Catalyst support

Abstract

There is described a support for a catalyst and a supported catalyst. The support / catalyst comprises ceramic material and may comprise catalytic material. The support / catalyst has a pore size distribution wherein ≥20% of the pores have a pore size diameter of ≥5 µm. Also described is a method for making the support / catalyst and methods for the use of the support / catalyst, such as in pre-reforming, steam reforming and shift conversion reactions.

Description

CATALYST SUPPORTFIELD

[0001] The present disclosure relates to a support for a catalyst and a supported catalyst. More specifically, the present disclosure relates to a support and a supported catalyst for use in pre-reforming, steam reforming and / or shift conversion. The disclosure extends to a method for the production of syngas (hydrogen and carbon monoxide), or down-stream derivative thereof, using the catalyst.BACKGROUND

[0002] Steam methane reforming (SMR) is a method of producing syngas by reaction of hydrocarbons with water. Syngas is a mixture of hydrogen and carbon monoxide in various ratios that is used globally, on an industrial scale, as a source of hydrogen or as a fuel. For example, syngas is used in the industrial preparation of ammonia, methanol, lubricants, and oxo alcohols. Syngas is also used to directly reduce iron ore.

[0003] Pre-reforming is the process by which heavier hydrocarbons and methane are steam reformed, with some reformed products methanated, to increase the methane content of the exiting gas to SMR. In addition, another requirement of the pre-reformer is to tolerate and remove sulphur in the form of hydrogen sulphide from the feed stream.

[0004] A pre-reforming step is common in modern SMR plants. The adiabatic pre-reformer is usually positioned upstream of the main steam reformer and conventionally uses a catalyst with high nickel content and small pellet size.

[0005] Pre-reforming increases feed flexibility, reduces energy consumption and lower investment costs.

[0006] Three desired reactions occur in the pre-reformer and each of them will reach equilibrium:Steam reforming reactionCH4+ H2O CO + 3H2CnHm + nH2O — > nCO + (n+m / 2)H2Water gas shift reactionCO + H2O H2+ CO2MethanationCO + 3H2CH4+ H2O

[0007] The overall reaction is endothermic for a light feed (e.g. natural gas), while for heavier feeds, such as LPG (liquefied petroleum gas), the overall reaction is exothermic. For naphtha, there is an endotherm, followed by an exotherm. Overall, for heavier feeds the reaction is exothermic.

[0008] Carbon laydown is a major deactivation mechanism for pre-reforming catalysts, particularly when processing heavier feedstock such as naphtha. There are two different types of carbon laydown which cause issues. These are (i) polymeric gum, which occurs when the pre-reformer temperature is too low, and (ii) whisker carbon, which occurs when the temperature is too high.

[0009] Therefore, a catalyst / catalyst bed with higher activity and improved resistance to carbon deposition is desired.

[0010] There is a requirement for a further improved catalyst for use in the production of syngas. It is therefore an object of aspects of the present disclosure to address one or more of the above-mentioned, or other, problems.SUMMARY

[0011] According to a first aspect of the disclosure there is provided a support for a catalyst, wherein the support comprises ceramic material; and wherein the support has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm.

[0012] The support may be operable to be formed into a catalyst for use in a packed-bed reactor for the production of syngas, or a derivative thereof, such as in pre-reforming, steam reforming and / or shift conversion. The support may be a supported catalyst by further comprising catalytic material.

[0013] According to a second aspect of the disclosure there is provided a catalyst, wherein the catalyst comprises ceramic material and catalytic material, wherein the catalyst has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm.

[0014] According to a third aspect of the disclosure there is provided a method for producing a support or supported catalyst, comprising: a. contacting a composition for producing a support / supported catalyst, suitably a composition, such as a gel-cast composition, with an initiator and optionally a polymerisation accelerator; b. arranging the resulting composition of step (a) in a mould;c. demoulding the composition to produce a green body, d. optionally, drying the green body at room temperature or baking the green body at elevated temperature; e. calcining the green body; f. optionally, contacting the support with catalytic material. g. optionally, calcining the product of step f.

[0015] According to a fourth aspect of the disclosure there is provided an apparatus comprising a reactor, such as for pre-reforming, steam reforming and / or shift conversion, wherein the reactor comprises a packing member and / or catalyst, such as in a packed bed, wherein the packing member / catalyst comprises ceramic material, a catalytic material (when present), and wherein the packing member / catalyst has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm.

[0016] According to a fifth aspect of the disclosure, there is provided a method for the production of methane, such as from higher hydrocarbons, for example a pre-reforming method, wherein the method comprises a catalyst bed, wherein catalyst bed comprises a packing member or catalyst comprising ceramic material, a catalytic material (when present), and wherein the packing member / catalyst has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm, to produce methane.

[0017] According to a sixth aspect of the disclosure, there is provided a method for the production of carbon oxides and hydrogen (or syngas), such as from methane, for example a steam reforming method, wherein the method comprises a catalyst bed, wherein catalyst bed comprises a packing member or catalyst comprising ceramic material, a catalytic material (when present), and wherein the packing member / catalyst has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm, to produce the carbon oxides and hydrogen.

[0018] According to a seventh aspect of the disclosure, there is provided a method for the production of carbon dioxide and hydrogen, such as from carbon monoxide and water (or syngas feed), for example a shift conversion method, wherein the method comprises a catalyst bed, wherein catalyst bed comprises a packing member or catalyst comprising ceramic material, a catalytic material (when present), and wherein the packing member / catalyst has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm, to produce the carbon dioxide and hydrogen.

[0019] Advantageously, the support / supported catalyst of the present disclosure may provide improved catalyst activity, reduced pressure drop and / or improved catalyst strength. The supported catalyst may advantageously provide improved resistance to carbon deposition and / or improved sulphur pick-up.

[0020] The support / supported catalyst of the present disclosure may improve the accessibility of reactant gases to active sites within the catalyst, especially for lower temperature reaction applications, such as pre-reforming reactions and shift reactions.

[0021] The improved strength that may be achieved with supports / supported catalysts of the present disclosure may provide increased lifetime and reduced waste.

[0022] The uniform packing and / or relative large size of a support / supported catalyst as described herein may reduce the pressure drop across the reactor thereby reducing operating costs. The support / supported catalyst of the present disclosure may provide improved uniformity in the void space within a packed column while also significantly reducing the flow dead zone relative to the pellet volume.

[0023] The support / supported catalysts may further provide a combination of desirable properties including high selectivity (such as >90%), long lifetime (such as 3-4 years), low cost, high attrition and / or high crush strength as desired.

[0024] References hereon to ‘support’ includes a reference to the catalyst of the disclosure, where applicable.

[0025] The support may have a pore size distribution wherein >25% of the pores have a pore size diameter of >5 pm, such as >30%, or >35%.

[0026] The support may have a pore size distribution wherein >20% of the pores have a pore size diameter of >10 pm, such as >25%, or >30%.

[0027] The support may have a pore size distribution wherein >30% of the pores have a pore size diameter of >1 pm, such as >40%, >50%, >60% or >70%.

[0028] The support may have a pore size distribution wherein <30% of the pores have a size of <0.1 pm, such as <20%, <15%, <10%, or <5%. The support may have a pore size distribution wherein <20% of the pores have a size of <0.05pm, such as <15%, <10%, <7.5%, or <5%. The support may have a pore size distribution wherein <10% of the pores have a size of <0.02 pm, such as <7%, <5%, or <3%.

[0029] Total pore volume, pore size and pore size distribution as used herein were measured by mercury intrusion porosimetry, using ASTM D4284 - 12(2017)e1 , StandardTest Method for Determining Pore Volume Distribution of Catalysts and Catalyst Carriers by Mercury Intrusion Porosimetry. It is understood that references to pore size are references to pore diameter.

[0030] The support may have a multimodal pore size distribution. The term multimodal distribution as used herein means a distribution having two or more modes (represented as peaks / local maxima). The modes of a multimodal distribution may be independent or may overlap.

[0031] The support may have a multimodal pore size distribution comprising at least a first mode and a second mode, wherein the first mode has a local maxima at a pore size diameter of >50 nm, such as >500nm or >750nm, or >1 urn, and the second mode has a local maxima at a pore size diameter of >50 nm, such as >5um, or >10um.

[0032] The support may have a multimodal pore size distribution comprising at least a first mode and a second mode, wherein at least 20%, such as at least 30%, or at least 40% of the pores are present as the first mode, and wherein at least 20%, such as at least 25%, or at least 30% of the pores are present as the second mode.

[0033] The support may have a BET specific surface area of >0.8 m2 / g, such as >1 m2 / g, or >1 .2 m2 / g. The support may have a BET specific surface area of <5 m2 / g, such as <3 m2 / g, or <2 m2 / g. The support may have a BET specific surface area of from 0.8 to 5 m2 / g, such as from 1 to 3 m2 / g, or from 1.2 to 2 m2 / g.

[0034] Specific surface area as used herein was measured with BET analysis, using ASTM-D3663-20, “Standard Test Method for Surface Area of Catalysts and Catalyst Carriers”.

[0035] The support may have a total pore volume of >0.3 cm3 / g, such as >0.35 cm3 / g, or >0.4 cm3 / g. The support may have a total pore volume of <0.7 cm3 / g, such as <0.6 cm3 / g, or <0.5 cm3 / g. The support may have a total pore volume of from 0.3 to 0.7 cm3 / g, such as from 0.35 to 0.6 cm3 / g or from 0.4 to 0.5 cm3 / g.

[0036] The support may have a macrostructure selected from multi-lobe, for example a trilobe, quadralobe or pentalobe; a ring; a sphere; an ellipsoid, a cube; a cuboid; a cylinder; or a cog.

[0037] The support may have a substantially spherical and / or ellipsoidal macrostructure.

[0038] The macrostructure may comprise at least one linear groove on the outer face of the macrostructure, such as at least two, at least three or at least four linear grooves.The macrostructure comprises at least two linear parallel grooves, such as at least three or at least four. The grooves may be substantially hemispherical in a lateral crosssection. The outer face of the macrostructure may be free of linear grooves.

[0039] The support may comprise a fluid communication intra-particle channel extending through the support from a first aperture on a first side of the support to a second aperture on a substantially opposing second side of the support.

[0040] The support / supported catalyst may not comprise a fluid communication intra- particle channel extending through the support / supported catalyst from a first aperture on a first side of the support / supported catalyst to a second aperture on a substantially opposing second side of the support / supported catalyst.

[0041] When the support / supported catalyst does not comprise a fluid communication intra-particle channel, fluid may substantially not be able to flow through the support / supported catalyst in use from a first side of the support / supported catalyst to a substantially opposite second side of the support / supported catalyst. Accordingly, to pass the support / supported catalyst fluid may be forced to flow around the outer surface of the support / supported catalyst. As such, in the context of the present disclosure, the phrase “does not comprise a fluid communication intra-particle channel extending through the support / supported catalyst from a first aperture on a first side of the support / supported catalyst to a second aperture on a substantially opposing second side of the support / supported catalyst” may be interpreted to mean that substantially no fluid flow is achieved through the body of the support / supported catalyst in use from a first side of the support / supported catalyst to a substantially opposite second side of the support / supported catalyst. Typically, the “fluid communication intra-particle channels” refers to channels formed by the shape of the mould, or by a post-moulding process. It will be understood that such “fluid communication intra-particle channels” in the context of the present disclosure do not include microscopic porosity (such as of <500um in diameter, or <250um) that may be present in the material of the support / supported catalyst.

[0042] The support / supported catalyst may comprise no fluid communication intra-particle channels in the support / supported catalyst extending from a first aperture to a second aperture.

[0043] Advantageously, it has surprisingly been found that the combination of surface structures with the absence of a flow channel through the body of the support / supportedcatalyst leads to increased strength while also increasing flow speed, directing flow over the surface and providing a more uniform flow for the production of an alkylene oxide.

[0044] The support may have a largest dimension of at least 6 mm, such as at least 9, at least 11 mm, at least 15 mm. The support may have a largest dimension of up to 35mm, such as up to 25mm, up to 20mm.

[0045] The support may comprise surface structures on the outer face of the macrostructure.

[0046] The height, suitably the mean average height, of the surface structures of the support may be up to 30% of the largest dimension of the support, such as up to 20%, preferably up to 15%.

[0047] By “surface structures” it is meant structures that represent a deviation of the shape of the outer surface of the support / supported catalyst from the shape that would be expected based on the macrostructure of the support / supported catalyst. Such surface structures may be significantly smaller than the size of the features of the macrostructure of the support / supported catalyst. The surface structures may be considered to be surface texturing on the macrostructure of the support / supported catalyst. It will be understood that such “surface structures” in the context of the present disclosure do not include microscopic surface roughness.

[0048] For example, the support / supported catalyst may have a spherical macrostructure with a diameter of 10 mm. The outer surface of the said support / supported catalyst is partially consistently curved as would be expected for a spherical macrostructure, but the outer surface of the support / supported catalyst also comprises a plurality of surface structures that deviate from the expected curved shape of the outer surface in the form of 12 discrete mounds wherein each mound has a height of 2mm.

[0049] It will be appreciated that normal features of macrostructures such as the castellations of a cog or the lobes of multilobe are considered to be part of the macrostructure and are not considered to be surface structures according to the present disclosure.

[0050] The support / supported catalyst may comprise surface structures on at least two sides of the support / supported catalyst.

[0051] The support / supported catalyst may comprise surface structures extending over >20% of the outer surface of the support / supported catalyst, such as over >30%, >40%, >60% or >80% of the outer surface.

[0052] By “comprise surface structures extending over”, it is meant that at least the specified percentage of the outer surface of the support / supported catalyst deviates from the expected shape of the outer surface of the support / supported catalyst based on the macrostructure. It will be appreciated that the amount of the surface that deviates is calculated based on the surface area of the expected shape of the outer surface, and missing portions thereof, rather than on the surface area of the surface structures. For example, the support / supported catalyst may have a spherical macrostructure with an expected outer surface area of 314 cm2, of which 200 cm2deviates from the expected consistent curvature of a spherical macrostructure, and as such the support / supported catalyst comprises surface structures extending over 63% of the outer surface. For the purposes of this calculation, the expected outer surface area that is occupied by any apertures connecting a fluid communication channel is added to the sum of the remaining expected outer surface area.

[0053] The height, suitably the mean average height, of the surface structures of the support / supported catalyst may be <10mm, preferably <7mm, more preferably <6mm, most preferably <5mm. The height, suitably the mean average height, of the surface structures of the support / supported catalyst may be >0.1 mm, such as >0.3mm, preferably >0.5mm, more preferably >0.7mm, most preferably >0.8mm. The height of the surface structures herein is measured using callipers with a depth measurement function. It will be appreciated that “height” in this context refers to the distance from the lowest point of the surface structure to the highest point of the surface structure.

[0054] The support / supported catalyst may comprise a plurality of repeating surface structures having substantially the same shape. Preferably, the support / supported catalyst comprises at least 5 repeating surface structures, more preferably at least 10, such as at least 15, or at least 20, most preferably at least 25.

[0055] A surface structure may be in the form of a ridge, trough, mound and / or depression.

[0056] A surface structure in the form of a ridge or trough is typically elongate and may be in the form of an annular ridge / trough, wherein said annular ridge / trough is not restricted to a circular ring shape. The annular ridge / trough may be in the form of a substantially circular shape or a regular convex polygon, such as a triangle, square, pentagon, hexagon, heptagon, octagon, nonagon, or decagon. Preferably the annular ridge / trough is in the form of a regular convex polygon, more preferably pentagon, hexagon or heptagon, most preferably hexagon. The portion of the outer surface that is contained within an annular ridge / trough may be according to the expected shape of the outersurface of the supported catalyst or may be flat, sloped and / or curved. For example, the portion of the outer surface contained within an annular ridge may be in the form of an inverted pyramid. The surface structures may comprise a plurality of connected annular ridge / trough structures, suitably interconnected annular ridge / trough structures such that a ridge of at least a first annular surface structure forms part of a second annular surface structure.

[0057] A surface structure in the form of a mound or depression may be a curved, pyramidal and / or stepped mound / depression. A stepped mound / depression may comprise between 2 to 10 steps, such as between 3 and 8 steps. The mound or depression may interconnect such that adjacent mounds / depressions abut or are merged together.

[0058] The support / supported catalyst may comprise surface structures extending over <20% of the outer surface of the support / supported catalyst, such as over <10%, or <5%. The support / supported catalyst may be substantially free of surface structures on the outer surface of the support / supported catalyst.

[0059] The support / supported catalyst may comprise a substantially uniform outer face according to the macrostructure of the support / supported catalyst. As used herein “uniform outer face” may mean <10% deviation by area from an equivalent uniform surface of an identically sized macrostructure body, such as <5% or <2%. For example, a 16mm spherical macrostructure may have an equivalent uniform outer face surface area of 804 mm2, wherein the support of the present disclosure has an outer face wherein <10% of the outer face of the support deviates from the equivalent uniform outer face, such that the claim support has a uniform outer face surface area of 723 mm2.

[0060] The support / supported catalyst, such as a support / supported catalyst having a diameter or largest dimension of >8mm, or >9mm, such as <17mm to >8mm, or packed bed, may have a geometric surface area per volume (GSA) of >0.7cm2 / cm3, such as a GSA of >1cm2 / cm3, preferably a GSA of >1.2cm2 / cm3, more preferably a GSA of >1 .3cm2 / cm3, most preferably a GSA of >1.4cm2 / cm3.

[0061] The support / supported catalyst, such as a support / supported catalyst having a diameter or largest dimension of <10mm to >5mm, or packed bed, may have a GSA of >1.2cm2 / cm3, such as >1.5cm2 / cm3, preferably a GSA of >1.7cm2 / cm3, more preferably a GSA of >1.9cm2 / cm3, most preferably a GSA of >2.1cm2 / cm3.

[0062] The support / supported catalyst, such as a support / supported catalyst having a diameter or largest dimension of <9mm, such as <9mm to >7mm, or packed bed, may have a GSA of >1.3cm2 / cm3, such as >1.4cm2 / cm3, preferably a GSA of >1.5cm2 / cm3, more preferably a GSA of >1.6cm2 / cm3, most preferably a GSA of >1.7cm2 / cm3.

[0063] The support / supported catalyst, such as a support / supported catalyst having a diameter or largest dimension of <7mm, such as <7mm to >5mm, or packed bed, may have a GSA of >1.7cm2 / cm3, such as >1.8cm2 / cm3, preferably a GSA of >1.9cm2 / cm3, more preferably a GSA of >2.0cm2 / cm3, most preferably a GSA of >2.1cm2 / cm3.

[0064] GSA per volume herein is calculated by measuring the external dimensions of the support / supported catalyst, including all macrostructure and surface structure features and calculating the surface area. The calculated surface area is then divided by the calculated volume of the support / supported catalyst. Suitable 3D modelling software can be used to provide these calculations.

[0065] The support / supported catalyst, such as a support / supported catalyst having a diameter or largest dimension of >9 mm may have a side crush strength of > 3 kg / mm, such as > 5 kg / mm or > 7 kg / mm.

[0066] The support / supported catalyst, such as a support / supported catalyst having a diameter or largest dimension of > 11 mm, may have a side crush strength of >3kg / mm, such as > 5 kg / mm, > 7 kg / mm or > 9 kg / m.

[0067] The support / supported catalyst, such as a support / supported catalyst having a diameter or largest dimension of > 15 mm, may have a side crush strength of >3kg / mm, such as > 5 kg / mm, > 7 kg / mm or > 9 kg / m.

[0068] Side crush strength as used herein was measured by ASTM D4179.

[0069] The support / supported catalyst of the present disclosure may be a cast support, such as a gel cast support, suitably by slip casting. The support may be obtainable by cast moulding, such as a by gel cast moulding.

[0070] The surface structures of the support, when present, may be formed during the moulding step of the support, i.e. the step in which the green body of the support is formed, suitably by appropriate formations provided in the shape of the mould. As such, the surface structures may not be post-fabricated after the moulding of the green body of the support.

[0071] The support may be obtainable by gel casting a composition comprising a ceramic material, an organic binder component and optionally a pore forming material.

[0072] The support may be formed from a cast moulding composition, preferably a gel cast moulding composition. The support may be formed from a moulding composition comprising an organic binder component, a ceramic material, and optionally a pore forming material.

[0073] The organic binder component may be operable to be substantially removed from the support after moulding of the support, such as with heat treatment. The organic binder may be removed by calcination of the support.

[0074] The organic binder component may comprise a polymerisable component, suitably including a polymerisable monomer and a crosslinking member, wherein the binder component is operable to polymerise to form a (co)polymer.

[0075] The polymerisable monomer may comprise one or more type of ethylenically unsaturated monomers, such as an acrylic monomer or derivative thereof such as an acrylamide monomer, and / or a vinyl monomer, such as a monomer selected from one or more of methacrylamide (MAM), N-(hydroxymethyl)acrylamide (hMAM), hydroxyethyl acrylamide (hEAM) and / or N-vinyl-2-pyrrolidinone (NVP). Preferably, the polymerisable monomer comprises one or more acrylamide monomers, more preferably a monomer selected from one or more of methacrylamide (MAM), N-(hydroxymethyl)acrylamide (hMAM) and hydroxyethyl acrylamide (hEAM). Most preferably, the polymerisable monomer comprises MAM.

[0076] The crosslinking member may be selected from one or more of a diethylenically unsaturated monomer, such as a diacrylic monomer or derivative thereof such as a diacrylamide monomer; an acrylic salt and / or a polyethylene glycol substituted acrylic monomer. The crosslinking member may be selected from one or more of poly(ethylene glycol) di methacrylate (PEGDMA), N,N’-methylenebis(acrylamide) (BIS), ammonium acrylate and PEG methylethylmethacrylate (PEGMEM), preferably one more of poly(ethylene glycol) dimethacrylate (PEGDMA), and N,N’-methylenebis(acrylamide) (BIS).

[0077] The organic binder component may be formed from 40 to 95wt% of polymerisable monomer and from 60 to 5wt% of crosslinking member, such as from 50 to 90wt% of polymerisable monomer and from 50 to 10wt% of crosslinking member, or from 55 to 85wt% of polymerisable monomer and from 45 to 15wt% of crosslinking member, or from60 to 80wt% of polymerisable monomer and from 40 to 20wt% of crosslinking member, such as from 65 to 75wt% of polymerisable monomer and from 35 to 25wt% of crosslinking member.

[0078] The composition may further comprise a polymerisation accelerator, operable to accelerate the polymerisation of the binder component. The polymerisation accelerator may be any suitable accelerator. For example, the accelerator may be tetramethylethylenediamine (TEMED).

[0079] The composition may further comprise an initiator operable to initiate polymerisation of the binder component. The initiator may be any suitable initiator. The initiator may be a free radical initiator. For example, the initiator may be ammonium persulphate and / or potassium persulphate.

[0080] The pore forming material may be operable to be removed from the supported catalyst after moulding of the support, such as with heat treatment. The pore forming material may be operable to be removed by calcination of the support. The pore forming material may be any suitable pore forming material known in the art. The pore forming material may be selected from one or more of microbeads, starch, seeds and / or cellulose. The pore forming material may comprise olive stone.

[0081] The pore forming material may comprise a particle size distribution wherein Dw is from 80 to 200pm, such as from 100 to 180pm, or from 130 to 160pm. The pore forming material may comprise a particle size distribution wherein the D50 is from 180 to 320pm, such as from 200 to 300pm, or from 230 to 280pm. The pore forming material may comprise a particle size distribution wherein the D90 is from 300 to 550pm, such as from 330 to 500pm, or from 360 to 450pm.

[0082] The ceramic material of the support or composition may comprise a refractory ceramic material. The ceramic material may comprise aluminium oxide, aluminium silicate, magnesium aluminate, calcium aluminate, zirconia, silica, titanate, carbon and / or magnesium oxide, or precursors thereof. The ceramic material may comprise aluminium oxide, calcium aluminate or precursors thereof. The ceramic material may comprise aluminium oxide, such as a-aluminium oxide, or precursors or derivatives thereof.

[0083] The ceramic material may be obtained from at least two ceramic material fractions, for example, the ceramic material may be a product of the combination or two or more commercially available ceramic material products which may each be considered torepresent a ceramic material fraction and which may be combined to obtain the ceramic material of the support. The ceramic material may comprise a (first) ceramic material fraction having a particle size distribution wherein D10 is from 0.1 to 10pm, such as from 0.3 to 5pm, or from 0.3 to 3pm. The ceramic material may comprise a (first) ceramic material fraction having a particle size distribution wherein the D50 is from 0.5 to 30pm, such as from 1 to 20pm, or from 1.5 to 10pm. The ceramic material may comprise a (first) ceramic material fraction having a particle size distribution wherein the D90 is from 2 to 70pm, such as from 5 to 50pm, or from 8 to 40pm.

[0084] At least 30% of the fractions of the ceramic material by total weight of the ceramic material may have a D10 of from 0.1 to 10pm, such as from 0.3 to 5pm, or from 0.3 to 3pm; a D50 of from 0.5 to 30pm, such as from 1 to 20pm, or from 1.5 to 10pm; and / or a D90 of from 2 to 70pm, such as from 5 to 50pm, or from 8 to 40pm, such as at least 50wt% or at least 60wt%.

[0085] Particle size including D10 particle size, D50 particle size, D90 particle size and particle size distributions as used herein were measured by laser diffraction, using the Particle Size Analyser “Malvern Mastersizer 3000” with an EV cell attachment according to ASTM B822-20.

[0086] The ceramic material may be obtained from a ceramic material fraction comprising a primary crystal size of <3 pm, such as <2 pm or <1.5 pm, such as at least 15% of the ceramic material by total weight of the ceramic material, or at least 20wt% or at least 25wt%.

[0087] The ceramic material may be obtained from a ceramic material fraction comprising a BET surface area of >3 m2 / g, such as >5 m2 / g or >8 m2 / g, such as at least 15% of the ceramic material by total weight of the ceramic material, or at least 20wt% or at least 25wt%.

[0088] The ceramic material may comprise a ceramic powder. The ceramic powder may be ball milled or spray dried. Advantageously, it has been found that ball milled or spray dried ceramic powder provides easier casting behaviour.

[0089] The composition or support may comprise a promoter, operable to increase the reactivity of the main reaction, and / or decrease undesirable side reactions. The promoter may be selected from one or more of oxides of lanthanum, copper, magnesium, manganese, potassium, calcium, zirconium, barium, cerium, sodium, lithium, molybdenum, yttrium, cobalt, and chromium. The promoter may be selected from oneor more of oxides of lanthanum, copper, magnesium, calcium, zirconium, rhenium, tungsten and molybdenum.

[0090] The composition may further comprise a liquid carrier, such as an aqueous carrier. The composition may be an aqueous ceramic slurry.

[0091] The composition may comprise further additives. For example, the composition may comprise a dispersant, such as a polymeric salt, for example a salt of a polyacrylic, preferably an ammonium salt of a polyacrylic. A suitable dispersant may be selected from one or more of Ecodis P90, Narlex LD42 and Dispex A40.

[0092] The composition may comprise from 0.1 to 10% of polymerisable monomer by dry weight of the composition, preferably from 0.5 to 8wt%, more preferably from 1 to 6wt%, such as from 1 .5 to 5wt%, most preferably from 2 to 4 wt%.

[0093] The composition may comprise from 0.1 to 10% of crosslinking member by dry weight of the composition, preferably from 0.5 to 8wt%, more preferably from 0.75 to 6wt%, such as from 1 to 5wt%, most preferably from 1 to 4 wt%.

[0094] The composition may comprise from 50 to 95% of ceramic material by dry weight of the composition, preferably from 50 to 90wt%, more preferably from 55 to 85wt%, most preferably from 60 to 80wt%.

[0095] The support may comprise at least 75% of ceramic material by total weight of the catalyst, such as at least 85wt%, or at least 90wt%, or at least 95wt%, or at least 97wt% ceramic material.

[0096] The ceramic material of the support or composition may comprise >50% aluminium oxide or derivative thereof, by total weight of the ceramic material, such as >75 wt% aluminium oxide or derivative thereof, or > 90 wt% aluminium oxide or derivative thereof, >95 wt% aluminium oxide or derivative thereof, or >99 wt% aluminium oxide or derivative thereof.

[0097] The support may comprise >50% aluminium oxide or derivative thereof, by weight of the support, such as >75 wt% aluminium oxide or derivative thereof, or > 80 wt% aluminium oxide or derivative thereof, >85 wt% aluminium oxide or derivative thereof, or >90 wt% aluminium oxide or derivative thereof.

[0098] The composition may comprise >5 wt% of pore forming material by dry weight of the composition, such as >8 wt%, >12 wt%.

[0099] The composition may comprise <40 wt% of pore forming material by dry weight of the composition, such as <30 wt%, <20 wt%.

[0100] The composition may comprise from 5 to 40% of pore forming member by dry weight of the composition, such as from 8 to 30wt%, or from 12 to 20wt%.

[0101] The composition may comprise from 0.1 to 5% of initiator by dry weight of the composition, preferably from 0.5 to 4wt%, more preferably from 0.75 to 3.5wt%, most preferably from 1 to 3wt%.

[0102] The composition may comprise up to 5% of accelerator by dry weight of the composition, preferably up to 3wt%, more preferably up to 2wt%, most preferably up to 1.5wt%.

[0103] The composition may comprise from 0.1 to 10% of dispersant by dry weight of the composition, preferably from 0. 5 to 8wt%, more preferably 0.75 to 6wt%, most preferably from 1 to 5wt%.

[0104] The composition (or slip) may have a solids content of from 45 to 99% by total weight of the composition, such as from 50 to 95wt%, preferably from 55 to 90wt%, most preferably from 60 to 85wt%.

[0105] The composition may be formed by combining a pre-formed aqueous binder component with the ceramic material. The aqueous binder component may comprise a polymerisable monomer, a crosslinking member and water.

[0106] The supported catalyst of the present disclosure comprises catalytic material. The catalytic material is operable to provide catalytic activity in the desired reaction, such as in a pre-reforming, steam reforming and / or shift conversion reaction.

[0107] The catalyst may have a pore size distribution wherein >25% of the pores have a pore size diameter of >5 pm, such as >30%, >35%, >40%, >45% or >50%.

[0108] The catalyst may have a pore size distribution wherein >20% of the pores have a pore size diameter of >10 pm, such as >25%, >30%, >35% or >30%.

[0109] The catalyst may have a pore size distribution wherein >10% of the pores have a pore size diameter of >20 pm, such as >15%, >20%.

[0110] The catalyst may have a pore size distribution wherein >30% of the pores have a pore size diameter of >1 pm, such as >35%, >45%, or >50%.

[0111] The catalyst may have a BET specific surface area of >1 m2 / g, such as >1.5 m2 / g, or >2 m2 / g. The catalyst may have a BET specific surface area of <10 m2 / g, such as <6 m2 / g, or <4 m2 / g. The catalyst may have a BET specific surface area of from 1 to 10 m2 / g, such as from 1.5 to 6 m2 / g, or from 2 to 4 m2 / g.

[0112] The catalyst may have a total pore volume of >0.1 cm3 / g, such as >0.15 cm3 / g, or >0.17 cm3 / g. The catalyst may have a total pore volume of <0.5 cm3 / g, such as <0.3 cm3 / g, or <0.2 cm3 / g. The catalyst may have a total pore volume of from 0.1 to 0.5 cm3 / g, such as from 0.15 to 0.3 cm3 / g or from 0.17 to 0.2 cm3 / g.

[0113] The catalytic material may comprise a metal, such as a Group 6, Group 8, Group 9, Group 10, Group 11 and / or Group 12 metal or compound thereof, for example chromium, iron, cobalt, rhodium, iridium, nickel, palladium, platinum; copper, silver, gold, zinc, cadmium, mercury, and / or lanthanum. The catalytic material may comprise chromium, iron, nickel, palladium, platinum; copper, zinc and / or lanthanum. The catalytic material, such as for a pre-forming or steam reforming may comprise nickel. The catalytic material, such as for shift conversion may comprise iron, chromium, copper and / or zinc, such as an iron-chromium compound for high-temperature shift conversion and / or a copper-zinc compound for a low temperature shift conversion.

[0114] The supported catalyst may comprise catalytic material in an amount of >5% by total weight of the supported catalyst, such as >7wt% or >10wt%. The supported catalyst may comprise catalytic material in an amount of <50% by total weight of the supported catalyst, such as <40wt% or <35wt%. The supported catalyst may comprise catalytic material in an amount of from 5 to 50% by total weight of the supported catalyst, such as from 7 to 40wt% or from 10 to 35wt%.

[0115] The supported catalyst may comprise catalytic material in an amount of <30% by total weight of the catalyst, such as <25wt% or <20wt%. The catalyst may comprise catalytic material in an amount of from 5 to 30% by total weight of the catalyst, such as from 7 to 25wt% or from 10 to 20wt%.

[0116] The supported catalyst may comprise a gas accessibility of at least 85%, such as at least 95% or at least 98%.

[0117] As used herein, gas accessibility was measured by placing the catalyst sample in a heated column (400 °C) under nitrogen gas. Hydrogen sulphide of 3000ppm in nitrogen balance at flow rate of 270 ml / min was passed over the catalyst sample. Sulphur was detected at the gas outlet from the column, and the run continued until 3000ppm H2S was detected at the gas outlet from the column, which indicated that no further H2S adsorption was taking place on the catalyst sample. To calculate the sulphur pickup and gas accessibility, the amount of sulphur adsorbed by the sample was measured and compared against the theoretical sulphur capacity of the weight of the sample used.

[0118] According to the third aspect of the present disclosure there is provided a method for producing a support and optionally a supported catalyst, suitably a support or supported catalyst according to the first or second aspect of the present disclosure, comprising the steps of: a. contacting a composition for producing a support / supported catalyst, suitably a gel cast composition as defined in relation to the first and second aspect, with an initiator and optionally a polymerisation accelerator; b. arranging the resulting composition of step (a) in a mould; c. demoulding the composition to produce a green body, d. optionally, drying the green body at room temperature or baking the green body at elevated temperature; e. calcining the green body; f. optionally, contacting the support with catalytic material, g. optionally, calcining the product of step f.

[0119] The composition may be mixed before arranging in the mould to form a homogeneous slurry, suitably before addition of initiator and the optional accelerator. The composition may be mixed after addition of the initiator and the optional accelerator to form a homogeneous slurry.

[0120] The mould is preferably a cast mould. The mould may be operable to form surface structures on the green body.

[0121] The green body produced by step (c) may be dried by baking the green body at >60°C, such as >70°C or >90°C or >100°C. Suitably, the green body may be baked for >10 hours, such as >15 hours or >20 hours, for example >24 hours.

[0122] The green body may be calcined at >1000°C, preferably >1200°C, more preferably >1400°C, most preferably >1450°C. Suitably, the green body is fired until substantially all of the binder and pore forming material has been removed from the support / supported catalyst.

[0123] Advantageously, the present disclosure enables the green support / supported catalyst body to be removed from the mould while it is in a form that is still relatively rubbery, allowing for easier handling. This leads to a lower scrap rate than other types of casting techniques.

[0124] The catalytic material may be arranged onto the support by any suitable method. The catalyst material may be applied to the support after formation of the support. The composition used to from the support may be substantially free of catalytic material, such as comprise <10wt% catalytic material by dry weight of the composition, such as <5wt% or <2wt%.

[0125] The catalytic material may be applied by solution impregnation, physical vapor deposition, chemical vapor deposition or other suitable technique. Typically, by solution impregnation.

[0126] An aqueous solution of the catalytic material may be used. For example, a suitable solution may comprise a solution of a suitable compound of a catalytic metal, such as a nickel compound.

[0127] The solution may be applied to the support by dipping the support into the solution. The support may be dried at a temperature of from 105° to 150° C. The support may then be calcined, suitably in air, for example at a temperature of from 550 to 600 °C.

[0128] According to a further aspect of the present disclosure there is provided a method for producing a support or a supported catalyst, suitably a support or supported catalyst according to the first or second aspect of the present disclosure, the method comprising the steps of: a. optionally, producing a digital model of a support / supported catalyst; b. producing a precursor according to the model using additive manufacturing, preferably printing with a 3D printer; c. forming a cast mould from the precursor; d. cast moulding a moulding composition, suitably a moulding composition as defined in relation to the first or second aspect, to form a support or catalyst; suitably according to the method of the third aspect of the present disclosure.

[0129] The support / supported catalyst of the present disclosure may be used in reactions wherein the reactor has an internal temperature of up to 675°C, such as up to 620°C or up to 600°C.

[0130] According to the sixth aspect of the disclosure, there is provided a method for the production of carbon oxides and hydrogen (or syngas), such as from methane, for example a steam reforming method. The method, and / or the associated apparatus, such as according to the forth aspect of the present disclosure, may comprise a catalyst bed comprising up to 30% of a supported catalyst comprising ceramic material and a catalytic material, wherein the catalyst has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm, by total volume of the catalyst bed, such as up to 25vol% or up to 20vol% of the supported catalyst.

[0131] The catalyst bed portion comprising the supported catalyst may be arranged proximal or adjacent to the feed inlet of the reactor.

[0132] The supported catalyst for use in steam reforming may have been pre-reduced with hydrogen prior to contacting with the steam reforming reaction medium.

[0133] Advantageously, the use of a catalyst bed portion of the supported catalyst of the present disclosure in such a manner in a steam reforming reaction may provide anticarbon benefits due to improved low temperature gasification, for example at temperatures up to 600°C.

[0134] According to the seventh aspect of the disclosure, there is provided a method for the production of carbon dioxide and hydrogen, such as from carbon monoxide and water (or syngas feed), for example a shift conversion method. The shift conversion may be high-, medium- or low-temperature shift conversion.

[0135] The supports / catalysts of the present disclosure provide numerous improvements compared to commercially available supports / catalysts which are not according to the present disclosure.

[0136] As used herein, the term “higher hydrocarbons” may mean a hydrocarbon CnHm, wherein n is at least 2, and m is at least 2, suitably, a hydrocarbon heavier than methane.

[0137] As used herein, the term carbon oxides may mean carbon monoxide and / or carbon dioxide.

[0138] As used herein, unless otherwise expressly specified, the term “macropore” means a pore with a width exceeding 50 nm. As used herein, unless otherwise expresslyspecified, the term “mesopore” means a pore with a width of between 2 nm and 50 nm. As used herein, unless otherwise expressly specified, the term “micropore” means a pore with a width less than 2 nm.

[0139] As used herein, references to “dry weight” refer to the weight of the respective components / composition in the absence of any carrier liquid, such as water.

[0140] As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word "about", even if the term does not expressly appear. The term “about” when used herein means + / - 10% of the stated value. Also, the recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Also, any numerical range recited herein is intended to include all sub-ranges subsumed therein.

[0141] Singular encompasses plural and vice versa. For example, although reference is made herein to “an” organic binder component, “a” ceramic material, “a” pore forming material, and the like, one or more of each of these and any other components can be used. As used herein, the term "polymer" refers to oligomers and both homopolymers and copolymers, and the prefix "poly" refers to two or more. Including, for example and like terms means including for example but not limited to. The terms "comprising", "comprises" and "comprised of” as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. Additionally, although the present disclosure has been described in terms of “comprising”, the processes, materials, and coating compositions detailed herein may also be described as “consisting essentially of” or “consisting of”.

[0142] As used herein, the term "and / or," when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a list is described as comprising group A, B, and / or C, the list can comprise A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

[0143] Where ranges are provided in relation to a genus, each range may also apply additionally and independently to any one or more of the listed species of that genus.

[0144] All of the features contained herein may be combined with any of the above aspects in any combination.

[0145] For a better understanding of the present disclosure, and to show how embodiments of the same may be carried into effect, reference will now be made, by way of example, to the following experimental data and figures.BRIEF DESCRIPTION OF DRAWINGS

[0146] Figure 1 shows a perspective view of an embodiment of a supported catalyst according to the present disclosure.EXAMPLES

[0147] Support Examples 1-3 according to the present disclosure was produced from a moulding composition formed by mixing the components provided below (Table 1) using the following method.

[0148] An aqueous monomer solution containing the chain forming monomer, the chain linking monomer and the water was formed. To this the dispersant was added. The pore former was then introduced and mixed until fully dispersed. The alumina powders were then mixed to form an aqueous slurry. The polymerisation catalyst and initiator were then added to the aqueous slurry. The amounts of each component in the resulting slurry were as shown in Table 1.Table 1 - Summary of components of composition used to prepare Support Examples 1-3.The components used were all commercially available.1ceramic material fraction with a D50 of 2-4 pm, a primary crystal size of 1 pm, and a BET surface area of 8-15 m2 / g.2ceramic material fraction with a D50 of 4-6 pm.3ceramic material fraction with a D50 of 12-18 pm. 4D50 of 255-265 pm

[0149] The resulting aqueous slurry was then cast into a 9.5 mm diameter sphere mould having negative impressions operable to form surface structures on the moulded support. Once the slurry had gelled into a solid green body after 5-6 mins, it was then demoulded. At this point the green body support had a rubbery, jelly-like consistency. The green body was then dried at 110 °C for a minimum of 24 hours. The dried green body was then fired to 1450 C, at which point the polymeric binder, dispersant and pore former were burnt off to leave the solid support example 1. Support Example 1 had a side crush strength of 5.6 kg / mm.

[0150] Support Example 2 was prepared using the same composition, mould shape and method as Support Example 1 , apart from that a 11.5 mm diameter mould was used. Support Example 2 had a mean side crush strength of 8.0 kg / mm.

[0151] Support Example 3 was prepared using the same composition and method as Support Example 1 , apart from that a 16 mm diameter mould was used. Support Example 3 had a mean side crush strength of 7.9 kg / mm.

[0152] Supported Catalyst Example 1 according to the present disclosure was produced by impregnation of Support Example 1 with nickel. Supported Catalyst Example 1 had 18.2 % Ni by total weight of the supported catalyst, a total pore volume of 0.17 cm3 / g, and a specific surface area of 2.7 m2 / g. Supported Catalyst Example 1 had a mean side crush strength of 8.0 kg / mm.

[0153] As shown in Figure 1 , Supported Catalyst Example 1 (100) had a 9.5 mm diameter spherical macrostructure. The outer face of the spherical macrostructure of Supported Catalyst Example 1 comprised surface structures in the form of a plurality of interconnected hexagon-shaped annular ridges 102 extending over the whole of the outer surface. The portions of the surface structures that extended between the inner edges of the annular ridges were in the form of an open ended inverted hexagonal pyramid 104 projecting into the macrostructure.

[0154] Supported Catalyst Example 2 according to the present disclosure was produced by impregnation of Support Example 2 with nickel. Supported Catalyst Example 2 had18.2 wt% Ni, a total pore volume of 0.17 cm3 / g, and a specific surface area of 2.7 m2 / g. Supported Catalyst Example 1 had a mean side crush strength of 10.3 kg / mm.

[0155] Supported Catalyst Example 3 according to the present disclosure was produced by impregnation of Support Example 3 with nickel. Supported Catalyst Example 3 had 18.2 wt% Ni, a total pore volume of 0.17 cm3 / g. and a specific surface area of 2.7 m2 / g. Supported Catalyst Example 3 had a mean side crush strength of 10.3 kg / mm.

[0156] Each of Supported Catalyst Examples 1 to 3 had a pore size distribution wherein >30% of the pores had a pore size diameter of >5 pm, >20% had a pore size diameter of >10 pm, >60% had a pore size diameter of >1 pm and <15% had a pore size diameter of <0.1 pm.

[0157] Comparative Supported Catalyst Example 1 was a commercially available catalyst with a cylindrical shape and average diameter of 3.3 mm. The Comparative Supported Catalyst Example 1 had a total pore volume of 0.155 cm3 / g, and a total surface area of 113.6 m2 / g. The Comparative Supported Catalyst Example 1 had a pore size distribution with 47.7% of pores having an average pore size diameter of <0.01 pm, 38.6% of pores having an average pore size diameter of between 0.01 and 0.05 pm, and 6.3% of pores having an average pore size of at least 1 pm. The Comparative Supported Catalyst Example 1 had a nickel content of 29.4% by total weight of the catalyst.

[0158] Test Run

[0159] Supported Catalyst Examples 1 and 3 were tested against Comparative Supported Catalyst Example 1 in a test rig comprising a reactor tube with a catalyst bed for the prereforming of a heavy feed with steam. The heavy feed contained 6% Propane, 14% Ethane, 80% Methane. The reactor tube had a diameter of 1.5 inch and the catalyst bed had a volume of 90ml. The steam-to-carbon ratio (S / C) of the reaction was 2.9. The reaction was run for 5 hours with a reaction temperature of 450 °C and 600 °C. The amount of hydrogen and methane was measured after reaction in the test rig and displayed in Table 1 (450 °C) and Table 2 (600 °C).Table 2 - Composition of heavy feed after pre-reforming in test rig at 450 °C.Table 3 - Composition of heavy feed after pre-reforming in test rig at 600 °C.

[0160] The supported catalysts of the present disclosure have a higher reforming performance than the comparative example catalyst 1 at both 450 °C and 600 °C, with more hydrogen being produced. A larger improvement is observable in particular at lower temperatures.

[0161] Carbon Fixation

[0162] Carbon fixation of the catalysts after test run 1 was complete was measured according to ASTM E1941. The Comparative Supported Catalyst Example 1 contained 3.1 wt% carbon and 3.2 wt% carbon after pre-reforming at 450 °C and 600 °C respectively. Supported Catalyst Examples 1 and 3 had negligible carbon fixated, with approximately 0.1 wt% carbon after pre-reforming at 450 °C and 600 °C respectively.

[0163] Sulphur Pick Up Test

[0164] Supported Catalyst Examples 1 and 3, and Comparative Example Catalyst 1 were placed in a heated column at 400 °C and 3000 ppm H2S was passed over the catalysts. The amount of sulphur adsorbed by the catalyst was used to calculate the sulphur capacity as a percentage of the theoretical maximum sulphur capacity.

[0165] Comparative Supported Catalyst Example 1 adsorbed 13.78 % sulpur in the column, which is -80% of its maximum theoretical sulphur capacity. Supported Catalyst Examples 1 and 3 maximised their theoretical sulphur adsorption capacity at 100%.

[0166] Accordingly, the catalytic material in the supported catalysts of the present disclosure was 100% available for reactivity with the sulphur, whereas the catalytic material in the comparative catalyst was not completely accessible to reactant gases (only 80% available).

[0167] Attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0168] All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and / or steps are mutually exclusive.

[0169] Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[0170] The present disclosure is not restricted to the details of the foregoing embodiment(s). The present disclosure extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

CLAIMS1 . A support for a catalyst, wherein the support comprises ceramic material; and wherein the support has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm.

2. A support according to claim 1 , wherein the support has a pore size distribution wherein >25% of the pores have a pore size diameter of >5 pm, such as >30%, or >35%.

3. A support according to claim 1 or 2, wherein the support has a pore size distribution wherein >20% of the pores have a pore size diameter of >10 pm, such as >25%, or >30%.

4. A support according to any preceding claim, wherein the support has a pore size distribution wherein <30% of the pores have a size of <0.1 pm, such as <20%, <15%, <10%, or <5%.

5. A support according to any preceding claim, wherein the support has a total pore volume of >0.3 cm3 / g, such as >0.35 cm3 / g, or >0.4 cm3 / g.

6. A supported catalyst comprising catalytic material, wherein the support catalyst is obtained from a support according to any preceding claim.

7. A supported catalyst according to claim 6, wherein the catalyst is obtained from the support by impregnation of the supported with the catalytic material, such as by dipping of the support in a solution comprising the catalytic material.

8. A supported catalyst, wherein the supported catalyst comprises ceramic material and catalytic material; and wherein the supported catalyst has a pore size distribution wherein >20% of the pores have a pore size diameter of >5 pm.

9. A support / catalyst according to any preceding claim, wherein the support / catalyst has a substantially spherical and / or ellipsoidal macrostructure.

10. A support / catalyst according to any preceding claim, wherein the support / catalyst has a diameter / largest dimension of at least 9 mm, such as at least 11 mm, at least 15 mm.

11. A support / catalyst according to any preceding claim, wherein the support / catalyst comprises surface structures extending over >20% of the outer surface of the support / catalyst, such as over >30%, >40%, >60% or >80% of the outer surface.

12. A support / catalyst according to any preceding claim, wherein the support / catalyst comprises a substantially uniform outer face.

13. A support / catalyst according to any preceding claim, wherein the support / catalyst has a side crush strength of > 3 kg / mm, such as > 5 kg / mm or > 7 kg / mm.

14. A support / catalyst according to any preceding claim, wherein the support / catalyst is a cast support, such as a gel cast support.

15. A support / catalyst according to any preceding claim, wherein the support / catalyst is obtainable by gel casting a composition comprising a ceramic material, an organic binder component and a pore forming material.

16. A support / catalyst according to claim 15, wherein the organic binder component comprises a polymerisable component, suitably including a polymerisable monomer and a crosslinking member, wherein the binder component is operable to polymerise to form a (co)polymer.

17. A support / catalyst according to claim 16, wherein the polymerisable monomer comprises one or more acrylamide monomers.

18. A support / catalyst according to claim 16 or 17, wherein the crosslinking monomer comprises poly(ethylene glycol) di methacrylate (PEGDMA) and / or N,N’-methylenebis(acrylamide) (BIS).

19. A support / catalyst according to any of claims 16 to 18, wherein the organic binder component is formed from 55 to 85wt% of polymerisable monomer and from 45 to 15wt% of crosslinking member.

20. A support / catalyst according to any of claims 15 to 19, wherein the pore forming material comprises a particle size distribution wherein Dw is from 80 to 200pm, such as from 100 to 180pm, or from 130 to 160pm.21 . A support / catalyst according to any of claims 15 to 20, wherein the pore forming material comprises a particle size distribution wherein the D50 is from 180 to 320pm, such as from 200 to 300pm, or from 230 to 280pm.

22. A support / catalyst according to any of claims 15 to 21 , wherein the pore forming material comprises a particle size distribution wherein the Dgo is from 300 to 550pm, such as from 330 to 500pm, or from 360 to 450pm.

23. A support / catalyst according to any of claims 15 to 22, wherein the ceramic material is obtained from a ceramic material fraction having a particle size distribution wherein Dw is from 0.1 to 10pm, such as from 0.3 to 5pm, or from 0.3 to 3pm, and / or a D50 from 0.5 to 30pm, such as from 1 to 20pm, or from 1.5 to 10pm; and / or a Dgo from 2 to 70pm, such as from 5 to 50pm, or from 8 to 40pm.

24. A support / catalyst according to any of claims 15 to 23, wherein the ceramic material is obtained from a ceramic material fraction comprising a primary crystal size of <3 pm, such as <2 pm or <1.5 pm, such as at least 15% of the ceramic material by total weight of the ceramic material, or at least 20wt% or at least 25wt%.

25. A support / catalyst according to any of claims 15 to 24, wherein the ceramic material is obtained from a ceramic material fraction having a BET surface area of >3 m2 / g, such as >5 m2 / g or >8 m2 / g, such as at least 15% of the ceramic material by total weight of the ceramic material, or at least 20wt% or at least 25wt%.

26. A support / catalyst according to any of claims 15 to 25, wherein the composition comprises >5 wt% of pore forming material by dry weight of the composition, such as >8 wt%, >12 wt%.

27. A support / catalyst according to any of claims 15 to 26, wherein the composition comprises <40 wt% of pore forming material by dry weight of the composition, such as <30 wt%, <20 wt%.

28. A catalyst according to any of claims 6 to 27, wherein the catalyst has a pore size distribution wherein >25% of the pores have a pore size diameter of >5 pm, such as >30%, >35%, >40%, >45% or >50%.

29. A catalyst according to any of claims 6 to 28, wherein the catalyst has a pore size distribution wherein >20% of the pores have a pore size diameter of >10 pm, such as >25%, >30%, >35% or >30%.

30. A catalyst according to any of claims 6 to 29, wherein the catalyst has a pore size distribution wherein >10% of the pores have a pore size diameter of >20 pm, such as >15%, >20%.31 . A catalyst according to any of claims 6 to 30, wherein the catalyst has a pore size distribution wherein >30% of the pores have a pore size diameter of >1 pm, such as >35%, >45%, or >50%.

32. A catalyst according to any of claims 6 to 31 , wherein the catalyst has a BET specific surface area of >1 m2 / g, such as >1.5 m2 / g, or >2 m2 / g; and / or the catalyst has a BET specific surface area of <10 m2 / g, such as <6 m2 / g, or <4 m2 / g.

33. A catalyst according to any of claims 6 to 32, wherein the catalyst has a total pore volume of >0.1 cm3 / g, such as >0.15 cm3 / g, or >0.17 cm3 / g, and / or the catalyst has a total pore volume of <0.5 cm3 / g, such as <0.3 cm3 / g, or <0.2 cm3 / g.

34. A catalyst according to any of claims 6 to 33, wherein the catalytic material comprises chromium, iron, cobalt, rhodium, iridium, nickel, palladium, platinum; copper, silver, gold, zinc, cadmium, mercury, and / or lanthanum.

35. A catalyst according to any of claims 6 to 34, wherein the catalytic material comprises nickel.

36. A catalyst according to any of claims 6 to 35, wherein the supported catalyst comprises catalytic material in an amount of <30% by total weight of the catalyst, such as <25wt% or <20wt%.

37. A method for producing a support or supported catalyst, such as a support / catalyst according to any preceding claim, comprising: a. contacting a composition for producing a support / supported catalyst, suitably a composition, such as a gel-cast composition, with an initiator and optionally a polymerisation accelerator; b. arranging the resulting composition of step (a) in a mould; c. demoulding the composition to produce a green body, d. optionally, drying the green body at room temperature or baking the green body at elevated temperature;e. calcining the green body; f. optionally, contacting the support with catalytic material. optionally, calcining the product of step f.

38. An apparatus comprising a reactor, such as for pre-reforming, steam reforming and / or shift conversion, wherein the reactor comprises a supported catalyst according to any of claims 6 to 36.

39. A method for the production of methane, such as from higher hydrocarbons, for example a pre-reforming method, wherein the method comprises use of a catalyst bed, wherein catalyst bed comprises a supported catalyst according to any of claims 6 to 36, to produce methane.

40. A method for the production of carbon oxides and hydrogen (or syngas), such as from methane, for example a steam reforming method, wherein the method comprises use of a catalyst bed, wherein catalyst bed comprises a supported catalyst according to any of claims 6 to 36, to produce the carbon oxides and hydrogen.41 . A method according to claim 40, wherein the catalyst bed comprises up to 30% of a supported catalyst according to any of claims 6 to 36.

42. A method according to claim 40 or 41 , wherein the catalyst bed portion comprising the supported catalyst according to any of claims 6 to 36 is arranged proximal or adjacent to the feed inlet of the reactor.

43. A method according to any of claims 40 to 42, wherein the catalyst bed comprises supported catalyst according to any of claims 6 to 36 that has been pre-reduced with hydrogen prior to contacting with the steam reforming reaction medium.

44. A method for the production of carbon dioxide and hydrogen, such as from carbon monoxide and water (or syngas feed), for example a shift conversion method, wherein the method comprises use of a catalyst bed, wherein catalyst bed comprises a supported catalyst according to any of claims 6 to 36, to produce the carbon dioxide and hydrogen.

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