e.g., 65-90 wt%, or 70-90 wt%, or 75-90 wt%, or 80-90 wt%, calculated on an oxide basis. In various embodiments, the refractory oxide support comprises aluminum in an amount of 60-85 wt%, e.g., 65-85 wt%, or 70-85 wt%, or 75-85 wt%, calculated on an oxide basis.

[0025] Rare earth-stabilized zirconia and / or silica-stabilized zirconia can also be a desirable refractory oxide support material. In various embodiments as otherwise described herein, the refractory oxide support comprises zirconium in an amount of 60-98 wt%, e.g., 65-98 wt%, or 70-98 wt%, or 75-98 wt%, or 80-98 wt%, calculated on an oxide basis. In various embodiments, the refractory oxide support comprises zirconium in an amount of 60-95 wt%, e.g., 65-95 wt%, or 70-95 wt%, or 75-95 wt%, or 80-95 wt%, calculated on an oxide basis. In various embodiments, the refractory oxide support comprises zirconium in an amount of 60-90 wt%, e.g., 65-90 wt%, or 70-90 wt%, or 75-90 wt%, or 80-90 wt%, calculated on an oxide basis. In various embodiments, the refractory oxide support comprises zirconium in an amount of 60-85 wt%, e.g., 65-85 wt%, or 70-85 wt%, or 75-85 wt%, calculated on an oxide basis.

[0026] Rare earth-stabilized titania and / or silica-stabilized titania can also be a desirable refractory oxide support material. In various embodiments as otherwise described herein, the refractory oxide support comprises titanium in an amount of 60-98 wt%, e.g., 65-98 wt%, or 70- 98 wt%, or 75-98 wt%, or 80-98 wt%, calculated on an oxide basis. In various embodiments, the refractory oxide support comprises titanium in an amount of 60-95 wt%, e.g., 65-95 wt%, or 70- 95 wt%, or 75-95 wt%, or 80-95 wt%, calculated on an oxide basis. In various embodiments, the refractory oxide support comprises titanium in an amount of 60-90 wt%, e.g., 65-90 wt%, or 70-90 wt%, or 75-90 wt%, or 80-90 wt%, calculated on an oxide basis. In various embodiments,Clariant International Ltd 2024US702-WO-PCT the refractory oxide support comprises titanium in an amount of 60-85 wt%, e.g., 65-85 wt%, or 70-85 wt%, or 75-85 wt%, calculated on an oxide basis.

[0027] Of course, combinations of two or more of alumina-, zirconia- and titania- based materials can be used. In various embodiments as otherwise described herein, a total amount of aluminum, zirconium and titanium is in the range of 60-98 wt%, e.g., 65-98 wt%, or 70-98 wt%, or 75-98 wt%, or 80-98 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, zirconium and titanium is in the range of 60-95 wt%, e.g., 65-95 wt%, or 70-95 wt%, or 75-95 wt%, or 80-95 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, zirconium and titanium is in the range of 60-90 wt%, e.g., 65-90 wt%, or 70-90 wt%, or 75-90 wt%, or 80-90 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, zirconium and titanium is in the range of 60-85 wt%, e.g., 65-85 wt%, or 70-85 wt%, or 75-85 wt%, calculated on an oxide basis.

[0028] In various embodiments the refractory oxide support comprises one or more rare earths selected from cerium, lanthanum and yttrium.

[0029] For example, in various embodiments, the refractory oxide support comprises cerium. Cerium will typically be present in oxidic form, e.g., as CeO2. It can stabilize against attrition as well as help minimize coke formation during use. For example, in various embodiments as otherwise described herein, in the refractory oxide support cerium is present in an amount of 2-40 wt%, e.g., 2-35 wt%, or 2-30 wt%, or 2-25 wt%, or 2-20 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support cerium is present in an amount 5-40 wt%, e.g., 5-35 wt%, or 5-30 wt%, or 5-25 wt%, or 5-20 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support cerium is present in an amount of 10-40 wt%, e.g., 10-35 wt%, or 10-30 wt%, or 10-25 wt%, or 10-20 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support cerium is present in an amount of 15-40 wt%, e.g., 15-35 wt%, or 15-30 wt%, or 15-25 wt%, calculated on an oxide basis.Clariant International Ltd 2024US702-WO-PCT

[0030] In various embodiments as otherwise described herein, the refractory oxide support comprises lanthanum. Lanthanum can help to enhance phase stabilization of the support and maintain surface area, The lanthanum can be, for example, present in an amount of 0.1 -5 wt%, e.g., 0.1-3 wt%, or 0.1-2 wt%, or 0.1 -1 wt%, or 0.1 -0.5 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support lanthanum is present in an amount of 0.2- 5 wt%, e.g., 0.2-3 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.2-0.7 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support lanthanum is present in an amount of 0.5-5 wt%, e.g., 0.5-3 wt%, or 0.5-2 wt%, or 0.5-1 .2 wt%, or 0.5-1 .2 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support lanthanum is present in an amount of 1 -5 wt%, e.g., 1-3 wt%, or 1 -2 wt%, or 1 -1.5 wt%, calculated on an oxide basis.

[0031] In various embodiments as otherwise described herein, the refractory oxide support comprises yttrium. Yttrium can \ help to enhance phase stabilization of zirconia and to maintain surface area, The yttrium can be, for example, present in an amount of 0.1 -5 wt%, e.g., 0.1 -3 wt%, or 0.1-2 wt%, or 0.1 -1 wt%, or 0.1 -0.5 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support yttrium is present in an amount of 0.2-5 wt%, e.g., 0.2-3 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.2-0.7 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support yttrium is present in an amount of 0.5-5 wt%, e.g., 0.5-3 wt%, or 0.5-2 wt%, or 0.5-1 .2 wt%, or 0.5-1 .2 wt%, calculated on an oxide basis. In various embodiments, in the refractory oxide support yttrium is present in an amount of 1-5 wt%, e.g., 1-3 wt%, or 1-2 wt%, or 1 -1 .5 wt%, calculated on an oxide basis.

[0032] In various embodiments, a total amount of lanthanum and yttrium in the refractory oxide support is at least 0.5 wt%, e.g., at least 0.7 wt%, or at least 1 wt%, or at least 2 wt%, calculated on an oxide basis.The materials can be provided with a variety of amounts of aluminum, zirconium, titanium, cerium, lanthanum and yttrium. Aluminum, zirconium, titanium, cerium, lanthanum andClariant International Ltd 2024US702-WO-PCT yttrium in oxidic form can desirably make up a substantial portion of the refractory oxide support. For example, in various embodiments, a total amount of aluminum, zirconium, titanium, cerium, lanthanum and yttrium in the refractory oxide support is at least 70 wt%, for example, in the range of 70-99 wt%, e.g., 70-95 wt%, or 70-90 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, zirconium, titanium, cerium, lanthanum and yttrium in the refractory oxide support is at least 80 wt%, for example, in the range of 80-99 wt%, e.g., 80-98 wt%, or 80-90 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, zirconium, titanium, cerium, lanthanum and yttrium in the refractory oxide support is at least 90 wt%, for example, in the range of 90-99 wt%, e.g., 90-98 wt%, or 90-95 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, zirconium, titanium, cerium, lanthanum and yttrium in the refractory oxide support is at least 95 wt%, for example, in the range of 95-99 wt%, e.g., 95-98 wt%, calculated on an oxide basis.

[0034] The present inventors have found that inclusion of cerium together with aluminum, optionally in combination with lanthanum and / or yttrium in a refractory oxide support can provide the catalyst material with a variety of benefits. Further, the bulk support material together with the cerium and lanthanum can, upon exposure to high temperatures under reducing conditions such as those found during reforming and other high-temperature hydrogen-consuming or hydrogen-generating processes, form perovskites of the formula CeAIOs and LaAIOs, which can impart excellent thermal stability and mechanical stability to the catalyst material, and further can help prevent the formation of carbon coke thereon. Thus, in various embodiments as described herein, the refractory oxide support comprises rare earth-stabilized alumina, stabilized with cerium, and optionally lanthanum and / or yttrium, each in substantially oxidic form.

[0035] The materials can be provided with a variety of amounts of aluminum, cerium, lanthanum and yttrium. Aluminum, cerium, lanthanum and yttrium in oxidic form can desirably make up a substantial portion of the refractory oxide support. For example, in various embodiments, a total amount of aluminum, cerium, lanthanum and yttrium in the refractory oxideClariant International Ltd 2024US702-WO-PCT support is at least 70 wt%, for example, in the range of 70-99 wt%, e.g., 70-95 wt%, or 70-90 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, cerium, lanthanum and yttrium in the refractory oxide support is at least 80 wt%, for example, in the range of 80-99 wt%, e.g., 80-98 wt%, or 80-90 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, cerium, lanthanum and yttrium in the refractory oxide support is at least 90 wt%, for example, in the range of 90-99 wt%, e.g., 90-98 wt%, or 90-95 wt%, calculated on an oxide basis. In various embodiments, a total amount of aluminum, cerium, lanthanum and yttrium in the refractory oxide support is at least 95 wt%, for example, in the range of 95-99 wt%, e.g., 95-98 wt%, calculated on an oxide basis.

[0036] In various embodiments, the refractory oxide support further comprises silica, e.g., in an amount up to 30 wt% silicon, e.g., up to 20 wt%, or up to 15 wt%, calculated on an oxide basis. In various embodiments, silica is present in an amount in the range of 2-30 wt%, e.g., 2- 20 wt%, or 2-15 wt%, calculated on an oxide basis. In various embodiments, silica is present in an amount in the range of 5-30 wt%, e.g., 5-20 wt%, or 5-15 wt%, calculated on an oxide basis. In various embodiments, silica is present in an amount in the range of 2-10 wt%, e.g., 2-8 wt%, or 2-6 wt%, calculated on an oxide basis. In various embodiments silica is present in an amount in the range of 5-10 wt%, e.g., 5-8 wt%, calculated on an oxide basis.

[0037] The present inventers note that a refractory oxide support with a high surface area can be especially desirable. For example, in various embodiments as described herein, the refractory oxide support of the metallic catalytic component has a surface area of at least 50 m2 / g, e.g., at least 100 m2 / g, or at least 125 m2 / g, or at least 150 m2 / g, or at least 200 m2 / g, or at least 300 m2 / g, as measured using the BET method.

[0038] As the person of ordinary skill in the art will appreciate, catalytic metal species are typically disposed on refractory oxide supports for use in industrial catalysis processes.Accordingly, in various embodiments, the catalyst materials as otherwise described herein further include one or more catalytic metals disposed on the support. A wide variety of catalyticClariant International Ltd 2024US702-WO-PCT metals for known in various processes. Examples include nickel, ruthenium, rhodium, palladium, platinum, copper, cobalt, silver, iron, chromium, manganese, and molybdenum. For example, various metals are capable of catalyzing hydrogen generation processes such as reforming processes and nitrogen cracking processes. In various embodiments, the catalyst materials of the disclosure include disposed on the refractory oxide support, one or more of nickel, rhodium, and ruthenium. The person of ordinary skill in the art is familiar with such catalytic activities of these metals. For example, in various embodiments as otherwise described herein, the catalyst material comprises nickel disposed on the refractory oxide support. In various embodiments, the catalyst material comprises ruthenium disposed on the refractory oxide support. In various embodiments, the catalyst material comprises rhodium disposed on the refractory oxide support.

[0039] The person of ordinary skill in the art will appreciate that “disposed on” a support does not require a particular form of the metal; it can be present, e.g., in any one or more of disposed within pores of the support, disposed on an exterior surface of the support, or intimately combined with the support.

[0040] It can be beneficial to use a combination of catalytic metals in the catalyst materials. The present inventors note that a combination of nickel and one or more of ruthenium, rhodium, palladium, and platinum can be especially useful in the catalysis of hydrogen production. Accordingly, in various embodiments as described herein, the catalyst material comprises nickel and one or more of ruthenium, rhodium, palladium, and platinum disposed on the refractory oxide support. The person of ordinary skill in the art can, based on the state of the art, determine an appropriate ratio of ruthenium, rhodium, palladium, and / or platinum to nickel for the desired hydrogen production process. In some embodiments, an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is at least 0.005:1 , e.g., at least 0.01 :1 , or at least 0.015:1 . In some embodiments, an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is up toClariant International Ltd 2024US702-WO-PCT100:1 , e.g., up to 10:1 , or up to 5:1 . In some embodiments, an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is up to 1 :1 , e.g., up to 0.5:1 , or up to 0.2:1 . In some embodiments, an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is up to 0.1 :1 , e.g., up to 0.05:1 , or up to 0.03:1 . For example, in some embodiments, an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is in the range of 0.005:1 to 100:1 , e.g., 0.005:1 to 10:1 , or 0.005:1 to 5:1 , or 0.005:1 to 1 :1 , or 0.005:1 to 0.5:1 , or 0.005:1 to 0.2:1 , or 0.005:1 to 0.1 :1 , or 0.005:1 to 0.05:1 , or 0.005:1 to 0.03:1 . In some embodiments, an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is in the range of 0.01 :1 to 100:1 , e.g., 0.01 :1 to 10:1 , or 0.01 :1 to 5:1 , or 0.01 :1 to 1 :1 , or 0.01 :1 to 0.5:1 , or 0.01 :1 to 0.2:1 , or 0.01 :1 to 0.1 :1 , or 0.01 :1 to 0.05:1 , or 0.01 :1 to 0.03:1 . In some embodiments, an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is in the range of 0.015:1 to 100:1 , e.g., 0.015:1 to 10:1 , or 0.015:1 to 5:1 , or 0.015:1 to 1 :1 , or 0.015:1 to 0.5:1 , or 0.015:1 to 0.2:1 , or 0.015:1 to 0.1 :1 , or 0.015:1 to 0.05:1 , or 0.015:1 to 0.03:1.

[0041] The catalytic metal(s) can be provided to the catalyst material in any desirable fashion. While in some embodiments catalytic metal(s) can be included in the same washcoat from which the refractory oxide can be coated, in many cases it will be a more efficient use of material to impregnate the catalytic metals(s) into the refractory oxide support, as is conventional in the art.

[0042] The catalytic metal(s) can be present in a variety of amounts in the catalyst materials of the disclosure. In various embodiments as otherwise described herein, the one or more catalytic metals are present in a total amount up to 20 wt%, e.g., up to 15 wt%, up to 10 wt%, up to 5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%. In various embodiments, the one or more catalytic metals are present in a total amount in the range of 0.001-20 wt%, e.g., in the range of 0.001-15 wt%, or 0.001-10 wt%,Clariant International Ltd 2024US702-WO-PCT or 0.001 -5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%. In various embodiments, the one or more catalytic metals are present in a total amount in the range of 0.1-20 wt%, e.g., in the range of 0.1 -15 wt%, or 0.1 -10 wt%, or 0.1-5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%. In various embodiments, the one or more catalytic metals are present in a total amount in the range of 0.5-20 wt%, e.g., in the range of 0.5-15 wt%, or 0.5-10 wt%, or 0.5-5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%. In various embodiments, the one or more catalytic metals are present in a total amount in the range of 1 -20 wt%, e.g., in the range of 1 -15 wt%, or 1 -10 wt%, or 1-5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%. In various embodiments, the one or more catalytic metals are present in a total amount in the range of 2-20 wt%, e.g., in the range of 2-15 wt%, or 2-10 wt%, or 2-5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%.

[0043] The present inventors have noted that metallic substrates can be very desirable for improving heat transfer in catalyst systems. Metallic substrates typically have high thermal conductivity compared to their ceramic counterparts. Additionally, depending on form, metallic substrates can contribute less pressure drop and provide for higher catalyst utilization. The present inventors note, however, that it can be difficult to achieve a durable adhesion of conventional reforming and cracking catalyst materials (e.g., based on a-AhOs and CaAli2Oig) to metallic substrates, especially under the high temperatures of reforming and cracking processes. The present inventors found that the presently described catalyst materials can provide especially good adhesion to metallic substrates without degrading during high temperature applications.

[0044] Accordingly, the metallic substrate is formed from a metal. A variety of metals can be suitable for use, as is recognized is the art. For example, in various embodiments, the metalClariant International Ltd 2024US702-WO-PCT is selected from alloys containing iron and chromium, e.g., iron-chromium-aluminum alloys, nickel-chromium-iron and iron-chromium alloys, optionally with aluminum, molybdenum, and / or niobium. In other embodiments, the metal is selected from nickel-chromium alloys, optionally with iron, aluminum, molybdenum, and / or niobium. In various embodiments, the metal is a stainless steel.

[0045] The metallic catalytic components can be provided in a variety of forms. It can be advantageous to reduce the heat transfer resistance contributed by the metallic catalytic component during high-temperature processes, especially when substantially endothermic or exothermic. One way to reduce heat transfer resistance is to improve the gas flow as it flows across the metallic catalytic component. This can be achieved by using metallic substrates configured such that gases can flow through or across them with less resistance.

[0046] For example, in various embodiments, the metallic substrate is in the form of a foil or sheet. Such foils and sheets can themselves be shaped, e.g., via corrugation, folding, or forming into a spiral or other shape. A plurality of foils and sheets can be arranged together in an assembly, e.g., of parallel sections, such that gases can flow across them with little resistance. The foil or sheet can be, e.g., in the range of 0.025-3 mm in thickness, e.g., in the range of 0.025-1 mm, or 0.025-0.5 mm, or 0.025-0.1 mm, or 0.05-3 mm, or 0.05-1 mm, or 0.05- 0.5 mm, or 0.1 -3 mm, or 0.1 -1 mm. Foils and sheets are especially desirable when formed from metal as described above.

[0047] In other embodiments, the metallic substrate of the metallic catalytic component has a honeycomb, channel, or foam substructure that allows reactant gases to pass therethrough.

[0048] Similarly, in some embodiments, the metallic substrate has a structured surface comprising a plurality of subsurfaces, e.g., has a corrugated surface or a surface comprising a plurality of slats.

[0049] In order to allow for installation into metal tubes as described above, it can be desirable for a metallic substrate to be flexible. As used herein, a flexible substrate is aClariant International Ltd 2024US702-WO-PCT substrate that is able to bend, fold, flex or deform without breaking, while maintaining structural integrity.

[0050] The amount of catalyst material disposed on the metallic substrate is not particularly limited, so long as sufficient catalyst is disposed on the metallic substrate, and the coating is durable enough to withstand the harsh reaction conditions of hydrogen production. In various embodiments as otherwise described herein, the catalyst material is disposed on the metallic substrate with a loading in the range of 30-200 g / m2, e.g., in the range of 30-180 g / m2, or 50- 200 g / m2, or 50-180 g / m2, or 70-200 g / m2, or 70-180 gm2.

[0051] The metallic catalytic components described herein can be enclosed in an enclosure. The enclosure can take a variety of forms, e.g., a tube or a canister. Such enclosed systems can be provided as part of a reactor system, e.g., the tube of a tubular reactor being an enclosure, or can be pre-assembled for modular installation into a reactor (e.g., as in a CANS system). In certain embodiments, the enclosure is an EARTH® reforming tube, which is described in U.S. Patent 10,472,236, which is hereby incorporated by reference in its entirety. In various embodiments, the metallic catalytic component is held in a flexed position in the enclosure, i.e. , it is held such that it is squeezed or expanded beyond the shape it would take if not disposed within the enclosure.

[0052] The enclosure and the metallic catalytic components can together define a volume, and it can be desirable to have a sufficient amount of catalyst material present in the enclosed volume. In various embodiments, the catalyst material is present in the volume in an amount in the range of 25-300 g catalyst material per liter of enclosed volume, e.g., in the range of 25-200 g / L, or 50-300 g / L, or 50-200 g / L, or 100-300 g / L, or 100-200 g / L. Desirably, the one or more catalytic metals are present in the volume in an amount of at least 0.1 g / L, e.g., at least 0.5 g / L, at least 1 g / L or at least 2 g / L, e.g., 0.1-30 g / L, or 0.5-30 g / L, or 1 -30 g / L, or 2-30 g / L, or 0.1-20 g / L, or 0.5-20 g / L, or 1 -20 g / L, or 2-20 g / L, or 0.1-10 g / L, or 0.5-10 g / L or 1 -10 g / L, or 2-10 g / L, on an elemental basis.Clariant International Ltd 2024US702-WO-PCT

[0053] Processes for Making Catalyst Materials and Metallic Catalytic Components

[0054] The person of ordinary skill in the art can use conventional processes for synthesizing catalyst materials and metallic catalytic components as described herein. While particular washcoating processes are described here, the person of ordinary skill in the art will understand that the materials of the disclosure can be made in a variety of manners.

[0055] Another aspect of the disclosure is a process for preparing a metallic catalytic component as described herein. The process includes providing a substrate (e.g., a flexible metallic substrate as described above); providing a suspension of refractory oxide components in a first aqueous liquid; coating the substrate with the suspension to provide a wet coating on the substrate; and drying and calcining the wet-coated substrate to provide a refractory oxide coating on the substrate.

[0056] The refractory oxide components are not particularly limited. The person of ordinary skill in the art would be able to choose appropriate compounds and refractory oxides in desired amounts that will provide the metallic catalytic component with a desired composition coating. Components can be provided as oxides themselves, for example, in colloidal form.Advantageously, the inventors note that certain refractory oxide components provided in colloidal form can act as binders to enhance the adhesion of the refractory oxide support to the metallic substrate. Various colloidal materials can have similar pH ranges, and as such, the refractory oxide components provided in colloidal form is not particularly limited. For example, in various embodiments as described herein, at least a portion of the cerium, silicon, aluminum, zirconium, titanium, and / or mixtures or combinations thereof of the suspension is provided in colloidal form. The pH and the solids content of the colloidal liquid is not particularly limited.

[0057] Components can also be provided as oxides in larger particle sizes as well, for example as alumina, zirconia or titania, each of which can be doped as described above.Clariant International Ltd 2024US702-WO-PCT

[0058] As an alternative, components can be provided as precipitated salts (e.g., in the form of nitrates, carbonates or hydroxides) as is common in catalyst synthesis via precipitation; these salts can be converted to oxides upon calcining.

[0059] The first aqueous liquid is also not particularly limited and the person of ordinary skill in the art would be able to choose an appropriate liquid that will suspend the refractory oxide components. As the person of ordinary skill in the art will appreciate, a convenient choice for the first aqueous liquid is water.In some cases it can be desirable to mill the suspension to reduce overall particle size. The person of ordinary skill in the art can determine the desired particle size in the suspension, and determine a milling method and time based on the desired particle size. In various embodiments as described herein, the suspension has a particle size distribution of a D50 value in the range of 0.1 - 20 microns and a D90 value in the range of 10 - 100 microns.

[0061] Further, the solids content of the suspension is not particularly limited. For example, in various embodiments as described herein, the suspension has a solids content in the range of 30-60%, e.g., in the range of 30-50%, or 30-40%, or 35-50%, or 40-50%. But the person of ordinary skill in the art can determine a solids content to provide a desired viscosity for application.

[0062] One example of a suspension for coating includes one or more metal oxides such as alumina, zirconia and titania. The alumina, zirconia and / or titania can be rare earth-stabilized as provided herein. As one alternative, sufficient amounts of stabilizing rare earth can be provided in the suspension along with the alumina, zirconia and / or titania.

[0063] The person of ordinary skill in the art can select amounts of materials for the suspension that provide a desired composition for the refractory oxide material, on an as calcined basis.

[0064] The person of ordinary skill in the art can determine an appropriate way to apply the suspension to a substrate, which may depend on the size or shape of the substrate. In someClariant International Ltd 2024US702-WO-PCT embodiments as described herein, the suspension is applied to a metallic substrate by dipping the substrate into the suspension. However, other methods for applying catalyst material to substrates are known in the art. For example, in various embodiments as described herein, the suspension is applied to a substrate by brushing, pressure spray, drop-spin coating, rolling, electrostatic coating, ultrasonic spraying, or air spraying. Removal of excess suspension from the wet-coated substrate may be desirable in some cases, and can be performed in a variety of ways, e.g., via air-knife or vacuum suction.

[0065] It can be advantageous to have the substrate set in a desired shape prior to the application of the suspension, facilitating subsequent installation of the metallic catalytic component in an enclosure (as described above). The holder is not particularly limited in its size or shape. As such, in various embodiments as described herein, the substrate is provided while disposed inside or around a holder to maintain a particular shape. Examples of holders for flexible metallic substrates are depicted in FIG. 1 .

[0066] The wet-coated substrate can then be dried and calcined. The drying can be performed in a separate operation, for example, at an elevated temperature for a drying time. The person of ordinary skill in the art would be able to select appropriate drying conditions and apparatuses. For example, in some embodiments, the elevated temperature is in the range of 75-200 °C. In some embodiments, the drying time is in the range of 1 to 48 hours. But the drying can also happen as part of an initial stage in a calcining operation.

[0067] As noted above, the process further includes calcining the dried substrate to provide a catalyst material disposed on the metal substrate. The calcining step can be conducted at calcining temperature for a calcining time. For example, in some embodiments the calcining temperature is at least 450 °C. In some embodiments, the calcining temperature is in the range of 0.5 to 24 hours.

[0068] Catalytic metal(s) can be included in the material in any convenient manner.Particulate catalytic metal compounds can be included in the washcoat suspension. ForClariant International Ltd 2024US702-WO-PCT example, in various embodiments as described herein, one or more catalytic metals are included in the washcoat suspension in particulate form, e.g., in the form of oxides or insoluble salts such as carbonates.

[0069] Alternatively, impregnation methods can be used. In various embodiments, the process further includes providing a solution of one or more catalytic metals in a second aqueous liquid; applying the solution of one or more catalytic metals to the refractory oxide coating to impregnate the refractory oxide coating therewith; drying and calcining the impregnated refractory-oxide coated substrate. The second aqueous fluid can be, e.g., water, and the catalyst metals can be conveniently dissolved therein in the form of nitrate or acetate salts.

[0070] The person of ordinary skill in the art can determine the best way to apply the metallic solution to the refractory oxide coating. In some embodiments as described herein, the metallic solution is applied to a metallic catalyst component using incipient wetness impregnation.

[0071] The impregnated material can be dried and calcined substantially as described above.

[0072]

[0073] Processes for Using Metallic Catalytic Components in Hydrogen Production

[0074] The materials described herein can be used in a variety of processes for the endothermic production of hydrogen, such as steam methane reforming, dry methane reforming, and LPG reforming, and ammonia cracking.

[0075] An additional aspect of this disclosure provides a method for using a metallic catalytic component as described herein for hydrogen production. In particular embodiments, this disclosure provides a process for reforming or cracking a feedstock to provide hydrogen, the process comprising: providing a metallic catalytic component as described herein, wherein at least a portion (e.g., at least 10 atom%, at least 25 atom% or at least 50 atom%) of theClariant International Ltd 2024US702-WO-PCT catalytic metal(s) is in a metallic form; and contacting the metallic catalytic component with a feed stream comprising one or more of C1-C4 alkanes and ammonia and, optionally, water and / or carbon dioxide, at a reaction temperature of at least 500 °C (e.g., 500-900 °C) to provide a stream comprising hydrogen.The person of ordinary skill in the art is familiar with processes to activate reforming and cracking catalysts with treatment in hydrogen in order to provide catalytic metals in metallic form (i.e., reduced to a zero oxidation state). After calcining, the metal of the catalyst material will generally be in an oxidic form.

[0077] The person of ordinary skill in the art can determine the appropriate reducing conditions to activate the metallic catalytic component. For example, in some embodiments, the hydrogen content in the reducing gas stream is in the range of 1-10 vol%. In various embodiments, the reduction of the metallic catalytic component is carried out at a temperature in the range of 800-1000 °C. In various embodiments, the metallic catalytic component is reduced for a time in the range of 4-8 hrs.

[0078] In various embodiments, the feed stream comprises methane and water, and the product stream includes carbon monoxide and hydrogen. Such processes are known as steam methane reforming processes. In various embodiments, the water feed stream content in the range of 20-40 mol%. In various embodiments, the methane content in the SMR feed stream is in the range of 5-15 mol%. In some embodiments, methane can come from natural gas, petroleum refineries. In various embodiments, the SMR feed stream further comprises inerts (i.e., not water or methane). In some embodiments, the inerts comprise nitrogen. In some embodiments, the inerts content in the SMR feed stream is in the range of 35-75 mol%. In various embodiments, the metallic catalytic component is contacted with the SMR feed stream at a temperature of at least 500 °C. In various embodiments, the metallic catalytic component is contacted with the SMR feed stream for a time in the range of 1-48 hours. In various embodiments, the metallic catalytic component is contacted with the SMR feed with a gasClariant International Ltd 2024US702-WO-PCT hourly space velocity in the range of 1000-1000000 h’1, and a pressure in the range of 1 -100 bar.

[0079] In various embodiments, the feed stream comprises methane and carbon dioxide, and the product stream includes carbon monoxide and hydrogen. Such processes are known as dry methane reforming processes. The person of ordinary skill in the art, based on the above, can select reaction conditions for dry methane reforming processes.

[0080] In various embodiments, the feed stream comprises propane and / or butane and water, and the product stream includes carbon monoxide and hydrogen. Such processes are known as LPG reforming processes. The person of ordinary skill in the art, based on the above, can select reaction conditions for LPG reforming processes.

[0081] In various embodiments, the feed stream comprises ammonia, and the product stream includes nitrogen and hydrogen. Such processes are known as ammonia cracking processes. The person of ordinary skill in the art, based on the above, can select reaction conditions for ammonia cracking processes.EXAMPLES

[0082] The Examples that follow are illustrative of specific embodiments of the materials of the disclosure. They are set forth for explanatory purposes only, and are not to be taken as limiting the scope of the disclosure.

[0083] Generally, in some cases the metallic substrate coating process can be one-step washcoating process. In such a process, the catalyst material components, including catalytic metal components, are directly washcoated onto metallic substrates. In the washcoating process, all catalyst material components are first mixed with the addition of binder and milled for certain time to obtain desirable particle size suspension. The suspension is then applied to the metallic substrates. The process of coating of the metallic substrate with the suspension is not particularly limited. For example, in various embodiments as described herein, the metallicClariant International Ltd 2024US702-WO-PCT substrate coated with the suspension by brush-painting, by high-pressure air spray coating, or by dipping the metallic substrate into the suspension. The extra suspension is removed by airknife or centrifuge or vacuum suction. After that, the coated substrates are dried and calcined at high temperature (e.g., 500-600 °C) to secure the catalyst materials coated on the metallic substrates.

[0084] As an alternative, catalyst materials can be made in two-step process, in which washcoating is used to form the refractory oxide as a coating, then impregnation is used to provide the catalytic metal(s). After formation of the refractory oxide coating as described above, the coated substrates are treated with catalytic metal solution, e.g., by dipping, brushpainting, or spraying, with any extra solution is removed by air-knife or centrifuge or vacuum suction; or by incipient wetness or other methods that deposit only a particular amount of material. After that, the metal solution coated substrates are dried and calcined at high temperature (e.g., 500-600 °C) to secure the metals supported on refractory oxides which are coated on the substrates in previous coating process.

[0085] For example, the coating of catalyst material can be applied to a flexible metallic foil substrate having width 1.5” and a length of 12” by brushing the washcoat suspension, pressure spraying the washcoat suspension, or drop-spin coating. Other technique to apply coating materials on the surface of the flexible metallic foil substrate may involve rolling (as with a paint roller), dipping, electrostatic coating, ultrasonic spraying, air spraying, etc.

[0086] The following examples were prepared:

[0087] Example 1

[0088] An alumina-based washcoat suspension is prepared by mixing 900 g Ce- and La- stabilized alumina with surface area 170 m2 / g, 260 g alumina colloid and 1 .0 liters water. The mixture is then milled to a suspension with a desired particle size distribution.Clariant International Ltd 2024US702-WO-PCT

[0089] A flexible metallic foil substrate strip, having size width 1.5”, a length of 12”. painted by brushing the washcoat suspension. The coated part is then dried at 150 °C and calcined at 500 °C. The resulting washcoat loading is 125 g / m2.

[0090] Example 2

[0091] A ceria-doped alumina based washcoat suspension is prepared by mixing 900 g La- and Y-stabilized alumina with surface area 170 m2 / g, 300 g ceria colloid, 200 g alumina colloid, and 1 .0 liters water. The mixture is then milled to a suspension with a desired particle size distribution

[0092] A flexible metallic foil substrate strip, having size width 1.5”, a length of 12”. painted by brushing the washcoat suspension. The coated part is then dried at 150 °C and calcined at 500 °C. The resulting washcoat loading is 125 g / m2.

[0093] Example 3A zirconia based washcoat suspension is prepared by mixing 900g SiO2-doped zirconia powder with a surface area 150 m2 / g, 250 g silica colloid and 1.5 liters water. The mixture is then milled to a suspension with a desired particle size distribution.

[0095] A flexible metallic foil substrate strip having size 1 .5”, a length of 12” and is dipped into the washcoat suspension. Extra suspension is removed by centrifuge spin. The coated part is then dried at 150 °C and calcined at 500 °C. The resulting washcoat loading is 120 g / m2.

[0096] Example 4

[0097] A ceria-zirconia based washcoat suspension is prepared by mixing 900 g ceriazirconia mixed oxide powder with a surface area 80 m2 / g, 20 g acetic acid and 0.75 liters water.The mixture is then milled to a suspension with a desired particle size distribution.Clariant International Ltd 2024US702-WO-PCT

[0098] A flexible metallic foil substrate strip having size 1 .5”, a length of 12” and is dipped into the washcoat suspension. Extra suspension is blown out using an air-knife. The coated part is then dried at 150 °C and calcined at 500 °C. The resulting washcoat loading is 120 g / m2.

[0099] Example 5A ceria-zirconia based washcoat suspension is prepared by mixing 900 g ceriazirconia mixed oxide powder with a surface area 80 m2 / g, 200 g alumina colloid, and 0.75 liters water. The mixture is then milled to a suspension with a desired particle size distribution.

[0101] A flexible metallic foil substrate strip having size 1 .5”, a length of 12” and is dipped into the washcoat suspension. Extra suspension is removed by centrifuge spin. The coated part is then dried at 150 °C and calcined at 500 °C. The resulting washcoat loading is 120 g / m2.

[0102] Example 6

[0103] A titania based washcoat suspension is prepared by mixing 900 g SiO2-doped titania powder which has about surface area 100 m2 / g, 240 g silica colloid and 1 .2 liters water, and followed by milling the mixture to a suspension with a desired particle size distribution.

[0104] A flexible metallic foil substrate having size 1 .5”, a length of 12” and is painted by brushing the washcoat suspension. The coated part is then dried at 150 °C and calcined at 500°C. The resulting washcoat loading is 125 g / m2.

[0105] Example 7 - Attritien Testing ef Ceated Flexible Metal Substrates

[0106] To measure the adhesion of the coating onto the metal substrate, washcoated flexible metallic foil substrates are subjected to vibration testing. One end of the sample is fixed in place, while the rest of the sample body relaxes and can freely move. An air nozzle is used to generate an air jet stream that induces high-frequency vibrations in the flexible metallic foil substrates. The flow rate and pressure of the air supply are controlled to ensure testingClariant International Ltd 2024US702-WO-PCT consistency. The attrition (%) is calculated based on the weight loss of the washcoat materials before and after the vibration testing. The lower the attrition (%), the greater the adhesion of the washcoat to the flexible foil substrates. A photograph of the test apparatus along with a cartoon showing the positioning of the airflow with respect to the sample is provided in FIG. 2.

[0107]

[0108] The results of the attrition testing on the as-prepared washcoated flexible metallic foil substrates (500 °C calcined samples) and on samples further calcined at 1000 °C (representing high-temperature applications such as steam methane reforming) are shown in Table 1.

[0109] Table 1 . Attrition testing results

[0110] Example 8 - addition of catalytic nickel

[0111] Nickel nitrate solution is deposited on a flexible corrugated substrate, formed into a cylinder with a 2 inch diameter, coated with the wash coat described in Example 2, by incipient wetness impregnation. This is followed by drying at 120 °C and calcination at 500 °C. The resulting nickel load is 20 g / m2.

[0112] Clariant International Ltd 2024US702-WO-PCT

[0113] Example 9 - catalytic activity.The flexible corrugated metal substrate catalyst sample of Example 8 was evaluated for catalytic activity in steam methane reforming. The flexible catalyst sample is directly inserted in reactor metal tube with 2 inch inner diameter. It was subjected to a steam methane reforming gas stream (15 vol% methane, 45 vol% water, and nitrogen) under a gas hourly space velocity of 6500 h’1. The methane conversion was measured by gas chromatography analysis of the outlet gas composition. The relationship between methane conversion and reaction temperature is shown in FIG. 3. In general, the flexible metal substrate catalyst of Example 8 shows high methane conversion, close to equilibrium methane conversion. Without intending to be bound by theory, the inventors believe that the high methane conversion is due to improved heat transfer between the flexible metallic substrate and reactor tube.

[0114] Other aspects of the disclosure are described with respect to the following enumerated embodiments, which may be combined in any fashion and in any number that is not technically or logically inconsistent.Embodiment 1 . A metallic catalytic component comprising: a metallic substrate; and disposed on the metallic substrate, a catalyst material comprising a refractory oxide support, the refractory oxide support.Embodiment 2. The metallic catalytic component of embodiment 1 , wherein the refractory oxide support comprises rare-earth-stabilized alumina.Clariant International Ltd 2024US702-WO-PCTEmbodiment 3. The metallic catalytic component of embodiment 2, wherein the refractory oxide support comprises aluminum in an amount in the range of 60-98 wt%, e.g., 65-98 wt%, or 70-98 wt%, or 75-98 wt%, or 80-98 wt%, calculated on an oxide basis.Embodiment 4. The metallic catalytic component of embodiment 2, wherein the refractory oxide support comprises aluminum in an amount in the range of 60-95 wt%, e.g., 65-95 wt%, or 70-95 wt%, or 75-95 wt%, or 80-95 wt%, calculated on an oxide basis.Embodiment 5. The metallic catalytic component of embodiment 2, wherein the refractory oxide support comprises aluminum in an amount in the range of 60-90 wt%, e.g., 65-90 wt%, or 70-90 wt%, or 75-90 wt%, or 80-90 wt%, calculated on an oxide basis.Embodiment 6. The metallic catalytic component of embodiment 2, wherein the refractory oxide support comprises aluminum in an amount in the range of 60-85 wt%, e.g., 65-85 wt%, or 70-85 wt%, or 75-85 wt%, calculated on an oxide basis.Embodiment 7. The metallic catalytic component of any of embodiments 1 -2, wherein the refractory oxide support comprises rare earth-stabilized zirconia and / or silica / stabilized zirconia.Embodiment 8. The metallic catalytic component of embodiment 7, wherein the refractory oxide support comprises zirconium in an amount in the range of 60-98 wt%, e.g., 65-98 wt%, or 70-98 wt%, or 75-98 wt%, or 80-98 wt%, calculated on an oxide basis.Embodiment 9. The metallic catalytic component of embodiment 7, wherein the refractory oxide support comprises zirconium in an amount in the range of 60-95 wt%, e.g., 65-95 wt%, or70-95 wt%, or 75-90 wt%, or 80-90 wt%, calculated on an oxide basis.Clariant International Ltd 2024US702-WO-PCTEmbodiment 10. The metallic catalytic component of embodiment 7, wherein the refractory oxide support comprises zirconium in an amount in the range of 60-85 wt%, e.g., 65-85 wt%, or 70-85 wt%, or 75-85 wt%, or 80-85 wt%, calculated on an oxide basis.Embodiment 11 . The metallic catalytic component of embodiment 7, wherein the refractory oxide support comprises zirconium in an amount in the range of 60-80 wt%, e.g., 65-80 wt%, or 70-80 wt%, or 75-80 wt%, calculated on an oxide basis.Embodiment 12. The metallic catalytic component of any of embodiments 1 -2 and 7, wherein the refractory oxide support comprises rare earth-stabilized titania and / or silica- stabilized titania.Embodiment 13. The metallic catalytic component of embodiment 12, wherein the refractory oxide support comprises titanium in an amount in the range of 60-98 wt%, e.g., 65-98 wt%, or 70-98 wt%, or 75-98 wt%, or 80-98 wt%, calculated on an oxide basis.Embodiment 14. The metallic catalytic component of embodiment 12, wherein the refractory oxide support comprises titanium in an amount in the range of 60-95 wt%, e.g., 65-95 wt%, or 70-95 wt%, or 75-95 wt%, or 80-95 wt%, calculated on an oxide basis.Embodiment 15. The metallic catalytic component of embodiment 12, wherein the refractory oxide support comprises titania in an amount in the range of 60-90 wt%, e.g., 65-90 wt%, or 70-90 wt%, or 75-90 wt%, or 80-90 wt%, calculated on an oxide basis.Clariant International Ltd 2024US702-WO-PCTEmbodiment 16. The metallic catalytic component of embodiment 12, wherein the refractory oxide support comprises titania in an amount in the range of 60-85 wt%, e.g., 65-85 wt%, or 70-85 wt%, or 75-85 wt%, calculated on an oxide basis.Embodiment 17. The metallic catalytic component of any of embodiments 1 -16, wherein a total amount of aluminum, zirconium and titanium in the refractory oxide support is in the range of 60-98 wt%, e.g., 65-98 wt%, or 70-98 wt%, or 75-98 wt%, or 80-98 wt%, calculated on an oxide basisEmbodiment 18. The metallic catalytic component of any of embodiments 1 -16, wherein a total amount of aluminum, zirconium and titanium in the refractory oxide support is in the range of 60-95 wt%, e.g., 65-95 wt%, or 70-95 wt%, or 75-95 wt%, or 80-95 wt%, calculated on an oxide basisEmbodiment 19. The metallic catalytic component of any of embodiments 1 -16, wherein a total amount of aluminum, zirconium and titanium in the refractory oxide support is in the range of 60-90 wt%, e.g., 65-90 wt%, or 70-90 wt%, or 75-90 wt%, or 80-90 wt%, calculated on an oxide basisEmbodiment 20. The metallic catalytic component of any of embodiments 1 -16 wherein a total amount of aluminum, zirconium and titanium in the refractory oxide support is in the range of 60-85 wt%, e.g., 65-85 wt%, or 70-85 wt%, or 75-85 wt%, or 80-85 wt%, calculated on an oxide basisClariant International Ltd 2024US702-WO-PCTEmbodiment 21 . The metallic catalytic component of any of embodiments 1 -20, wherein the refractory oxide support comprises rare earth-stabilized alumina, rare earth-stabilized zirconia, or rare earth-stabilized titania.Embodiment 22. The metallic catalytic component of any of embodiments 1 -21 , wherein the refractory oxide support comprises one or more rare earths selected from cerium, lanthanum and yttrium.Embodiment 23. The metallic catalytic component of any of embodiments 1 -21 , wherein the refractory oxide support comprises cerium.Embodiment 24. The metallic catalytic component of embodiment 23, wherein the cerium is present in the refractory oxide support in an amount in the range of 2-35 wt%, e.g., 2-30 wt%, or 2-25 wt%, or 2-20 wt%, calculated on an oxide basis.Embodiment 25. The metallic catalytic component of embodiment 23, wherein the cerium is present in the refractory oxide support in an amount in the range of 5-40 wt%, e.g., 5-35 wt%, or 5-30 wt%, or 5-25 wt%, or 5-20 wt%, calculated on an oxide basis.Embodiment 26. The metallic catalytic component of embodiment 23, wherein the cerium is present in the refractory oxide support in an amount in the range of 10-40 wt%, e.g., 10-35 wt%, or 10-30 wt%, or 10-25 wt%, or 10-20 wt%, calculated on an oxide basis.Embodiment 27. The metallic catalytic component of embodiment 23, wherein the cerium is present in the refractory oxide support in an amount in the range of 15-40 wt%, e.g., 15-35 wt%, or 15-30 wt%, or 15-25 wt%, calculated on an oxide basis.Clariant International Ltd 2024US702-WO-PCTEmbodiment 28. The metallic catalytic component of any of embodiments 1 -27, wherein the refractory oxide support comprises lanthanum.Embodiment 29. The metallic catalytic component of embodiment 28, wherein the lanthanum is present in an amount in the range of 0.1 -3 wt%, e.g., 0.1-2 wt%, or 0.1 -1 wt%, or 0.1 -0.5 wt%, calculated on an oxide basis.Embodiment 30. The metallic catalytic component of embodiment 28, wherein the lanthanum is present in an amount in the range of 0.2-5 wt%, e.g., 0.2-3 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.2-0.7 wt%, calculated on an oxide basis.Embodiment 31 . The metallic catalytic component of embodiment 28, wherein the lanthanum is present in an amount in the range of 0.5-5 wt%, e.g., 0.5-3 wt%, or 0.5-2 wt%, or 0.5-1.2 wt%, or 0.5-1.2 wt%, calculated on an oxide basis.Embodiment 32. The metallic catalytic component of embodiment 28, wherein the lanthanum is present in an amount in the range of 1-5 wt%, e.g., 1-3 wt%, or 1-2 wt%, or 1-1.5 wt%, calculated on an oxide basis.Embodiment 33. The metallic catalytic component of embodiment 28, wherein the lanthanum is present in an amount in the range of 2-5 wt%, e.g., 2-4 wt%, or 2-3.5 wt%, or 2-3 wt%, calculated on an oxide basis.Embodiment 34. The metallic catalytic component of any of embodiments 1 -33, wherein the refractory oxide support comprises yttrium.Clariant International Ltd 2024US702-WO-PCTEmbodiment 35. The metallic catalytic component of embodiment 34, wherein the yttrium is present in an amount in the range of 0.1-3 wt%, e.g., 0.1 -2 wt%, or 0.1-1 wt%, or 0.1 -0.5 wt%, calculated on an oxide basis.Embodiment 36. The metallic catalytic component of embodiment 34, wherein the yttrium is present in an amount in the range of 0.2-5 wt%, e.g., 0.2-3 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.2-0.7 wt%, calculated on an oxide basis.Embodiment 37. The metallic catalytic component of embodiment 34, wherein the yttrium is present in an amount in the range of 0.5-5 wt%, e.g., 0.5-3 wt%, or 0.5-2 wt%, or 0.5-1 .2 wt%, or 0.5-1 .2 wt%, calculated on an oxide basis.Embodiment 38. The metallic catalytic component of embodiment 34, wherein the yttrium is present in an amount in the range of 1 -5 wt%, e.g., 1 -3 wt%, or 1 -2 wt%, or 1 -1.5 wt%, calculated on an oxide basis.Embodiment 39. The metallic catalytic component of embodiment 34, wherein the yttrium is present in an amount in the range of 2-5 wt%, e.g., 2-4 wt%, or 2-3.5 wt%, or 2-3 wt%, calculated on an oxide basis.Embodiment 40. The metallic catalytic component of any of embodiments 28-39, wherein a total amount of lanthanum and yttrium in the refractory oxide support is at least 0.5 wt%, e.g., at least 0.7 wt%, or at least 1 wt%, or at least 2 wt%, calculated on an oxide basis.Clariant International Ltd 2024US702-WO-PCTEmbodiment 41 . The metallic catalytic component of any of embodiments 1 -40, wherein a total amount of aluminum, zirconium, titanium, cerium, lanthanum and yttrium, in the refractory oxide support is at least at least 70 wt%, for example, in the range of 70-99 wt%, e.g., 70-95 wt%, or 70-90 wt%, calculated on an oxide basis.Embodiment 42. The metallic catalytic component of any of embodiments 1 -40, wherein a total amount of aluminum, cerium, lanthanum and yttrium, in the refractory oxide support is at least 80 wt%, for example, in the range of 80-99 wt%, e.g., 80-98 wt%, or 80-90 wt%, calculated on an oxide basis.Embodiment 43. The metallic catalytic component of any consistent embodiment above, wherein the refractory oxide coating on the substrate comprises: aluminum, present in the refractory oxide coating in an amount in the range of 60-98 wt%, calculated on an oxide basis; cerium, present in the refractory oxide coating in an amount in the range of 2-40 wt%, calculated on an oxide basis; lanthanum, present in the refractory oxide coating in an amount in the range of 0.1 -5 wt%, calculated on an oxide basis; and yttrium, present in the refractory oxide coating in an amount in the range of 0.1-5 wt%, calculated on an oxide basis.Embodiment 44. The metallic catalytic component of any of embodiments 1 -43, wherein a total amount of aluminum, cerium, lanthanum and yttrium, in the refractory oxide support is at least 90 wt%, for example, in the range of 90-99 wt%, e.g., 90-98 wt%, or 90-95 wt%, calculated on an oxide basis.Clariant International Ltd 2024US702-WO-PCTEmbodiment 45. The metallic catalytic component of any of embodiments 1 -43, wherein a total amount of aluminum, cerium, lanthanum and yttrium, in the refractory oxide support is at least 95 wt%, for example, in the range of 95-99 wt%, e.g., 95-98 wt%, calculated on an oxide basis.Embodiment 46. The metallic catalytic component of any of embodiments 1 -6 and 17-45, wherein a total amount of aluminum, cerium, lanthanum and yttrium, in the refractory oxide support is at least at least 70 wt%, for example, in the range of 70-99 wt%, e.g., 70-95 wt%, or 70-90 wt%, calculated on an oxide basis.Embodiment 47. The metallic catalytic component of any of embodiments 1 -6 and 17-45 wherein a total amount of aluminum, cerium, lanthanum and yttrium, in the refractory oxide support is at least 80 wt%, for example, in the range of 80-99 wt%, e.g., 80-98 wt%, or 80-90 wt%, calculated on an oxide basis.Embodiment 48. The metallic catalytic component of any of embodiments 1 -6 and 17-45, wherein a total amount of aluminum, cerium, lanthanum and yttrium, in the refractory oxide support is at least 90 wt%, for example, in the range of 90-99 wt%, e.g., 90-98 wt%, or 90-95 wt%, calculated on an oxide basis.Embodiment 49. The metallic catalytic component of any of embodiments 1 -6 and 17-42, wherein a total amount of aluminum, cerium, lanthanum and yttrium, in the refractory oxide support is at least 95 wt%, for example, in the range of 95-99 wt%, e.g., 95-98 wt%, calculated on an oxide basis.Clariant International Ltd 2024US702-WO-PCTEmbodiment 50. The metallic catalytic component of any consistent embodiment above, wherein the refractory oxide support comprises silica-stabilized zirconia or silica-stabilized titania.Embodiment 51 . The metallic catalytic component of any of embodiments 1 -49, wherein the refractory oxide support further comprises silica, e.g., in an amount up to 30 wt% silicon, e.g., up to 20 wt%, or up to 15 wt%, calculated on an oxide basis.Embodiment 52. The metallic catalytic component of embodiment 51 , wherein silica is present in an amount in the range of 2-30 wt%, e.g., 2-20 wt%, or 2-15 wt%, calculated on an oxide basis.Embodiment 53. The metallic catalytic component of embodiment 51 , wherein silica is present in an amount in the range of 5-30 wt%, e.g., 5-20 wt%, or 5-15 wt%, calculated on an oxide basis.Embodiment 54. The metallic catalytic component of embodiment 51 , wherein silica is present in an amount in the range of 2-10 wt%, e.g., 2-8 wt%, or 2-6 wt%, calculated on an oxide basis.Embodiment 55. The metallic catalytic component of embodiment 51 , wherein silica is present in an amount in the range of 5-10 wt%, e.g., 5-8 wt%, calculated on an oxide basis.Embodiment 56. The metallic catalytic component of any of embodiments 1 -55, wherein the refractory oxide support has a surface area of at least 50 m2 / g, e.g., at least 100 m2 / g, or at least 125 m2 / g, or at least 150 m2 / g, or at least 200 m2 / g, or at least 300 m2 / g.Clariant International Ltd 2024US702-WO-PCTEmbodiment 57. The metallic catalytic component of any of embodiments 1 -56, the catalyst material further comprising one or more catalytic metals disposed on the refractory oxide support.Embodiment 58. The metallic catalytic component of embodiment 57, wherein the one or more catalytic metals include one or more of nickel, ruthenium, rhodium, palladium, platinum, copper, cobalt, silver, chromium, manganese, and molybdenum.Embodiment 59. The metallic catalytic component of embodiment 57, wherein the one or more catalytic metals comprise nickel.Embodiment 60. The metallic catalytic component of any of embodiments 57-59, wherein the one or more catalyst metals comprises one or more of ruthenium, rhodium, palladium, or platinum, for example, in combination with nickel.Embodiment 61 . The metallic catalytic component of embodiment 60, wherein an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is at least 0.005:1 , e.g., at least 0.01 :1 , or at least 0.015:1 .Embodiment 62. The metallic catalytic component of embodiment 60 or embodiment 61 , wherein an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is up to 100:1 , e.g., up to 10:1 , or up to 5:1.Clariant International Ltd 2024US702-WO-PCTEmbodiment 63. The metallic catalytic component of embodiment 60 or embodiment 61 , wherein an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is up to 1 :1 , e.g., up to 0.5:1 , or up to 0.2:1 .Embodiment 64. The metallic catalytic component of embodiment 60 or embodiment 61 , wherein an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is up to 0.1 :1 , e.g., up to 0.05:1 , or up to 0.03:1 .Embodiment 65. The metallic catalytic component of embodiment 60, wherein an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is in the range of 0.005:1 to 100:1 , e.g., 0.005:1 to 10:1 , or 0.005:1 to 5:1 , or 0.005:1 to 1 :1 , or 0.005:1 to 0.5:1 , or 0.005:1 to 0.2:1 , or 0.005:1 to 0.1 :1 , or 0.005:1 to 0.05:1 , or 0.005:1 to 0.03:1.Embodiment 66. The metallic catalytic component of embodiment 60, wherein an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is in the range of 0.01 :1 to 100:1 , e.g., 0.01 :1 to 10:1 , or 0.01 :1 to 5:1 , or 0.01 :1 to 1 :1 , or 0.01 :1 to 0.5:1 , or 0.01 :1 to 0.2:1 , or 0.01 :1 to 0.1 :1 , or 0.01 :1 to 0.05:1 , or 0.01 :1 to 0.03:1 .Embodiment 67. The metallic catalytic component of embodiment 60, wherein an atomic ratio of the total amount of ruthenium, rhodium, palladium, and platinum to the amount of nickel is in the range of 0.015:1 to 100:1 , e.g., 0.015:1 to 10:1 , or 0.015:1 to 5:1 , or 0.015:1 to 1 :1 , or 0.015:1 to 0.5:1 , or 0.015:1 to 0.2:1 , or 0.015:1 to 0.1 :1 , or 0.015:1 to 0.05:1 , or 0.015:1 to0.03:1.Clariant International Ltd 2024US702-WO-PCTEmbodiment 68. The metallic catalytic component of embodiment 57, wherein the one or more catalytic metals comprises rhodium.Embodiment 69. The metallic catalytic component of embodiment 57, wherein the one or more catalytic metals comprises ruthenium.Embodiment 70. The metallic catalytic component of any of embodiments 57-69, wherein the one or more catalytic metals are present in a total amount up to 20 wt%, e.g., up to 15 wt%, up to 10 wt%, up to 5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%.Embodiment 71 . The metallic catalytic component of any of embodiments 57-69, wherein the one or more catalytic metals are present in a total amount in the range of 0.001-20 wt%, e.g., in the range of 0.001-15 wt%, or 0.001 -10 wt%, or 0.001 -5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%.Embodiment 12.. The metallic catalytic component of any of embodiments 57-69, wherein the one or more catalytic metals are present in a total amount in the range of 0.1 -20 wt%, e.g., in the range of 0.1 -15 wt%, or 0.1 -10 wt%, or 0.1 -5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%.Embodiment 73. The metallic catalytic component of any of embodiments 57-69, wherein the one or more catalytic metals are present in a total amount in the range of 0.5-20 wt%, e.g., in the range of 0.5-15 wt%, or 0.5-10 wt%, or 0.5-5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%.Clariant International Ltd 2024US702-WO-PCTEmbodiment 74. The metallic catalytic component of any of embodiments 57-69, wherein the one or more catalytic metals are present in a total amount in the range of 1-20 wt%, e.g., in the range of 1-15 wt%, or 1 -10 wt%, or 1 -5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%.Embodiment 75. The metallic catalytic component of any of embodiments 57-69, wherein the one or more catalytic metals are present in a total amount in the range of 2-20 wt%, e.g., in the range of 2-15 wt%, or 2-10 wt%, or 2-5 wt%, calculated on an elemental basis with reference to a mass of the refractory oxide support of 100 wt%.Embodiment 76. The metallic catalytic component of any of embodiments 1 -75 wherein the metallic substrate is formed from a metal selected from alloys containing iron and chromium, e.g., iron-chromium-aluminum alloys, nickel-chromium-iron alloys and iron-chromium alloys, each optionally with aluminum, or molybdenum, and / or niobium.Embodiment 77. The metallic catalytic component of any of embodiments 1 -75 wherein the metallic substrate is formed from a metal selected from nickel-chromium alloys, optionally with iron, aluminum, molybdenum, and / or niobium.Embodiment 78. The metallic catalytic component any of embodiments 1 -75, wherein the metallic substrate is formed from stainless steel.Embodiment 79. The metallic catalytic component of any of embodiments 1 -78, wherein the metallic substrate is in the form of a foil or a sheet, e.g., a corrugated foil or sheet.Clariant International Ltd 2024US702-WO-PCTEmbodiment 80. The metallic catalytic component of embodiment 79, wherein the foil or sheet has a thickness in the range of 0.025-3 mm, e.g., in the range of 0.025-1 mm, or 0.025- 0.5 mm, or 0.025-0.1 mm, or 0.05-3 mm, or 0.05-1 mm, or 0.05-0.5 mm, or 0.1-3 mm, or 0.1 -1 mm.Embodiment 81 . The metallic catalytic component of any of embodiments 1 -80, wherein the metallic substrate has a honeycomb, channel, or foam substructure that allows gases to pass therethrough.Embodiment 82. The metallic catalytic component of any of embodiments 1 -81 , wherein the metallic substrate has a structured surface comprising a plurality of subsurfaces, e.g., has a corrugated surface or a surface comprising a plurality of slats.Embodiment 83. The metallic catalytic component of any of embodiments 1 -82, wherein the metallic substrate is flexible.Embodiment 84. The metallic catalytic component of any of embodiments 1 -83, wherein the catalyst material is disposed on the metallic substrate with a loading in the range of 30-200 g / m2, e.g., in the range of 30-180 g / m2, or 50-200 g / m2, or 50-180 g / m2, or 70-200 g / m2, or 70- 180 g / m2.Embodiment 85. The metallic catalytic component of any of embodiments 1 -84, enclosed by an enclosure (e.g., a tube or a canister), the enclosure and the metallic catalytic component defining a volume.Clariant International Ltd 2024US702-WO-PCTEmbodiment 86. The metallic catalytic component of embodiment 85, wherein the metallic catalytic component is held in a flexed position in the enclosure.Embodiment 87. The metallic catalytic component of embodiment 85 or embodiment 86, wherein the catalyst material is present in the volume in an amount in the range of 25-300 g catalyst material per liter of enclosed volume, e.g., in the range of 25-200 g / L, or 50-300 g / L, or 50-200 g / L, or 100-300 g / L, or 100-200 g / L.Embodiment 88. The metallic catalytic component of embodiment 87, wherein the one or more catalytic metals are present in the volume in an amount of at least 0.1 g / L, e.g., at least 0.5 g / L, at least 1 g / L or at least 2 g / L, e.g., 0.1-30 g / L, or 0.5-30 g / L, or 1-30 g / L, or 2-30 g / L, or 0.1-20 g / L, or 0.5-20 g / L, or 1-20 g / L, or 2-20 g / L, or 0.1 -10 g / L, or 0.5-10 g / L or 1-10 g / L, or 2- 10 g / L , on an elemental basis.Embodiment 89. A process for preparing a metallic catalytic component of any of embodiments 1-88, the method comprising: providing a metallic substrate; providing a suspension of refractory oxide components in a first aqueous liquid; coating the metallic substrate with the suspension to provide a wet coating on the substrate; and drying and calcining the wet-coated substrate to provide a refractory oxide coating on the substrate.Embodiment 90. The process of embodiment 89, wherein the substrate is provided while disposed inside or around a holder to maintain a particular shape during the coating.Clariant International Ltd 2024US702-WO-PCTEmbodiment 91 . The process of embodiment 88 or embodiment 90, wherein the metallic substrate is coated with the suspension by brush-painting, by high-pressure air spray coating, or by dipping the metallic substrate into the suspension.Embodiment 92. The process of any of embodiments 89-91 , wherein at least a portion of the refractory oxide components are provided in colloidal form.Embodiment 93. The process of any of embodiments 89-92, wherein one or more catalytic metals are included in the washcoat suspension in particulate form, e.g., in the form of oxides or insoluble salts such as carbonates.Embodiment 94. The process of any of embodiments 89-92, further comprising providing a solution of one or more catalytic metals in a second aqueous liquid; applying the solution of one or more catalytic metals to the refractory oxide coating to impregnate the refractory oxide coating therewith; drying and calcining the impregnated refractory-oxide coated substrate.Embodiment 95. A metallic catalytic component made by the process of any of embodiments 89-94.Embodiment 96. A process for installing a metallic catalytic component any of embodiments 1-88 and 95 in an enclosure, the process comprising flexing the metallic catalytic component to fit through an aperture of the enclosure.Clariant International Ltd 2024US702-WO-PCTEmbodiment 97. The metallic catalytic component of embodiments 1-88 and 95, enclosed by an enclosure (e.g., a tube or a canister), the enclosure and the metallic catalytic component defining a volume.Embodiment 98. The metallic catalytic component of embodiment 97, wherein the metallic catalytic component is held in a flexed position in the enclosure.Embodiment 99. The metallic catalytic component of embodiment 97 or embodiment 98, wherein the catalyst material is present in the volume in an amount in the range of 25-300 g catalyst material per liter of enclosed volume, e.g., in the range of 25-200 g / L, or 50-300 g / L, or 50-200 g / L, or 100-300 g / L, or 100-200 g / L.Embodiment 100. The metallic catalytic component of embodiment 99, wherein the one or more catalytic metals are present in the volume in an amount of at least 0.1 g / L, e.g., at least 0.5 g / L, at least 1 g / L or at least 2 g / L, e.g., 0.1-30 g / L, or 0.5-30 g / L, or 1-30 g / L, or 2-30 g / L, or 0.1 -20 g / L, or 0.5-20 g / L, or 1-20 g / L, or 2-20 g / L, or 0.1 -10 g / L, or 0.5-10 g / L or 1-10 g / L, or 2- 10 g / L , on an elemental basis.Embodiment 101. A process for reacting a feedstock to provide hydrogen, the process comprising: providing a metallic catalytic component of any of embodiments 1-88 and 95 and comprising one or more catalytic metals, wherein at least a portion (e.g., at least 10 atom%, at least 25 atom% or at least 50 atom%) of the catalytic metal(s) is in a metallic form;Clariant International Ltd 2024US702-WO-PCT contacting the metallic catalytic component with a feed stream comprising one or more of C1-C4 alkanes and ammonia and, optionally, water and / or carbon dioxide, at a reaction temperature of at least 500 °C to provide a stream comprising hydrogen.Embodiment 102. The process of embodiment 101 , wherein the reaction temperature is in the range of 500-900 °C.Embodiment 103. The process of embodiment 101 or embodiment 102, wherein the feed stream comprises methane and water, and the product stream includes carbon monoxide and hydrogen.Embodiment 104. The process of embodiment 101 or embodiment 102, wherein the feed stream comprises methane and carbon dioxide, and the product stream includes carbon monoxide and hydrogen.Embodiment 105. The process of embodiment 101 or embodiment 102, wherein the feed stream comprises propane and / or butane and water, and the product stream includes carbon monoxide and hydrogen.Embodiment 106. The process of embodiment 101 or embodiment 102, wherein the feed stream comprises ammonia, and the product stream includes nitrogen and hydrogen.

[0115] The particulars shown herein are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard,Clariant International Ltd 2024US702-WO-PCT no attempt is made to show structural details of the invention in more detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings and / or examples making apparent to those skilled in the art how the several forms of the invention may be embodied in practice. Thus, before the disclosed processes and devices are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatuses, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

[0116] The terms “a,” “an,” “the” and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0117] All methods described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0118] Unless the context clearly requires otherwise, throughout the description and the claims, the words ‘comprise’, ‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singularClariant International Ltd 2024US702-WO-PCT number, respectively. Additionally, the words “herein,” “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

[0119] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase “consisting of” excludes any element, step, ingredient or component not specified. The transition phrase “consisting essentially of” limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

[0120] Unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0121] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0122] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deletedClariant International Ltd 2024US702-WO-PCT from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

[0123] Some embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

[0124] Furthermore, it is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, but not of limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. Accordingly, the present invention is not limited to that precisely as shown and described.

Claims

Clariant International Ltd 2024US702-WO-PCTWhat is claimed is1 . A metallic catalytic component comprising: a metallic substrate, wherein the metallic substrate is flexible; and disposed on the metallic substrate, a catalyst material comprising a refractory oxide support.

2. The metallic catalytic component of claim 1 , wherein the refractory oxide support comprises rare earth-stabilized alumina, rare earth-stabilized zirconia, or rare earth-stabilized titania.

3. The metallic catalytic component of claim 1 , wherein the refractory oxide support comprises one or more rare earths selected from cerium, lanthanum and yttrium.

4. The metallic catalytic component of claim 3, wherein cerium is present in the refractory oxide support in an amount in the range of 2-35 wt%, calculated on an oxide basis.

5. The metallic catalytic component of claim 4, wherein a total amount of lanthanum and yttrium in the refractory oxide support is at least 0.5 wt%, calculated on an oxide basis.

6. The metallic catalytic component claim 1 , wherein the refractory oxide coating on the substrate comprises: aluminum, present in the refractory oxide coating in an amount in the range of 60-98 wt%, calculated on an oxide basis; cerium, present in the refractory oxide coating in an amount in the range of 2-40 wt%, calculated on an oxide basis;Clariant International Ltd 2024US702-WO-PCT lanthanum, present in the refractory oxide coating in an amount in the range of 0.1 -5 wt%, calculated on an oxide basis; and yttrium, present in the refractory oxide coating in an amount in the range of 0.1-5 wt%, calculated on an oxide basis.

7. The metallic catalytic component of claim 1 , wherein the refractory oxide support comprises silica-stabilized zirconia or silica-stabilized titania.

8. The metallic catalytic component of claim 7, wherein silica is present in an amount in the range of 2-30 wt%, calculated on an oxide basis.

9. The metallic catalytic component of claim 1 , the catalyst material further comprising one or more catalytic metals disposed on the refractory oxide support.

10. The metallic catalytic component of claim 9, wherein the one or more catalytic metals include one or more of nickel, ruthenium, rhodium, palladium, platinum, copper, cobalt, silver, chromium, manganese, and molybdenum.11 . The metallic catalytic component of claim 10, wherein the one or more catalytic metals comprise nickel.

12. The metallic catalytic component of claim 9, wherein the one or more catalyst metals comprises one or more of ruthenium, rhodium, palladium, or platinum, for example, in combination with nickel.Clariant International Ltd 2024US702-WO-PCT13. The metallic catalytic component of claim 1 , wherein the metallic substrate is in the form of a foil or a sheet, e.g., a corrugated foil or sheet.

14. A process for preparing a metallic catalytic component of claim 1 , the method comprising: providing a metallic substrate; providing a suspension of refractory oxide components in a first aqueous liquid; coating the metallic substrate with the suspension to provide a wet coating on the substrate; and drying and calcining the wet-coated substrate to provide a refractory oxide coating on the substrate.

15. A process for reacting a feedstock to provide hydrogen, the process comprising: providing a metallic catalytic component of claim 1 and comprising one or more catalytic metals, wherein at least 10 atom% of the catalytic metal(s) is in a metallic form; contacting the metallic catalytic component with a feed stream comprising one or more of C1-C4 alkanes and ammonia and, optionally, water and / or carbon dioxide, at a reaction temperature of at least 500 °C to provide a stream comprising hydrogen.

Images