Patent Description:
NH<NUM> is increasingly seen as an energy vector, especially since it can be used to store significant amounts of H<NUM>. Sustainable NH<NUM> (so called "blue" or "green" NH<NUM>) might be produced on a large scale from regenerative energy sources. The reforming of NH<NUM> (equation I) on site, where the H<NUM> is needed, might be the last step in closing an H<NUM> value chain based on renewable electricity. To have direct access to H<NUM> at elevated pressure (e.g. in the range of from <NUM> to <NUM> bara), the NH<NUM>-reforming itself could also be conducted at these pressures.

<NUM> NH<NUM> <IMG> N<NUM> + <NUM><NUM> ΔHr = +<NUM> kJ/mol     (I).

Typically, said endothermic reaction is carried out in processes at temperatures between <NUM> and <NUM> and pressures of up to <NUM> bara.

<CIT> relates to NH<NUM> decomposition catalyst systems. In particular, an NH<NUM> decomposition system is disclosed therein comprising a support material and a catalyst component, the catalyst component comprising Ru and at least one additional metal that catalyzes and/or promotes NH<NUM> decomposition.

<CIT> discloses a reactor for the generation of hydrogen from ammonia comprising an upstream catalytic ammonia oxidation zone and a downstream catalytic ammonia decomposition zone.

<CIT> relates to an adiabatic reaction cascade for the production of chlorine using a cerium oxide catalyst. The adiabatic reaction cascade particularly comprises at least two reaction stages connected in series with intermediate cooling.

<NPL>, a study on a flexible tool for methanol synthesis. Based on computational examination of multi-level layered loadings as applied to a methanol reaction system, a more effective utilization of the catalyst was found to be achievable by multi-level layering in view of an isothermal operation of the reactor.

However, there remains a need for an improved reactor design with respect to the reforming of NH<NUM>. Thus, it was an object of the present invention to provide a reactor for the reforming of NH<NUM>.

to N<NUM> and H<NUM>, in particular allowing a cost and resource-efficient conversion of NH<NUM>. More specifically, it was an object of the present invention to provide a novel reactor design for an adiabatic reactor, wherein especially the catalysts may be employed in a more efficient manner, thus allowing for an improved conversion and/or a more compact reactor design.

It has surprisingly been found that said problem can be solved by a novel zoned concept in a reactor, in particular by employing a high temperature active catalyst in the inlet part and a low temperature active catalyst in the outlet part of an adiabatic reactor.

Thus, the present invention relates to a zoned concept for adiabatic reactors, wherein each catalyst operates at advantageous temperatures, thus, allowing application of a comparatively large temperature window and an efficient use of the used catalysts. In particular, a high temperature active catalyst operating in a possible temperature window of from for example <NUM> to <NUM> can be placed in the upper (inlet) part of the reactor. As a function of the conversion along the reactor bed, the temperature of the stream decreases since the reforming of NH<NUM> is an endothermic reaction. When approaching a lower temperature of <NUM> the high temperature active catalyst becomes more and more inefficient. Then, a low temperature active catalyst allowing operation in a temperature window in the range of from for example <NUM> to <NUM> can be placed after the high temperature active catalyst in the lower (outlet) part of the adiabatic reactor. This catalyst should still be very active at <NUM> and as function of the ongoing NH<NUM>-conversion the temperature further decreases until <NUM>.

It was surprisingly found that the zoned concept within an adiabatic reactor enables a high NH<NUM> conversion, respectively reforming, in a relatively small reactor volume. Further, the present invention allows applying a large temperature window in the reactor, wherein each catalyst of a reaction zone is chosen based on its activity in a specific temperature range. This also allows for example the combination of a relatively cost-efficient high temperature catalyst, with a highly active low temperature catalyst, in its effective zones. Thus, the present invention enables use of any combination of low temperature active and high temperature active catalysts for this type of reaction. In sum, it was surprisingly found that the present invention not only allows an effective way of using specific catalysts with respect to the optimal temperature window, but also offers a solution which is economically favored. These findings are of advantage at any reaction pressure and are applicable in a broad variety.

Therefore, the present invention relates to a zoned reactor for the reforming of NH<NUM> to N<NUM> and H<NUM>, wherein the reactor is an adiabatic rector, and wherein the reactor comprises.

Within the meaning of the present application, an adiabatic reactor preferably designates a reactor of which the reactor walls are thermally isolated such that no heat exchange with the outside of the reactor takes place. Accordingly, within the meaning of the present application, an adiabatic reactor preferably exchanges thermal energy and mass with the environment exclusively by way of the inlet and outlet of the reactor.

It is preferred that the inlet reaction zone displays a T50 light-off temperature higher than <NUM>, more preferably in the range of from higher than <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, wherein the T50 light-off temperature is preferably determined according to Reference Example <NUM>.

It is preferred that the outlet reaction zone displays a T50 light-off temperature equal to or lower than <NUM>, more preferably in the range of from <NUM> to equal or lower than <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, wherein the T50 light-off temperature is preferably determined according to Reference Example <NUM>.

It is preferred that the axial length L of the reactor is in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>.

It is preferred that the cross-section of the reactor is circular.

In the case where the cross-section of the reactor is circular, it is preferred that the reactor geometry is cylindrical, and that the reactor has a diameter D, wherein D is in the range of from <NUM> to <NUM>, preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>.

In the case where the reactor geometry is cylindrical, and wherein the reactor has a diameter D, it is preferred that the reactor displays an aspect ratio L:D of the axial length L of the reactor to the diameter D of the reactor in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, wherein the aspect ratio L:D more preferably is <NUM>:<NUM>.

It is preferred that n is an integer in the range of from <NUM> to <NUM>, wherein more preferably n is <NUM> or <NUM>, wherein the reactor more preferably comprises <NUM> reaction zones.

It is preferred that each of the reaction zones independently from one another has a length in the range of from (<NUM>·L/n) to (<NUM>·L/n), more preferably in the range of from (<NUM>·L/n) to (<NUM>·L/n), more preferably in the range of from (<NUM>·L/n) to (<NUM>·L/n), more preferably in the range of from (<NUM>-L/n) to (<NUM>·L/n), more preferably in the range of from (<NUM>·L/n) to (<NUM>·L/n), more preferably in the range of from (<NUM>-L/n) to (<NUM>·L/n), more preferably in the range of from (<NUM>-L)/n to (<NUM>-L)/n, more preferably in the range of from (<NUM>-L)/n to (<NUM>·L)/n, wherein each of the reaction zones more preferably has a length of L/n.

It is preferred that the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, more preferably from the group consisting of Ni-containing catalysts, Ru-containing catalysts, and mixtures thereof.

It is preferred that the one or more catalytic components comprised in the inlet reaction zone are selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, more preferably from the group consisting of Ni-containing catalysts, Ru-containing catalysts, and mixtures thereof, wherein the one or more catalytic components comprised in the inlet reaction zone are preferably one or more Ni-containing catalysts.

It is preferred that the one or more catalytic components comprised in the outlet reaction zone are selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, more preferably from the group consisting of Ni-containing catalysts, Ru-containing catalysts, and mixtures thereof, wherein the one or more catalytic components comprised in the outlet reaction zone are preferably one or more Ru-containing catalysts.

It is preferred that the one or more catalytic components comprised in each of the optional intermediate reaction zones between the inlet and outlet reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, wherein the one or more catalytic components comprised in each of the optional intermediate reaction zones between the inlet and outlet reaction zones more preferably comprise independently from one another one or more catalytic components selected from the group consisting of Ni-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures of two or more thereof.

In the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that the one or more Co-containing catalysts and/or the one or more Ni-containing catalysts comprise a further metal M selected from the group consisting of alkali metals, alkaline earth metals, Mo, and Fe, including mixtures of two or more thereof, more preferably from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, and Fe, including mixtures of two or more thereof, more preferably from the group consisting of K, Na, Cs, Ba, Mo, and Fe, including mixtures of two or more thereof, more preferably from the group consisting of K, Ba, Mo, and Fe, including mixtures of two or more thereof, wherein more preferably M is Fe or Mo.

Further in the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that the one or more Co-containing catalysts and/or the one or more Ni-containing catalysts further comprise one or more support materials onto which Co and/or Ni and/or M, preferably Co and M and/or Ni and M, are supported, wherein the support materials are preferably selected from the group consisting of Al<NUM>O<NUM>, SiO<NUM>, ZrO<NUM>, CeO<NUM>, MgO, CaO, and mixtures of two or more thereof, more preferably from the group consisting of Al<NUM>O<NUM>, SiO<NUM>, ZrO<NUM>, CeO<NUM>, and mixtures of two or more thereof, more preferably from the group consisting of Al<NUM>O<NUM>, SiO<NUM>, and mixtures thereof, wherein more preferably the support materials comprise, preferably consist of, Al<NUM>O<NUM>.

In the case where the one or more Ni-containing catalysts comprise a further metal M selected from the group consisting of alkali metals, alkaline earth metals, Mo, and Fe, including mixtures of two or more thereof, it is preferred that the Ni-containing catalysts display a M : Ni atomic ratio in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, and more preferably of from <NUM>:<NUM> to <NUM>:<NUM>. In the case where M is Fe, it is particularly preferred that the Ni-containing catalysts display a Fe : Ni atomic ratio in the range of from <NUM>:<NUM> to <NUM>:<NUM>, preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>. In the case where M is Mo, it is preferred that the Ni-containing catalysts display a Mo : Ni atomic ratio in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>.

In the case where the one or more Co-containing catalysts comprise a further metal M selected from the group consisting of alkali metals, alkaline earth metals, Mo, and Fe, including mixtures of two or more thereof, it is preferred that the Co-containing catalysts display a M : Co atomic ratio in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably of from <NUM>:<NUM> to <NUM>:<NUM>, and more preferably of from <NUM>:<NUM> to <NUM>:<NUM>. In the case where M is Mo, it is preferred that the Co-containing catalysts display a Mo : Co atomic ratio in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>, more preferably in the range of from <NUM>:<NUM> to <NUM>:<NUM>.

Further in the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that the one or more Ni-containing catalysts and/or the one or more Co-containing catalysts further comprise Al and O.

In the case where the one or more Ni-containing catalysts and/or the one or more Co-containing catalysts further comprise Al and O, it is preferred that the one or more Ni-containing catalysts further comprise Mg, wherein the Ni : Mg : Al molar ratio is preferably in the range of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>), more preferably of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>), more preferably of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>), more preferably of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>), and more preferably of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>).

Further in the case where the one or more Ni-containing catalysts and/or the one or more Co-containing catalysts further comprise Al and O, it is preferred that the one or more Ni-containing catalysts comprise Ni in an amount in the range of from <NUM> to <NUM> wt. -%, preferably in the range of from <NUM> to <NUM> wt. -%, more preferably in the range of from <NUM> to <NUM> wt. -%, more preferably in the range of from <NUM> to <NUM> wt. -%, based on <NUM> wt. -% of the total weight of the one or more Ni-containing catalyst.

Further in the case where the one or more Ni-containing catalysts and/or the one or more Co-containing catalysts further comprise Al and O, it is preferred that from <NUM> to <NUM> wt. -% of the one or more Ni-containing catalysts consists of Ni, Mg, Al, and O, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, and more preferably from <NUM> to <NUM> wt.

Further in the case where the one or more Ni-containing catalysts and/or the one or more Co-containing catalysts further comprise Al and O, it is preferred that from <NUM> to <NUM> wt. -% of the one or more Ni-containing catalysts consists of Ni, M, Mg, Al, and O, preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, and more preferably from <NUM> to <NUM> wt.

In the case where the one or more Co-containing catalysts further comprise Al and O, it is preferred that the one or more Co-containing catalysts further comprises La, wherein the Co : La : Al molar ratio is preferably in the range of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>), more preferably of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>), more preferably of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>), more preferably of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>), and more preferably of from <NUM> : (<NUM> - <NUM>) : (<NUM> - <NUM>).

In the case where the one or more Co-containing catalysts further comprises La, it is preferred according to a first alternative that from <NUM> to <NUM> wt. -% of the one or more Co-containing catalysts consists of Co, La, Al, and O, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, and more preferably from <NUM> to <NUM> wt.

In the case where the one or more Co-containing catalysts further comprises La, it is preferred according to a second alternative that from <NUM> to <NUM> wt. -% of the one or more Co-containing catalysts consists of Co, M, La, Al, and O, preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, and more preferably from <NUM> to <NUM> wt.

Further in the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that the one or more Ru-containing catalysts further comprise one or more support materials onto which Ru is supported, wherein the support materials are preferably selected from the group consisting of metal oxides, wherein the metal of the metal oxides is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, and rare earth metals, including combinations of two or more thereof, Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, and Nd, including combinations of two or more thereof, Al, Ti, Zr, Mg, Ca, and La, including combinations of two or more thereof, Al, Zr, and Mg, including combinations of two or more thereof, wherein more preferably the one or more support materials comprise one or more metal oxides selected from the group consisting of Al<NUM>O<NUM>, ZrO<NUM>, and spinels, including mixtures of two or more thereof, preferably from the group consisting of ZrO<NUM> and spinels, including mixtures of two or more thereof, wherein more preferably the one or more support materials comprise ZrO<NUM> and/or MgAl<NUM>O<NUM>, preferably ZrO<NUM>, wherein more preferably the one or more support materials consist of ZrO<NUM> and/or MgAl<NUM>O<NUM>, preferably of ZrO<NUM>.

In the case where the one or more Ru-containing catalysts further comprise one or more support materials onto which Ru is supported, it is preferred that the one or more support materials display a pore volume in the range of from <NUM> to <NUM>/g, preferably of from <NUM> to <NUM>/g, more preferably of from <NUM> to <NUM>/g, and more preferably of from <NUM> to <NUM>/g, wherein the pore volume is preferably determined according to ISO <NUM>-<NUM>:<NUM>.

Further in the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that the one or more Ru-containing catalysts display a BET surface area in the range of <NUM> to <NUM><NUM>/g, more preferably of from <NUM> to <NUM><NUM>/g, more preferably of from <NUM> to <NUM><NUM>/g, more preferably of from <NUM> to <NUM><NUM>/g, more preferably of from <NUM> to <NUM><NUM>/g, and more preferably of from <NUM> to <NUM><NUM>/g, wherein the BET surface area is preferably determined according to ISO <NUM>:<NUM>.

Further in the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that the one or more Ru-containing catalysts display a pore volume in the range of <NUM> to <NUM>/g, more preferably of from <NUM> to <NUM>/g, more preferably of from <NUM> to <NUM>/g, more preferably of from <NUM> to <NUM>/g, and more preferably of from <NUM> to <NUM>/g, wherein the pore volume is preferably determined according to ISO <NUM>-<NUM>:<NUM>.

Further in the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that the one or more Ru-containing catalysts comprises Ru in an amount in the range of from <NUM> to <NUM> wt. -% based on <NUM> wt. -% of the total amount of the one or more support materials, more preferably of from <NUM> to <NUM> wt. -%, more preferably of from <NUM> to <NUM> wt. -%, more preferably of from <NUM> to <NUM> wt. -%, more preferably of from <NUM> to <NUM> wt. -%, and more preferably of from <NUM> to <NUM> wt.

Further in the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that from <NUM> to <NUM> wt. -% of the one or more Ru-containing catalysts consists of Ru and the one or more support materials, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, and more preferably from <NUM> to <NUM> wt.

Further in the case where the one or more catalytic components comprised in each of the n reaction zones are independently from one another selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof, it is preferred that the one or more Ru-containing catalysts further comprises one or more alkali metal and/or alkaline earth metal hydroxides, wherein the one or more alkali.

metal and/or alkaline earth metal hydroxides are preferably supported on the one or more support materials supporting Ru, wherein the alkali metal and/or alkaline earth metal hydroxides are preferably selected from the group consisting of Mg(OH)<NUM>, Ca(OH)<NUM>, Ba(OH)<NUM>, Sr(OH)<NUM>, LiOH, NaOH, and KOH, including mixtures of two or more thereof, more preferably from the group consisting of Mg(OH)<NUM>, Ca(OH)<NUM>, LiOH, NaOH, and KOH, including mixtures of two or more thereof, more preferably from the group consisting of LiOH, NaOH, and KOH, including mixtures of two or more thereof, wherein more preferably the catalyst further comprises KOH and/or LiOH, preferably KOH.

In the case where the one or more Ru-containing catalysts further comprises one or more alkali metal hydroxides, it is preferred that the one or more Ru-containing catalysts comprises the one or more alkali metal hydroxides in an amount in the range of from <NUM> to <NUM> wt. -% based on <NUM> wt. -% of the total amount of the one or more support materials, more preferably of from <NUM> to <NUM> wt. -%, more preferably of from <NUM> to <NUM> wt. -%, more preferably of from <NUM> to <NUM> wt. -%, more preferably of from <NUM> to <NUM> wt. -%, and more preferably of from <NUM> to <NUM> wt.

Further in the case where the one or more Ru-containing catalysts further comprises one or more alkali metal hydroxides, it is preferred that from <NUM> to <NUM> wt. -% of the one or more Ru-containing catalysts consists of Ru, the one or more alkali metal hydroxides, and the one or more support materials, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> wt. -%, and more preferably from <NUM> to <NUM> wt.

It is preferred that the one or more catalytic components are in the form of moldings and/or in powder form, more preferably in the form of moldings, more preferably in the form of 3D printed moldings, extrudates, or tablets, and more preferably in the form of extrudates or tablets.

It is preferred that the one or more catalytic components are comprised in a fixed-bed.

It is preferred that the reactor is operated in downflow or upflow mode, preferably in downflow mode.

Further, the present invention relates to a production unit for the reforming of NH<NUM> to N<NUM> and H<NUM>, the production unit comprising k adiabatic reactors each comprising a reactor inlet and a reactor outlet, wherein at least one of the reactors is a zoned reactor according to any one of the embodiments disclosed herein, wherein k is an integer in the range of from <NUM> to <NUM>, wherein the reactors are arranged in sequence along the reaction stream, and wherein a heating component is arranged upstream of each of the k reactors.

It is preferred that one and the same heating unit is arranged upstream of each of the k reactors.

Alternatively, it is preferred that a separate heating unit is arranged upstream of each of the k reactors.

It is preferred that k is equal to or greater than <NUM>, wherein k is more preferably an integer in the range of <NUM> to <NUM>, more preferably in the range of <NUM> to <NUM>, wherein k is more preferably <NUM> or <NUM>.

It is preferred that the production unit comprises one or two zoned reactors according to any of the embodiments disclosed herein.

Yet further, the present invention relates to a process for the reforming of NH<NUM> to N<NUM> and H<NUM>, the process comprising.

It is preferred that the feed gas stream provided in (ii) comprises from <NUM> to <NUM> vol. -% of NH<NUM>, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, and more preferably from <NUM> to <NUM> vol.

It is preferred that the feed gas stream provided in (ii) comprises from <NUM> to <NUM> vol. -% of N<NUM>, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, and more preferably from <NUM> to <NUM> vol.

It is preferred that the feed gas stream provided in (ii) comprises from <NUM> to <NUM> vol. -% of H<NUM>, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, and more preferably from <NUM> to <NUM> vol.

It is preferred that the feed gas stream provided in (ii) comprises from <NUM> to <NUM>,<NUM> ppmv of H<NUM>O, more preferably from <NUM> to <NUM>,<NUM> ppmv, more preferably from <NUM> to <NUM>,<NUM> ppmv, more preferably from <NUM>,<NUM> to <NUM>,<NUM> ppmv, more preferably from <NUM>,<NUM> to <NUM>,<NUM> ppmv, more preferably from <NUM>,<NUM> to <NUM>,<NUM> ppmv.

It is preferred that the total amount of NH<NUM>, N<NUM>, and H<NUM> comprised in the feed gas stream provided in (ii) is in the range from <NUM> to <NUM> wt. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, more preferably from <NUM> to <NUM> vol. -%, and more preferably from <NUM> to <NUM> vol.

It is preferred that feeding in (iii) is performed at a temperature in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>, more preferably in the range of from <NUM> to <NUM>.

It is preferred that feeding in (iii) is performed at a pressure in the range of from <NUM> to <NUM> bara, more preferably in the range of from <NUM> to <NUM> bara, more preferably in the range of from <NUM> to <NUM> bara.

It is preferred that the feed gas stream is fed into the reactor according to any one of the embodiments disclosed herein at a gas hourly space velocity in the range of from <NUM> to <NUM>-<NUM>, more preferably in the range of from <NUM> to <NUM>-<NUM>, more preferably in the range of from <NUM> to <NUM>-<NUM>.

It is preferred that the reactor provided in (i) is operated in downflow or upflow mode, more preferably in downflow mode.

Yet further, the present invention relates to a use of a reactor according to any one of the embodiments disclosed herein or of the production unit according to any one of the embodiments disclosed herein, for the reforming of NH<NUM> to N<NUM> and H<NUM>.

The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The reactor of any one of embodiments <NUM> to <NUM>", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The reactor of any one of embodiments <NUM>, <NUM>, <NUM>, and <NUM>". Further, it is explicitly noted that the following set of embodiments is not the set of claims determining the extent of protection, but represents a suitably structured part of the description directed to general and preferred aspects of the present invention.

The present invention is illustrated by the following examples, reference examples, and comparative examples.

Prior to the catalytic testing, the catalyst samples were placed into a reactor and activated in a reducing atmosphere of <NUM> vol. -% H<NUM> in Ar at a temperature of <NUM> (dwell time <NUM>, heating rate <NUM>/min). After activating the catalyst, a feed stream containing ammonia (<NUM> vol. -% NH<NUM>, <NUM> vol. % H<NUM>O, <NUM> vol. % of Ar) was fed into the reactor, wherein the partial pressure of NH<NUM> (p(NH<NUM>)) was set to <NUM> bara. The gas hourly space velocity (GHSV) with respect to the NH<NUM> content was set to <NUM>-<NUM>. The temperature of the feed stream was varied from <NUM> to <NUM>. At each point of measurement, the temperature was held constant and the conversion rate was determined in the steady-state (conversion rate variation of ± <NUM> % or less).

A kinetic model for the Ni-containing catalyst according to Reference Example <NUM> and for the Ru-containing catalyst according to Reference Example <NUM> was developed using the MATLAB software (version R2021b).

<FIG> shows the parity plots of the simulated and experimental values for the Ni-containing catalyst (<FIG>) and for the Ru-containing catalyst (<FIG>). A very good agreement was found. Thus, the estimated kinetic parameters implemented in the assumed model were found to be highly valid.

Based on the kinetic model, NH<NUM>-reforming processes were simulated based on a cascade of adiabatic reactors within defined scenarios.

As scenario, a gas hourly space velocity of <NUM>-<NUM> (unless otherwise indicated) was set for the first reactor in the direction of the NH<NUM> feed stream. As reactors, adiabatic reactors were used, wherein the reactors were serially arranged, thus, as a cascade. Further, the volume of each reactor was defined by a length of <NUM> and a diameter of <NUM>. Thus, the aspect ratio of each reactor was <NUM>:<NUM>. Due to the volume increase as function of the reforming of NH<NUM>, the gas hourly space velocity is also increasing when comparing the GHSV at the reactor inlet of a reactor with that at the reactor outlet of said reactor. Further, the simulations were conducted at a pressure of <NUM> and <NUM> bara.

Thus, the reforming of NH<NUM> was simulated for the production units according to Comparative Examples <NUM>-<NUM> and Examples <NUM>-<NUM>, also with varying the temperature, the pressure, and the gas hourly space velocity. The numbering of the reactors indicates the direction of the gas stream from reactor <NUM> to reactor n.

The Ni-containing catalyst was provided following the process described in example E1 of <CIT>.

However, an aqueous solution of Nickel nitrate (<NUM> % Ni concentration) was used instead of the pulverulent nickel nitrate hexahydrate. The various ingredients were mixed to a paste which was extruded. The extrudates were crushed and sieved to a target fraction having a particle size of from <NUM> to <NUM> after drying and low temperature calcination.

The sieved powder was then mixed with <NUM> weight-% graphite (Asbury Graphite <NUM>) and <NUM> weight-% cellulose (Arbocel BWW <NUM>). The resulting mixture was tableted to moldings having a four-hole cross-section as shown in <FIG> of <CIT>. For calcination, the moldings were heated in an annealing furnace to a temperature of <NUM>,<NUM> to <NUM>,<NUM> which was held for <NUM> hours.

The nickel content of the calcined moldings was <NUM> weight-%, the magnesium content <NUM> weight-%, and the aluminium content was <NUM> weight-%.

As shown in <FIG>, the T50 light-off temperature determined according to Reference Example <NUM> of the Ni-containing catalyst of Example <NUM> was <NUM>.

Ru supported on ZrO<NUM> was provided according to Example <NUM> of <CIT> by impregnation of a ruthenium salt solution onto a zirconium oxide powder (D9-<NUM>, BASF, BET surface area: <NUM><NUM>/g, pore volume: <NUM>/g), for obtaining Ru supported on ZrO<NUM> at a loading of <NUM> weight-%. The catalyst was then extruded to form extrudates having a diameter of <NUM>.

A <NUM> sample of the obtained <NUM> weight-% Ru on ZrO<NUM> extrudates was subject to impregnation with a KOH solution. To this effect, <NUM> of the obtained extrudates were split to form fractions in the range of <NUM> to <NUM> microns, which were then impregnated via incipient wetness impregnation with <NUM> of KOH dissolved in <NUM> of water. The sample was then dried at <NUM> and subsequently calcined under inert atmosphere at <NUM> for <NUM> hours.

As shown in <FIG>, the T50 light-off temperature determined according to Reference Example <NUM> of the Ru-containing catalyst of Example <NUM> was <NUM>.

A production unit comprising four reactors was provided, wherein each reactor was filled with the Ni-containing catalyst according to Reference Example <NUM>.

According to Reference Example <NUM>, the reforming of NH<NUM> was simulated for said adiabatic reactor cascade at a pressure of <NUM> bara and an initial GHSV of <NUM>-<NUM> for the first reactor (<NUM>. <NUM>), and at a pressure of <NUM> bara and an initial GHSV of <NUM>-<NUM> for the first reactor (<NUM>. The initial temperature was set to <NUM> for each reactor in both simulations. The results for the simulated reforming of NH<NUM> are shown in <FIG> and Tables <NUM>-<NUM> below, respectively.

As can be gathered from the results shown in Table <NUM>, a maximum conversion of <NUM> % of NH<NUM> is possible with the four reactors filled with the Ni-containing catalyst.

As can be gathered from the results shown in Table <NUM>, a maximum conversion of <NUM> % of NH<NUM> is possible with the four reactors filled with the Ni-containing catalyst. When comparing the results shown in <FIG> and <FIG>, it can be seen that at a higher pressure the possible equilibrium conversion was shifted to lower values, and that also the conversions decreased. In particular, the NH<NUM> conversion after the fourth reactor was determined with <NUM> % at <NUM> bara to be lower than for the reforming at <NUM> bara, where a conversion of <NUM> % was determined.

A production unit comprising four reactors was provided, wherein each reactor was filled with the Ru-containing catalyst according to Reference Example <NUM>.

According to Reference Example <NUM>, the reforming of NH<NUM> was simulated for said adiabatic reactor cascade at a pressure of <NUM> bara and an initial GHSV of <NUM>-<NUM> for the first reactor. The initial temperature was set to <NUM> for each reactor in the simulations. The results for the simulated reforming of NH<NUM> are shown in <FIG> and Table <NUM> below.

As can be gathered from the results shown in Table <NUM>, a maximum conversion of <NUM> % of NH<NUM> is possible with the four reactors filled with the Ru-containing catalyst. Further, it can be seen from <FIG> that the third reactor reaches equilibrium conversion of <NUM> % at <NUM>.

Generally, the Ru-containing catalyst showed a higher conversion of NH<NUM> per reactor than the Ni-containing catalyst, but the reaction temperatures were also shifted to lower temperatures by <NUM>, in particular from <NUM> to <NUM> for the inlet temperature.

A production unit comprising four reactors was provided. The third reactor in the direction of the NH<NUM> feed stream was filled in the upstream reaction zone with the Ni-containing catalyst according to Reference Example <NUM> and in the downstream reaction zone with the Ru-containing catalyst according to Reference Example <NUM> to give a zoned reactor. The volume ratio of the reaction zone comprising the Ni-containing catalyst to the reaction zone comprising the Ru-containing catalyst was <NUM>:<NUM>. The other reactors were filled with the Ni-containing catalyst according to Reference Example <NUM>.

According to Reference Example <NUM>, the reforming of NH<NUM> was simulated for said adiabatic reactor cascade at a pressure of <NUM> bara and an initial GHSV of <NUM>-<NUM> for the first reactor (<NUM>. <NUM>), at a pressure of <NUM> bara and an initial GHSV of <NUM>-<NUM> for the first reactor (<NUM>. <NUM>), and at a pressure of <NUM> bara and an initial GHSV of <NUM>-<NUM> for the first reactor (<NUM>. The initial temperature was set to <NUM> for each reactor in all three simulations. The results for the simulated reforming of NH<NUM> are shown in <FIG> and Tables <NUM>-<NUM> below, respectively.

As can be gathered from the results shown in Table <NUM>, the third reactor, which was zoned, leads to a higher conversion. In particular, a conversion of <NUM> % was measured after the third reactor whereas a conversion of <NUM> % was measured after the third reactor for the production unit according to Comparative Example <NUM>, whereby the same conditions, in particular the same pressure, were applied. In addition thereto, the NH<NUM> conversion after the fourth reactor was significantly improved. In particular, a conversion of <NUM> % was determined after the fourth reactor, whereas a conversion of <NUM> % was determined after the fourth reactor for the production unit according to Comparative Example <NUM>. As can be taken from the results shown in <FIG>, the conversion was determined as being <NUM> % at the reactor inlet and <NUM> % at the reactor outlet, meaning that over <NUM>% of the total conversion in the production unit was achieved in the third reactor alone. In contrast thereto, the third reactor of the production unit according to Comparative Example <NUM> only achieved about <NUM> % of the total conversion in the production unit.

As can be gathered from the results shown in Table <NUM>, the third reactor, which was zoned, leads to a higher conversion. In particular, a conversion of <NUM> % was measured after the third reactor whereas a conversion of <NUM> % was measured after the third reactor for the production unit according to Comparative Example <NUM>, whereby the same conditions, in particular the same pressure, were applied. In addition thereto, the NH<NUM> conversion after the fourth reactor was significantly improved. In particular, a conversion of <NUM> % was measured after the fourth reactor, whereas a conversion of <NUM> % was measured after the fourth reactor for the production unit according to Comparative Example <NUM>. As can be taken from the results shown in <FIG>, the conversion was determined as being <NUM> % at the reactor inlet and <NUM> % at the reactor outlet, meaning that over <NUM> % of the total conversion in the production unit was achieved in the third reactor alone. In contrast thereto, the third reactor of the production unit according to Comparative Example <NUM> only achieved about <NUM> % of the total conversion in the production unit.

As can be gathered from the results shown in Table <NUM>, the third reactor, which was zoned, leads to a higher conversion. In particular, a conversion of <NUM> % was measured after the third reactor, wherein a GSHV of <NUM>-<NUM> was applied, whereas a conversion of <NUM> % was measured after the third reactor for the production unit according to Comparative Example <NUM>, wherein a GHSV of <NUM>-<NUM> was applied. Further, the NH<NUM> conversion after the fourth reactor was slightly lower than for the production unit according to Comparative Example <NUM>, but the GSHV was comparatively higher. In particular, a conversion of <NUM> % was measured after the fourth reactor, wherein a GHSV of <NUM>-<NUM> was applied, whereas a conversion of <NUM> % was measured after the fourth reactor for the production unit according to Comparative Example <NUM>, wherein a GHSV of <NUM>-<NUM> was applied. As can be taken from the results shown in <FIG>, the conversion was determined as being <NUM> % at the reactor inlet and <NUM> % at the reactor outlet, meaning that over <NUM> % of the total conversion in the production unit was achieved in the third reactor alone. In contrast thereto, the third reactor of the production unit according to Comparative Example <NUM> only achieved about <NUM> % of the total conversion in the production unit.

A production unit comprising four reactors was provided. The third reactor in the direction of the NH<NUM> feed stream was filled in the upstream reaction zone with the Ni-containing catalyst according to Reference Example <NUM> and in the downstream reaction zone with the Ru-containing catalyst according to Reference Example <NUM>. The volume ratio of the reaction zone comprising the Ni-containing catalyst to the reaction zone comprising the Ru-containing catalyst was varied as detailed in Table <NUM> below. The other reactors were filled with the Ni-containing catalyst according to Reference Example <NUM>.

According to Reference Example <NUM>, the reforming of NH<NUM> was simulated for said adiabatic reactor cascade at a pressure of <NUM> bara and an initial GHSV of <NUM>-<NUM> for the first reactor and an initial GHSV of <NUM>-<NUM> for the first reactor. The initial temperature was set to <NUM> for each reactor in all simulations. The results for the simulated reforming of NH<NUM> are shown in Table <NUM> below.

As can be gathered from the results shown in Table <NUM>, a volume ratio of <NUM>:<NUM> of the reaction zone comprising the Ru-containing catalyst to the reaction zone comprising the Ni-containing catalyst in the third reactor leads to high conversions of <NUM> % after reactor four. Even the implementation of a reaction zone comprising the Ru-containing catalyst of only <NUM> volume-% shows already a significant conversion improvement after the third reactor. In particular, a conversion of <NUM> % was measured after the third reactor, whereas a conversion of <NUM> % was measured after the third reactor for the production unit according to Comparative Example <NUM> at <NUM> bara.

A production unit comprising three reactors was provided. The first and second reactor in the direction of the NH<NUM> feed stream were respectively filled in the upstream reaction zone with the Ni-containing catalyst according to Reference Example <NUM> and in the downstream reaction zone with the Ru-containing catalyst according to Reference Example <NUM> to give two zoned reactors. The volume ratio of the reaction zone comprising the Ni-containing catalyst to the reaction zone comprising the Ru-containing catalyst was <NUM>:<NUM> for both reactors. The third reactor was filled with the Ni-containing catalyst according to Reference Example <NUM>.

According to Reference Example <NUM>, the reforming of NH<NUM> was simulated for said adiabatic reactor cascade at a pressure of <NUM> bara and an initial GHSV of <NUM>-<NUM> for the first reactor. The initial temperature was set to <NUM> for each reactor. The results for the simulated reforming of NH<NUM> are shown in <FIG> and Table <NUM> below, respectively.

Claim 1:
A zoned reactor for the reforming of NH<NUM> to N<NUM> and H<NUM>, wherein the reactor is an adiabatic rector, and wherein the reactor comprises
a reactor inlet and a reactor outlet, the reactor inlet and the reactor outlet being separated by the axial length L of the reactor, and
n reaction zones arranged in sequence and extending from the reactor inlet to the reactor outlet along the axial length L of the reactor, wherein n is an integer in the range of from <NUM> to <NUM>,
wherein the length of each of the n reaction zones in axial direction constitutes a fraction of the length L of the reactor, wherein the sum of the lengths of all of the reaction zones in axial direction is less than or equal to L,
wherein independently from one another, each of the n reaction zones comprises one or more catalytic components,
wherein the inlet reaction zone which is adjacent to the reactor inlet displays a higher light-off temperature T50 in the reforming of NH<NUM> to N<NUM> and H<NUM> than each of the one or more subsequent reaction zones downstream thereof,
wherein the outlet reaction zone which is adjacent to the reactor outlet displays a lower light-off temperature T50 in the reforming of NH<NUM> to N<NUM> and H<NUM> than each of the one or more preceding reaction zones upstream thereof, and
wherein each of the optional intermediate reaction zones between the inlet and outlet reaction zones respectively displays a light-off temperature T50 in the reforming of NH<NUM> to N<NUM> and H<NUM> which is lower than each of the one or more preceding reaction zones upstream thereof and which is higher than each of the one or more subsequent reaction zones downstream thereof,
wherein the T50 light-off temperature is determined according to Reference Example <NUM>.