Catalyst systems for reforming in cyclic flow reactors

A multi-zone reforming catalyst, comprising:

• a first support structure;
• first Ni-containing catalyst having reforming activity;
• a first metal oxide support layer that is thermally phase stable at 800° C. to 1600° C. comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, an oxide selected from the group consisting of α-Al2O3, LaAlO3, LaAl11O18, MgO, CaO, ZrO2, TiO2, CeO2, Y2O3, La2O3, SiO2, Na2O, K2O, and mixtures thereof, or a combination thereof,
• the first catalyst and the first metal oxide support layer comprising a first catalyst system supported by one or more surfaces of the first support structure, the first catalyst system comprising 0.5 wt % or more of a combined weight of the first catalyst system and the first support structure;
• a second support structure;
• a second catalyst having reforming activity comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof;
• and
• a second metal oxide support layer comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, an oxide selected from the group consisting of α-Al2O3, LaAlO3, LaAl11O18, MgO, CaO, ZrO2, TiO2, CeO2, Y2O3, La2O3, SiO2, Na2O, K2O, and mixtures thereof, or a combination thereof, the second catalyst and the second metal oxide support layer comprising a second catalyst system, the second catalyst system being different than the first catalyst system, the second catalyst system being supported by one or more surfaces of the second support structure.

A method for forming a catalyst system, comprising:

• forming a catalyst system comprising a catalyst and a metal oxide support layer that is thermally phase stable at 800° C. to 1600° C., the catalyst having reforming activity and comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the metal oxide support layer comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, an oxide selected from the group consisting of α-Al2O3, LaAlO3, LaAl11O18, MgO, CaO, ZrO2, TiO2, CeO2, Y2O3, La2O3, SiO2, Na2O, K2O, and mixtures thereof, or a combination thereof;
• supporting the catalyst system on one or more surfaces of a support structure, the supporting comprising;
• depositing an intermediate bonding layer on at least a portion of the one or more surfaces of the support structure, and
• supporting at least a portion of the catalyst system on the intermediate bonding layer;
• annealing the supported catalyst system and the support structure at an annealing temperature of 1000° C. or more to form an annealed catalyst system and support structure;
• and
• exposing the annealed catalyst system and support structure to cyclic reforming conditions comprising a peak temperature of 1000° C. or more in the presence of a hydrocarbon feed to form H2, the cyclic reforming conditions comprising a reforming step and a regeneration step,
• wherein the metal oxide support layer comprises one or more metal oxides, and wherein forming the catalyst system comprises mixing a powder comprising the catalyst with a powder comprising the one or more metal oxides of the metal oxide support layer, the powder comprising the one or more metal oxides of the metal oxide support layer having a surface area of 20 m2/g or less.

A method for reforming hydrocarbons in a cyclic reaction environment, comprising:

• reacting a mixture comprising fuel and 0.1 vol % or more of O2 under combustion conditions in a combustion zone within a reactor to heat one or more surfaces of a monolith in a reaction zone to a regenerated surface temperature of 800° C. or more, the reaction zone comprising a catalyst system supported on the one or more surfaces of the monolith;
• exposing a reactant stream comprising a reformable hydrocarbon to the one or more surfaces in the reaction zone to increase the temperature of the reactant stream;
• and
• exposing the reactant stream to the catalyst system in the reaction zone at a temperature of 800° C. or more to form a product stream comprising Hz, a direction of flow for the reactant stream within the reaction zone being reversed relative to a direction of flow for the mixture,
• wherein the catalyst system comprises a catalyst and a metal oxide support layer, the metal oxide support layer being thermally phase stable at 800° C. to 1600° C., the catalyst system comprising NiAl2O4, the catalyst system comprising 0.5 wt % or more of a combined weight of the catalyst system and the monolith.

A hydrocarbon reforming catalyst system and support structure, comprising:

• a support structure comprising a monolith;
• a catalyst having reforming activity, the catalyst comprising an Ni-containing catalyst;
• and
• a metal oxide support layer that is thermally phase stable at 800° C. to 1600° C.,
• the catalyst and the support layer comprising a catalyst system supported by one or more surfaces of the monolith, the catalyst system comprising NiAl2O4,the catalyst system comprising 0.5 wt % or more of a combined weight of the catalyst system and the monolith.