Zoned reactor for reforming of NH3

Abstract

The present invention relates to an adiabatic, zoned reactor for the reforming of NH3 to N2 and H2, in particular comprising n reaction zones (n being an integer ranging from 2 to 5, and independently of one another, each of the n reaction zones comprises one or more catalytic components, and each reaction zone from an inlet reaction zone to an outlet reaction zone exhibits a lower light-off temperature T50 in the reforming of NH3 to N2 and H2) arranged in sequence and extending along an axial length L of the reactor, and then the downstream one thereafter. Furthermore, the present invention relates to a production apparatus comprising said reactor, a method for the reforming of NH3 to N2 and H2, and the use of said reactor and said production apparatus.

Description

[Technical field]

[0001] The present invention relates to a zone cracking reactor, a production apparatus comprising said reactor, and a method for reforming NH3 to N2 and H2. Furthermore, the present invention relates to the use of said reactor and said production apparatus. A schematic diagram of a zone cracking reactor according to the present invention is shown in Figure 1. [Background technology]

[0002] NH3 is increasingly seen as an energy vector, since, among other things, it can be used to store significant amounts of H2. Sustainable NH3 (hence called "blue" or "green" NH3) can be produced on a large scale from renewable energy sources. On-site reforming of NH3 (equation I), where H2 is needed, could be the last step to close the H2 value chain based on renewable electricity. To obtain H2 directly at high pressures (e.g. in the range of 10-80 bara), the NH3 reforming itself would also need to be carried out at these pressures. 2NH3⇔N2+3H2ΔH r =+91.2kJ / mol (I)

[0003] Typically, the endothermic reaction is carried out in the process at a temperature of 250-750° C. and a pressure of up to 80 bara.

[0004] US 2020 / 0062590 A1 relates to an NH3 decomposition catalyst system. In particular, an NH3 decomposition system is disclosed therein, comprising a support material and a catalytic component, the catalytic component comprising Ru and at least one additional metal that catalyzes and / or promotes NH3 decomposition.

[0005] WO 2013 / 004649 A1 relates to an adiabatic reaction cascade for the production of chlorine using a cerium oxide catalyst, which in particular comprises at least two reaction stages connected in series with intermediate cooling.

[0006] S. Osborne et al. disclose a study on flexible tools for methanol synthesis in Nitrogen+Syngas, 373, September-October 2021, p.44-50. Based on a computational study of multi-level layered loading as applied to a methanol reaction system, it was found that more efficient utilization of the catalyst can be achieved by multi-level layering in consideration of the isothermal operation of the reactor. Summary of the Invention [Problem to be solved by the invention]

[0007] However, there is still a need for improved reactor designs for the reforming of NH3. It was therefore an object of the present invention to provide a reactor for the reforming of NH3 to N2 and H2, which allows for a cost- and resource-efficient conversion of NH3 in particular. More specifically, it was an object of the present invention to provide a new reactor design for adiabatic reactors, in which, inter alia, the catalyst can be used more efficiently, thus allowing for improved conversion and / or a more compact reactor design. [Means for solving the problem]

[0008] Surprisingly, it has been found that said object can be achieved by a novel zoning concept in the reactor, in particular by using a high-temperature active catalyst in the inlet section and a low-temperature active catalyst in the outlet section of the adiabatic reactor.

[0009] The present invention therefore relates to a zoning concept for an adiabatic reactor, where each catalyst operates at an advantageous temperature, thus allowing the application of a relatively large temperature window and an efficient use of the spent catalyst. In particular, a high-temperature active catalyst, operating for example with a possible temperature window of 750°C to 500°C, 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 NH3 is an endothermic reaction. When approaching the lower temperatures of 500°C, the high-temperature active catalyst becomes less and less effective. Then, a low-temperature active catalyst, allowing operation for example with a temperature window ranging from 500°C to 250°C, 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 500°C, and as a function of the ongoing NH3 conversion, the temperature decreases further to 250°C.

[0010] Surprisingly, it was found that the zoning concept in the adiabatic reactor allows high NH3 conversion, respectively reforming, in a relatively small reactor volume. Moreover, the present invention allows a large temperature window to be applied in the reactor, and each catalyst in the reaction zone is selected based on its activity in a specific temperature range. This also allows, for example, the combination of a relatively cost-effective high-temperature catalyst with a highly active low-temperature catalyst in the effective zone. Thus, the present invention allows any combination of low-temperature active catalysts and high-temperature active catalysts for this type of reaction. In short, it was surprisingly found that the present invention not only allows an effective way of using a specific catalyst for any temperature window, but also provides an economically favorable solution. These findings are advantageous at any reaction pressure and are widely applicable. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Therefore, the present invention provides a zoned reactor for the reforming of NH to N and H, wherein the reactor is an adiabatic reactor, the reactor comprising: a reactor inlet and a reactor outlet, the reactor inlet and the reactor outlet being separated by a length L in the axial direction of the reactor; n reaction zones (n is an integer ranging from 2 to 5) arranged in sequence and extending along an axial length L of the reactor from the reactor inlet to the reactor outlet; Including, the length of each of the n axial reaction zones constitutes a small fraction of the length L of the reactor, and the sum of all the lengths of the axial reaction zones is less than or equal to L; Independently of one another, each of the n reaction zones comprises one or more catalytic components; an inlet reaction zone adjacent to the reactor inlet exhibits a higher light-off temperature T50 in the reforming of NH3 to N2 and H2 than each of one or more subsequent reaction zones downstream thereof; an outlet reaction zone adjacent to the reactor outlet exhibits a lower light-off temperature T50 in the reforming of NH3 to N2 and H2 than each of the one or more preceding reaction zones upstream thereof; and Each of the optional intermediate reaction zones between the inlet and outlet reaction zones exhibits a light-off temperature T50 in the reforming of NH3 to N2 and H2 that is lower than each of the one or more preceding reaction zones upstream thereof and higher than each of the one or more subsequent reaction zones downstream thereof, the T50 light-off temperature being preferably measured according to Reference Example 1; Regarding the reactor.

[0012] Within the meaning of the present application, an adiabatic reactor preferably denotes a reactor whose reactor walls are insulated so 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 exclusively with the environment via the inlet and outlet of the reactor.

[0013] The inlet reaction zone preferably exhibits a T50 light-off temperature above 450°C, more preferably in the range of above 450°C to 850°C, more preferably in the range of 470 to 650°C, more preferably in the range of 490 to 570°C, more preferably in the range of 510°C to 540°C, more preferably in the range of 520 to 530°C, the T50 light-off temperature preferably being measured according to Reference Example 1.

[0014] The outlet reaction zone preferably exhibits a T50 light-off temperature of 450°C or less, more preferably in the range of 200 to 450°C or less, more preferably in the range of 300 to 430°C, more preferably in the range of 340 to 410°C, more preferably in the range of 360 to 390°C, more preferably in the range of 370 to 380°C, the T50 light-off temperature preferably being measured according to Reference Example 1.

[0015] The axial length L of the reactor is preferably in the range of 0.1 to 20 m, more preferably in the range of 0.5 to 10 m, more preferably in the range of 1.0 to 5.0 m, more preferably in the range of 1.5 to 2.5 m, and more preferably in the range of 1.89 to 1.93 m.

[0016] The reactor preferably has a circular cross section.

[0017] When the reactor has a circular cross section, it is preferred that the reactor shape is cylindrical and that the reactor has a diameter D in the range of 0.1 to 20 m, preferably in the range of 0.5 to 10 m, more preferably in the range of 1.0 to 5.0 m, more preferably in the range of 1.5 to 2.5 m, and more preferably in the range of 1.89 to 1.93 m.

[0018] When the reactor shape is cylindrical and the reactor has a diameter D, it is preferred that the reactor exhibits an aspect ratio L:D of the reactor axial length L to the reactor diameter D in the range of 0.01:1 to 1:0.01, more preferably in the range of 0.05:1 to 1:0.05, more preferably in the range of 0.1:1 to 1:0.1, more preferably in the range of 0.3:1 to 1:0.3, more preferably in the range of 0.5:1 to 1:0.5, more preferably in the range of 0.8:1 to 1:0.8, more preferably in the range of 0.9:1 to 1:0.9, and the aspect ratio L:D is more preferably 1:1.

[0019] n is an integer in the range of 2 to 5, more preferably in the range of 2 to 4, more preferably n is 2 or 3, and the reactor more preferably comprises two reaction zones.

[0020] Each of the reaction zones, independently of the other, preferably has a length in the range of (0.01·L / n) to (1.99·L / n), more preferably in the range of (0.05·L / n) to (1.95·L / n), more preferably in the range of (0.1·L / n) to (1.9·L / n), more preferably in the range of (0.2·L / n) to (1.8·L / n), more preferably in the range of (0.5·L / n) to (1.5·L / n), more preferably in the range of (0.9·L / n) to (1.1·L / n), more preferably in the range of (0.95·L) / n to (1.05·L) / n, more preferably in the range of (0.99·L) / n to (1.01·L) / n, each of the reaction zones more preferably having a length of L / n.

[0021] The one or more catalyst components contained in each of the reaction zones are preferably, independently of 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.

[0022] The one or more catalyst components contained in the inlet reaction zone are preferably 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, and the one or more catalyst components contained in the inlet reaction zone are preferably one or more Ni-containing catalysts.

[0023] The one or more catalyst components comprised in the outlet reaction zone are preferably 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, and the one or more catalyst components comprised in the outlet reaction zone are preferably one or more Ru-containing catalysts.

[0024] The one or more catalyst components contained in each of the optional intermediate reaction zones between the inlet and outlet reaction zones are preferably selected, independently from one another, from the group consisting of a Ni-containing catalyst, an Fe-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, and mixtures thereof, and the one or more catalyst components contained 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 catalyst components selected from the group consisting of a Ni-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, and mixtures of two or more thereof.

[0025] When the one or more catalyst components comprised in each of the n reaction zones are, independently of 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), more preferably M is Fe or Mo.

[0026] Furthermore, when the one or more catalyst components comprised in each of the n reaction zones are, independently of one another, selected from the group consisting of a Ni-containing catalyst, an Fe-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, 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 supports on which Co and / or Ni and / or M, preferably Co and M and / or Ni and M, are supported, the support material being preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, and mixtures thereof, and more preferably the support material comprises, preferably consists of, Al2O3.

[0027] When the one or more Ni-containing catalysts contain 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, the Ni-containing catalyst preferably exhibits an M:Ni atomic ratio in the range of 0.1:99.9 to 70:30, more preferably 0.1:99.9 to 50:50, more preferably 0.1:99 to 40:60, more preferably 0.1:99.9 to 30:70, more preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, more preferably 5:95 to 6:94. When M is Fe, it is particularly preferred that the Ni-containing catalyst exhibits an Fe:Ni atomic ratio in the range of 1:2 to 1:1, preferably in the range of 1:1.65 to 1:1.20, more preferably in the range of 1:1.45 to 1:1.40. When M is Mo, the Ni-containing catalyst preferably exhibits a Mo:Ni atomic ratio in the range of 1:1.50 to 1:0.50, more preferably in the range of 1:1.20 to 1:0.80, more preferably in the range of 1:1.10 to 1:0.90.

[0028] When the one or more Co-containing catalysts contain 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, the Co-containing catalyst preferably exhibits an M:Co atomic ratio in the range of 0.1:99.9 to 70:30, more preferably 0.1:99.9 to 50:50, more preferably 0.1:99 to 40:60, more preferably 0.1:99.9 to 30:70, more preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, more preferably 5:95 to 6:94. When M is Mo, the Co-containing catalyst preferably exhibits an Mo:Co atomic ratio in the range of 1:1.50 to 1:0.50, more preferably 1:1.20 to 1:0.80, more preferably 1:1.10 to 1:0.90.

[0029] Furthermore, when the one or more catalyst components contained in each of the n reaction zones are, independently of one another, selected from the group consisting of a Ni-containing catalyst, an Fe-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, 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.

[0030] When the one or more Ni-containing catalysts and / or the one or more Co-containing catalysts further contain Al and O, it is preferable that the one or more Ni-containing catalysts further contain Mg, and the molar ratio of Ni:Mg:Al is preferably in the range of 1:(0.1-12):(0.5-20), more preferably 1:(0.5-8):(1-12), more preferably 1:(1-5):(3-8), more preferably 1:(1.5-3):(3.5-5), more preferably 1:(2.0-2.4):(4.0-4.4).

[0031] Furthermore, when the one or more Ni-containing catalysts and / or the one or more Co-containing catalysts further contain Al and O, it is preferred that the one or more Ni-containing catalysts contain Ni in an amount in the range of 5 to 25 wt%, preferably in the range of 10 to 20 wt%, more preferably in the range of 14 to 17 wt%, and more preferably in the range of 15 to 16 wt%, based on 100 wt% of the total weight of the one or more Ni-containing catalysts.

[0032] Furthermore, when the one or more Ni-containing catalysts and / or the one or more Co-containing catalysts further contain Al and O, it is preferable that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the one or more Ni-containing catalysts consist of Ni, Mg, Al, and O.

[0033] Furthermore, when the one or more Ni-containing catalysts and / or the one or more Co-containing catalysts further contain Al and O, it is preferable that 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the one or more Ni-containing catalysts consists of Ni, M, Mg, Al, and O.

[0034] When the one or more Co-containing catalysts further contain Al and O, it is preferable that the one or more Co-containing catalysts further contain La, and the molar ratio of Co:La:Al is preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), more preferably 1:(1.3-1.7):(10-12).

[0035] When the one or more Co-containing catalysts further contain La, according to the first alternative, it is preferred that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the one or more Co-containing catalysts consists of Co, La, Al, and O.

[0036] When the one or more Co-containing catalysts further contain La, according to the second alternative, it is preferred that 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the one or more Co-containing catalysts consists of Co, M, La, Al, and O.

[0037] Furthermore, when the one or more catalyst components contained in each of the n reaction zones are, independently of 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 on which Ru is supported, the support materials being preferably selected from the group consisting of metal oxides, the metals of the metal oxides being preferably 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). More preferably the one or more support materials comprise one or more metal oxides selected from the group consisting of Al2O3, ZrO2 and spinel, (including combinations of two or more thereof), preferably from the group consisting of ZrO2 and spinel, (including combinations of two or more thereof), more preferably the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2, more preferably the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2.

[0038] When the one or more Ru-containing catalysts further comprise one or more support materials on which Ru is supported, it is preferred that the one or more support materials exhibit a pore volume in the range of 0.2-3 ml / g, preferably 0.4-1.5 ml / g, more preferably 0.6-1 ml / g, more preferably 0.8-0.85 ml / g, the pore volume preferably being measured according to ISO 15901-2:2022.

[0039] Furthermore, when the one or more catalyst components contained in each of the n reaction zones are independently selected from the group consisting of a Ni-containing catalyst, an Fe-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, and a mixture thereof, the one or more Ru-containing catalysts are each 20 to 800 m 2 / g, more preferably 30 to 500m2 / g, more preferably 40 to 300 m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, more preferably 70 to 75m 2 / g, the BET surface area preferably being measured according to ISO 9277:2010.

[0040] Furthermore, when the one or more catalyst components contained in each of the n reaction zones are independently 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 exhibit a pore volume in the range of 0.1 to 2 ml / g, more preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, more preferably 0.3 to 0.35 ml / g, the pore volume preferably being measured according to ISO 15901-2:2022.

[0041] Furthermore, when the one or more catalyst components contained in each of the n reaction zones are independently selected from the group consisting of a Ni-containing catalyst, an Fe-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, and mixtures thereof, it is preferred that the one or more Ru-containing catalysts contain Ru in an amount in the range of 0.5 to 15 wt %, more preferably 1 to 10 wt %, more preferably 2 to 8 wt %, more preferably 3 to 6.5 wt %, more preferably 4 to 6 wt %, and more preferably 4.5 to 5.5 wt %, based on 100 wt % of the total amount of the one or more support materials.

[0042] Furthermore, when the one or more catalyst components contained in each of the n reaction zones are independently selected from the group consisting of a Ni-containing catalyst, an Fe-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, and a mixture thereof, it is preferable that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the one or more Ru-containing catalysts consists of Ru and one or more support materials.

[0043] Furthermore, when the one or more catalyst components contained in each of the n reaction zones are, independently of 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 alkali metal and / or alkaline earth metal hydroxides, which are preferably supported on one or more support materials supporting Ru, and the alkali metal and / or alkaline earth metal hydroxides are preferably is selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH and KOH, (including mixtures of two or more thereof), more preferably from the group consisting of Mg(OH)2, Ca(OH)2, 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), more preferably the catalyst further comprises KOH and / or LiOH, preferably KOH.

[0044] When the one or more Ru-containing catalysts further comprise one or more alkali metal hydroxides, the one or more Ru-containing catalysts preferably comprise the one or more alkali metal hydroxides in an amount in the range of 0.5 to 15 wt %, more preferably 1 to 10 wt %, more preferably 2 to 8 wt %, more preferably 3 to 6.5 wt %, more preferably 4 to 6 wt %, more preferably 4.5 to 5.5 wt %, based on 100 wt % of the total amount of the one or more support materials.

[0045] Furthermore, when the one or more Ru-containing catalysts further contain one or more alkali metal hydroxides, it is preferable that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the one or more Ru-containing catalysts consists of Ru, one or more alkali metal hydroxides, and one or more support materials.

[0046] The one or more catalyst components are preferably in the form of a molded article and / or in powder form, more preferably in the form of a molded article, more preferably in the form of a 3D printed article, extrudate, or tablet, more preferably in the form of an extrudate or tablet.

[0047] The one or more catalyst components are preferably contained in a fixed bed.

[0048] The reactor is preferably operated in downflow or upflow mode, preferably in downflow mode.

[0049] The present invention further relates to an apparatus for reforming NH to N and H, the apparatus comprising k adiabatic reactors, each comprising a reactor inlet and a reactor outlet, at least one of the reactors being a zoned reactor according to any one of the embodiments disclosed herein, k being an integer ranging from 1 to 6, the reactors being arranged in sequence along the reaction flow, and a heating element being disposed upstream of each of the k reactors.

[0050] Preferably, one and the same heating device is arranged upstream of each of the k reactors.

[0051] Alternatively, and preferably, a separate heating device is placed upstream of each of the k reactors.

[0052] k is preferably 2 or more, more preferably an integer in the range of 3 to 6, more preferably an integer in the range of 3 to 5, and more preferably 3 or 4.

[0053] The production unit preferably includes one or two zoned reactors according to any of the embodiments disclosed herein.

[0054] Still further, the present invention provides a method for reforming NH3 to N2 and H2, the method comprising: (i) providing a zoned reactor according to any one of the embodiments disclosed herein; (ii) providing a feed gas stream comprising NH3; (iii) feeding the feed gas stream provided in (ii) into a reactor according to any one of the embodiments disclosed herein provided in (i), wherein the feeding is performed at a feed gas stream pressure in the range of 1 to 80 bara and at a feed gas stream temperature in the range of 175 to 825° C.; (iv) removing a product gas stream from the reactor or from the production apparatus provided in (i), the product gas stream comprising N2 and H2; The present invention relates to a method comprising the steps of:

[0055] The feed gas stream provided in (ii) preferably comprises 1-100% by volume of NH3, more preferably 3-99.99% by volume, more preferably 5-99.95% by volume, more preferably 10-99.9% by volume, more preferably 20-99.8% by volume, more preferably 30-99.7% by volume, more preferably 40-99.6% by volume, more preferably 50-99.5% by volume.

[0056] The feed gas stream provided in (ii) preferably comprises 0-50 vol.% N2, more preferably 0.01-30 vol.%, more preferably 0.03-15 vol.%, more preferably 0.05-5 vol.%, more preferably 0.1-1 vol.%, more preferably 0.12-0.5 vol.%, more preferably 0.14-0.16 vol.%.

[0057] The feed gas stream provided in (ii) preferably comprises 0-75 vol.% H, more preferably 0-60 vol.%, more preferably 0-50 vol.%, more preferably 0-40 vol.%, more preferably 0-35 vol.%, more preferably 0-30 vol.% H.

[0058] It is preferred that the feed gas stream provided in (ii) comprises 100-50,000 ppmv, more preferably 200-30,000 ppmv, more preferably 500-25,000 ppmv, more preferably 1,000-20,000 ppmv, more preferably 3,000-15,000 ppmv, more preferably 5,000-10,000 ppmv of HO.

[0059] The total amount of NH3, N2, and H2 contained in the feed gas stream provided in (ii) is preferably in the range of 90 to 100 wt%, more preferably 95 to 99.95 vol%, more preferably 98 to 99.9 vol%, more preferably 99 to 99.85 vol%, more preferably 99.7 to 99.8 vol%.

[0060] The feeding in (iii) is preferably carried out at a temperature in the range of 200 to 850°C, more preferably in the range of 225 to 775°C, more preferably in the range of 250 to 750°C.

[0061] The feeding in (iii) is preferably carried out at a pressure in the range of from 2 to 80 bara, more preferably in the range of from 4 to 50 bara, more preferably in the range of from 5 to 20 bara.

[0062] The feed gas flow rate is 2000-16000h -1 More preferably, in the range of 2500 to 9500 h -1 More preferably, in the range of 3000 to 6000 h -1 It is preferred that the gas be fed to the reactor according to any one of the embodiments disclosed herein at a gas hourly space velocity in the range of

[0063] The reactor provided in (i) is preferably operated in downflow or upflow mode, more preferably in downflow mode.

[0064] Furthermore, the present invention relates to the use of a reactor according to any one of the embodiments disclosed herein or a production apparatus according to any one of the embodiments disclosed herein for the reforming of NH3 to N2 and H2.

[0065] The present invention is further illustrated by the following set of embodiments and combinations of embodiments, which are derived from the dependencies and back references as indicated. In particular, it is pointed out that whenever a range of embodiments is mentioned, for example in conjunction with a term such as "the reactor according to any one of the embodiments 1 to 4", it means that any embodiment within this range is expressly disclosed to a person skilled in the art, i.e., the wording of this term should be understood by a person skilled in the art to be synonymous with "the reactor according to any one of the embodiments 1, 2, 3 and 4". Furthermore, it is explicitly pointed out that the following set of embodiments represents a properly structured part of the present description, which is directed to the general and preferred aspects of the present invention, and not a set of claims determining the scope of protection.

[0066] 1. A zoned reactor for the reforming of NH3 to N2 and H2, wherein the reactor is an adiabatic reactor, the reactor comprising: a reactor inlet and a reactor outlet, the reactor inlet and the reactor outlet being separated by a length L in the axial direction of the reactor; n reaction zones (n is an integer ranging from 2 to 5) arranged in sequence and extending along an axial length L of the reactor from the reactor inlet to the reactor outlet; Including, the length of each of the n axial reaction zones constitutes a small fraction of the length L of the reactor, and the sum of all the lengths of the axial reaction zones is less than or equal to L; Independently of one another, each of the n reaction zones comprises one or more catalytic components; an inlet reaction zone adjacent to the reactor inlet exhibits a higher light-off temperature T50 in the reforming of NH3 to N2 and H2 than each of one or more subsequent reaction zones downstream thereof; an outlet reaction zone adjacent to the reactor outlet exhibits a lower light-off temperature T50 in the reforming of NH3 to N2 and H2 than each of the one or more preceding reaction zones upstream thereof; and A reactor, wherein each of the optional intermediate reaction zones between the inlet and outlet reaction zones exhibits a light-off temperature T50 in the reforming of NH3 to N2 and H2 that is lower than each of one or more preceding reaction zones upstream thereof and higher than each of one or more subsequent reaction zones downstream thereof, the T50 light-off temperature being preferably measured according to Reference Example 1. 2. The reactor as described in embodiment 1, wherein the inlet reaction zone exhibits a T50 light-off temperature above 450°C, preferably in the range of above 450°C to 850°C, more preferably in the range of 470 to 650°C, more preferably in the range of 490 to 570°C, more preferably in the range of 510°C to 540°C, more preferably in the range of 520 to 530°C, wherein the T50 light-off temperature is preferably measured according to Reference Example 1. 3. The reactor according to embodiment 1 or 2, wherein the outlet reaction zone exhibits a T50 light-off temperature of 450°C or less, preferably in the range of 200 to 450°C or less, more preferably in the range of 300 to 430°C, more preferably in the range of 340 to 410°C, more preferably in the range of 360 to 390°C, more preferably in the range of 370 to 380°C, the T50 light-off temperature being preferably measured according to Reference Example 1. 4. The reactor according to any one of embodiments 1 to 3, wherein the axial length L of the reactor is in the range of 0.1 to 20 m, preferably in the range of 0.5 to 10 m, more preferably in the range of 1.0 to 5.0 m, more preferably in the range of 1.5 to 2.5 m, and more preferably in the range of 1.89 to 1.93 m. 5. The reactor of any one of embodiments 1 to 4, wherein the reactor has a circular cross section. 6. The reactor according to embodiment 5, wherein the reactor shape is cylindrical and the reactor has a diameter D, D being in the range of 0.1 to 20 m, preferably in the range of 0.5 to 10 m, more preferably in the range of 1.0 to 5.0 m, more preferably in the range of 1.5 to 2.5 m, more preferably in the range of 1.89 to 1.93 m. 7. The reactor according to embodiment 6, wherein the reactor exhibits an aspect ratio L:D of the axial length L of the reactor to the diameter D of the reactor in the range of 0.01:1 to 1:0.01, preferably in the range of 0.05:1 to 1:0.05, more preferably in the range of 0.1:1 to 1:0.1, more preferably in the range of 0.3:1 to 1:0.3, more preferably in the range of 0.5:1 to 1:0.5, more preferably in the range of 0.8:1 to 1:0.8, more preferably in the range of 0.9:1 to 1:0.9, and the aspect ratio L:D is more preferably 1:1. 8. The reactor according to any one of the preceding embodiments, wherein n is an integer in the range of 2 to 5, preferably in the range of 2 to 4, more preferably n is 2 or 3, and the reactor more preferably comprises two reaction zones. 9. The reactor according to any one of the embodiments 1 to 8, wherein each of the reaction zones, independently of one another, has a length in the range of (0.01·L / n) to (1.99·L / n), preferably in the range of (0.05·L / n) to (1.95·L / n), more preferably in the range of (0.1·L / n) to (1.9·L / n), more preferably in the range of (0.2·L / n) to (1.8·L / n), more preferably in the range of (0.5·L / n) to (1.5·L / n), more preferably in the range of (0.9·L / n) to (1.1·L / n), more preferably in the range of (0.95·L) / n to (1.05·L) / n, more preferably in the range of (0.99·L) / n to (1.01·L) / n, and each of the reaction zones preferably has a length of L / n. 10. The reactor according to any one of embodiments 1 to 9, wherein the one or more catalyst components contained in each of the n reaction zones are independently selected from the group consisting of a Ni-containing catalyst, an Fe-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, and mixtures thereof, preferably from the group consisting of a Ni-containing catalyst, a Ru-containing catalyst, and mixtures thereof. 11. The reactor of any one of embodiments 1 to 10, wherein the one or more catalyst 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, preferably from the group consisting of Ni-containing catalysts, Ru-containing catalysts, and mixtures thereof, and the one or more catalyst components comprised in the inlet reaction zone are preferably one or more Ni-containing catalysts. 12. The reactor of any one of embodiments 1 to 11, wherein the one or more catalyst 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, preferably from the group consisting of I-containing catalysts, Ru-containing catalysts, and mixtures thereof, and the one or more catalyst components comprised in the outlet reaction zone are preferably one or more Ru-containing catalysts. 13. The reactor of any one of embodiments 1-12, wherein the one or more catalyst components included in each of the optional intermediate reaction zones between the inlet and outlet reaction zones are independently selected from the group consisting of a Ni-containing catalyst, an Fe-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, and mixtures thereof, and the one or more catalyst components included in each of the optional intermediate reaction zones between the inlet and outlet reaction zones preferably comprise one or more catalyst components independently selected from the group consisting of a Ni-containing catalyst, a Co-containing catalyst, a Ru-containing catalyst, and mixtures of two or more thereof. 14. The reactor according to any one of embodiments 10 to 13, wherein 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), 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), more preferably wherein M is Fe or Mo. 15. The reactor according to any one of embodiments 10-14, wherein the one or more Co-containing catalysts and / or the one or more Ni-containing catalysts further comprise one or more support materials on which Co and / or Ni and / or M are supported, preferably Co and M and / or Ni and M are supported, and the support material is preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, and mixtures thereof, more preferably the support material comprises, preferably consists of, Al2O3. 16. The reactor according to embodiment 14 or 15, wherein the Ni-containing catalyst exhibits an M:Ni atomic ratio in the range of 0.1:99.9 to 70:30, preferably 0.1:99.9 to 50:50, more preferably 0.1:99 to 40:60, more preferably 0.1:99.9 to 30:70, more preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, more preferably 5:95 to 6:94. 17. The reactor of embodiment 16, wherein M is Fe and the Ni-containing catalyst exhibits an Fe:Ni atomic ratio in the range of 1:2 to 1:1, preferably in the range of 1:1.65 to 1:1.20, more preferably in the range of 1:1.45 to 1:1.40. 18. The reactor of embodiment 16, wherein M is Mo and the Ni-containing catalyst exhibits a Mo:Ni atomic ratio in the range of 1:1.50 to 1:0.50, preferably in the range of 1:1.20 to 1:0.80, more preferably in the range of 1:1.10 to 1:0.90. 19. The reactor according to embodiment 14 or 15, wherein the Co-containing catalyst exhibits an M:Co atomic ratio in the range of 0.1:99.9 to 70:30, preferably 0.1:99.9 to 50:50, more preferably 0.1:99 to 40:60, more preferably 0.1:99.9 to 30:70, more preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, more preferably 5:95 to 6:94. 20. The reactor of embodiment 19, wherein M is Mo and the Co-containing catalyst exhibits an atomic ratio of Mo:Co in the range of 1:1.50 to 1:0.50, preferably in the range of 1:1.20 to 1:0.80, more preferably in the range of 1:1.10 to 1:0.90. 21. The reactor of any one of embodiments 10 to 20, wherein the one or more Ni-containing catalysts and / or the one or more Co-containing catalysts further comprise Al and O. 22. The reactor according to embodiment 21, wherein the one or more Ni-containing catalysts further contain Mg, and the molar ratio of Ni:Mg:Al is preferably in the range of 1:(0.1-12):(0.5-20), more preferably 1:(0.5-8):(1-12), more preferably 1:(1-5):(3-8), more preferably 1:(1.5-3):(3.5-5), more preferably 1:(2.0-2.4):(4.0-4.4). 23. The reactor of embodiment 21 or 22, wherein the one or more Ni-containing catalysts contain Ni in an amount in the range of 5 to 25 wt%, preferably in the range of 10 to 20 wt%, more preferably in the range of 14 to 17 wt%, more preferably in the range of 15 to 16 wt%, based on 100 wt% of the total weight of the one or more Ni-containing catalysts. 24. The reactor according to any one of embodiments 21 to 23, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the one or more Ni-containing catalysts consists of Ni, Mg, Al, and O. 25. The reactor according to any one of embodiments 21 to 24, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the one or more Ni-containing catalysts consists of Ni, M, Mg, Al, and O. 26. The method of embodiment 21, wherein the one or more Co-containing catalysts further comprise La, and the molar ratio of Co:La:Al is preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), more preferably 1:(1.3-1.7):(10-12). 27. The method according to embodiment 26, wherein 95 to 100 wt%, preferably 97 to 100 wt%, more preferably 98 to 100 wt%, more preferably 99 to 100 wt%, more preferably 99.5 to 100 wt%, more preferably 99.9 to 100 wt% of the one or more Co-containing catalysts consists of Co, La, Al, and O. 28. The method according to embodiment 26, wherein 95 to 100 wt%, preferably 97 to 100 wt%, more preferably 98 to 100 wt%, more preferably 99 to 100 wt%, more preferably 99.5 to 100 wt%, more preferably 99.9 to 100 wt% of the one or more Co-containing catalysts consists of Co, M, La, Al, and O. 29. The one or more Ru-containing catalysts further comprise one or more support materials on which Ru is supported, the support material preferably being selected from the group consisting of metal oxides, the metals of the metal oxides being preferably 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). 29. The reactor according to any one of embodiments 10-28, wherein the one or more support materials comprise one or more metal oxides selected from the group consisting of Al2O3, ZrO2, and spinel, (including mixtures of two or more thereof), preferably from the group consisting of ZrO2 and spinel, (including mixtures of two or more thereof); more preferably the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2; more preferably the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2. 30. The reactor according to embodiment 29, wherein the one or more support materials exhibit a pore volume in the range of 0.2 to 3 ml / g, preferably 0.4 to 1.5 ml / g, more preferably 0.6 to 1 ml / g, more preferably 0.8 to 0.85 ml / g, the pore volume preferably being measured according to ISO 15901-2:2022. 31. One or more Ru-containing catalysts are used in the range of 20 to 800 m 2 / g, preferably 30 to 500m 2 / g, more preferably 40 to 300 m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, more preferably 70 to 75 m 2 31. The reactor according to any one of embodiments 10 to 30, wherein the reactor exhibits a BET surface area in the range of 100 / g, the BET surface area being preferably measured according to ISO 9277:2010. 32. The reactor according to any one of embodiments 10 to 31, wherein the one or more Ru-containing catalysts exhibit a pore volume in the range of 0.1 to 2 ml / g, preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, more preferably 0.3 to 0.35 ml / g, the pore volume being preferably measured according to ISO 15901-2:2022. 33. The reactor of any one of embodiments 10 to 32, wherein the one or more Ru-containing catalysts comprise Ru in an amount ranging from 0.5 to 15 wt%, preferably from 1 to 10 wt%, more preferably from 2 to 8 wt%, more preferably from 3 to 6.5 wt%, more preferably from 4 to 6 wt%, more preferably from 4.5 to 5.5 wt%, based on 100 wt% of the total amount of the one or more support materials. 34. The reactor according to any one of embodiments 10 to 33, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the one or more Ru-containing catalysts consists of Ru and one or more support materials. 35. The reactor according to any one of embodiments 10 to 34, wherein the one or more Ru-containing catalysts further comprise one or more alkali metal and / or alkaline earth metal hydroxides, which are preferably supported on one or more support materials supporting Ru, and the alkali metal and / or alkaline earth metal hydroxides are preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH, and KOH, including mixtures of two or more thereof, more preferably from the group consisting of Mg(OH)2, Ca(OH)2, 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, and more preferably the catalyst further comprises KOH and / or LiOH, preferably KOH. 36. The reactor of embodiment 35, wherein the one or more Ru-containing catalysts comprise one or more alkali metal hydroxides in an amount ranging from 0.5 to 15 wt%, preferably from 1 to 10 wt%, more preferably from 2 to 8 wt%, more preferably from 3 to 6.5 wt%, more preferably from 4 to 6 wt%, more preferably from 4.5 to 5.5 wt%, based on 100 wt% of the total amount of the one or more support materials. 37. The reactor according to embodiment 35 or 36, wherein 95-100% by weight, preferably 97-100% by weight, more preferably 98-100% by weight, more preferably 99-100% by weight, more preferably 99.5-100% by weight, more preferably 99.9-100% by weight of the one or more Ru-containing catalysts consists of Ru, one or more alkali metal hydroxides, and one or more support materials. 38. The reactor according to any one of the preceding embodiments, wherein the one or more catalyst components are in the form of a molded article and / or in powder form, preferably in the form of a molded article, more preferably in the form of a 3D printed article, extrudate, or tablet, more preferably in the form of an extrudate or tablet. 39. The reactor of any one of the preceding embodiments, wherein the one or more catalyst components are contained in a fixed bed. 40. The reactor according to any one of the preceding embodiments, wherein the reactor is operated in a downflow or upflow mode, preferably in a downflow mode. 41. A production apparatus for reforming NH3 into N2 and H2, the production apparatus comprising a reactor inlet and a reactor outlet, respectively; at least one of the reactors is the zoned reactor according to any one of embodiments 1 to 40; k is an integer in the range of 1 to 6; and the reactors are arranged in sequence along the reaction flow; A manufacturing apparatus, wherein a heating component is disposed upstream of each of the k reactors. 42. The manufacturing apparatus of embodiment 41, wherein one and the same heating device is disposed upstream of each of the k reactors. 43. The manufacturing apparatus of embodiment 41, wherein a separate heating device is disposed upstream of each of the k reactors. 44. The manufacturing apparatus according to any one of embodiments 41 to 43, wherein k is 2 or more, k is preferably an integer in the range of 3 to 6, preferably in the range of 3 to 5, and k is preferably 3 or 4. 45. The production apparatus of any one of embodiments 41-44, comprising one or two zoned reactors of any one of embodiments 1-40. 46. ​​A method for reforming NH3 into N2 and H2, the method comprising: (i) providing a zoned reactor according to any one of embodiments 1 to 40; (ii) providing a feed gas stream comprising NH3; (iii) feeding the feed gas stream provided in (ii) into a reactor according to any one of embodiments 1-40 provided in (i), wherein the feeding is performed at a feed gas stream pressure in the range of 1-80 bara and at a feed gas stream temperature in the range of 175-825° C.; (iv) removing a product gas stream from the reactor or from the production apparatus provided in (i), the product gas stream comprising N2 and H2; The method includes: 47. The method of embodiment 46, wherein the feed gas stream provided in (ii) comprises 1-100% by volume of NH3, preferably 3-99.99% by volume, more preferably 5-99.95% by volume, more preferably 10-99.9% by volume, more preferably 20-99.8% by volume, more preferably 30-99.7% by volume, more preferably 40-99.6% by volume, more preferably 50-99.5% by volume. 48. The method of embodiment 46 or 47, wherein the feed gas stream provided in (ii) comprises 0-50 vol.%, preferably 0.01-30 vol.%, more preferably 0.03-15 vol.%, more preferably 0.05-5 vol.%, more preferably 0.1-1 vol.%, more preferably 0.12-0.5 vol.%, more preferably 0.14-0.16 vol.% N2. 49. The method of any one of embodiments 46 to 48, wherein the feed gas stream provided in (ii) comprises 0-75% by volume H2, preferably 0-60% by volume, more preferably 0-50% by volume, more preferably 0-40% by volume, more preferably 0-35% by volume, more preferably 0-30% by volume. 50. The method of any one of embodiments 46 to 49, wherein the feed gas stream provided in (ii) comprises 100 to 50,000 ppmv, preferably 200 to 30,000 ppmv, more preferably 500 to 25,000 ppmv, more preferably 1,000 to 20,000 ppmv, more preferably 3,000 to 15,000 ppmv, more preferably 5,000 to 10,000 ppmv of HO. 51. The method according to any one of embodiments 46 to 50, wherein the combined amount of NH3, N2, and H2 in the feed gas stream provided in (ii) is in the range of 90 to 100% by volume, preferably 95 to 99.95% by volume, more preferably 98 to 99.9% by volume, more preferably 99 to 99.85% by volume, more preferably 99.7 to 99.8% by volume. 52. The method of any one of embodiments 46 to 51, wherein the providing in (iii) is carried out at a temperature in the range of 200 to 850°C, preferably in the range of 225 to 775°C, more preferably in the range of 250 to 750°C. 53. The method according to any one of embodiments 46 to 52, wherein the feeding in (iii) is carried out at a pressure in the range of 2 to 80 bara, preferably in the range of 4 to 50 bara, more preferably in the range of 5 to 20 bara. 54. The supply gas flow rate is 2000-16000 h -1 Preferably in the range of 2500 to 9500 h -1 More preferably, in the range of 3000 to 6000 h -1 The method of any one of embodiments 46 to 53, wherein the gas is fed into the reactor of any one of embodiments 1 to 40 at a gas hourly space velocity in the range of 55. The method of any one of embodiments 46 to 54, wherein the reactor provided in (i) is operated in downflow or upflow mode, preferably in downflow mode. 56. Use of the reactor according to any one of embodiments 1 to 40 or the production apparatus according to any one of embodiments 41 to 45 for reforming NH3 to N2 and H2.

[0067] The present invention is illustrated by the following examples, reference examples, and comparative examples. EXAMPLES

[0068] Reference Example 1: Measurement of T50 light-off temperature in reforming NH3 to N2 and H2 Prior to catalytic testing, the catalyst samples were placed in a reactor and activated in a reducing atmosphere of 5 vol.% H2 in Ar at a temperature of 350 °C (residence time 1 h, heating rate 2 °C / min). After catalyst activation, a feed stream containing ammonia (94.5 vol.% NH3, 0.5 vol.% H2O, 5 vol.% Ar) was fed into the reactor and the partial pressure of NH3 (p(NH3)) was set at 30 bara. The gas hourly space velocity (GHSV) for NH3 content was 4000 h -1 The temperature of the feed stream was varied from 350 to 650° C. At each point of measurement, the temperature was held constant and the conversion was measured at steady state (conversion variation of ±1% or less).

[0069] Reference Example 2: Simulation of catalytic activity Kinetic models of the Ni-containing catalyst from Reference Example 3 and the Ru-containing catalyst from Reference Example 4 were developed using MATLAB® software (version R2021b).

[0070] Figure 3 shows the parity plots of the simulated and experimental values ​​for the Ni-containing catalyst (Figure 3A) and for the Ru-containing catalyst (Figure 3B). Very good agreement was found. Thus, the estimated kinetic parameters implemented in the guaranteed model were found to be very reasonable.

[0071] Based on the kinetic model, the NH3-reforming process was simulated based on a series of adiabatic reactors within a prescribed scenario.

[0072] As a scenario, 3000h -1 A gas hourly space velocity of 1000 s (unless otherwise stated) was set for the first reactor in the direction of the NH3 feed flow. As reactors, adiabatic reactors were used, with the reactors arranged in series, thus as a cascade. Furthermore, the volume of each reactor was defined with a length of 1.9113 m and a diameter of 1.9113 m. Thus, the aspect ratio of each reactor was 1:1. Due to the volume increase as a function of the reforming of NH3, the gas hourly space velocity also increases when comparing the GHSV at the reactor inlet of a reactor with that at the reactor outlet of said reactor. Furthermore, the simulations were performed at pressures of 5 and 20 bara.

[0073] In this way, the reforming of NH3 was simulated for the production units according to Comparative Examples 1-2 and Examples 3-5, and also with varying temperature, pressure, and gas hourly space velocity. The numbering of the reactors indicates the direction of gas flow from reactor 1 to reactor n.

[0074] Reference Example 3: Provision of Ni-containing catalyst The Ni-containing catalyst was provided according to the method described in Example E1 of WO 2013 / 068905 A1.

[0075] However, instead of powdered nickel nitrate hexahydrate, an aqueous solution of nickel nitrate (14% Ni concentration) was used. The various raw materials were mixed into a paste, which was then extruded. The extrudate was crushed and sieved to target fractions with particle sizes between 200 and 900 μm after drying and low-temperature calcination.

[0076] The sieved powder was then mixed with 2.8% by weight of graphite (Asbury Graphite 3160) and 5.5% by weight of cellulose (Arbocel BWW 40). The resulting mixture was compressed into a molded part with a four-hole cross section as shown in FIG. 1 of WO 2020 / 157202 A. For sintering, the molded part was heated in an annealing furnace to a temperature of 1,030-1,050 ° C and held there for 4 hours.

[0077] The sintered product had a nickel content of 15.5 wt %, a magnesium content of 14.0 wt %, and an aluminum content of 29.5 wt %.

[0078] As shown in FIG. 2, the T50 light-off temperature of the Ni-containing catalyst of Example 1, measured according to Reference Example 1, was 525°C.

[0079] Reference Example 4: Provision of Ru-containing catalyst Ru supported on ZrO2 was prepared by the addition of zirconium oxide powder (D9-89, BASF, BET surface area: 78 m) to obtain Ru supported on ZrO2 at a loading of 5 wt%. 2 The catalyst was prepared according to Example 8 of WO 2015 / 086639 A2 by impregnation of a ruthenium salt solution onto a ruthenium sulphide-containing sulphide (0.01 ml / g, pore volume: 0.84 ml / g) of ruthenium sulphide. The catalyst was then extruded to form extrudates with a diameter of 3 mm.

[0080] A 5 g sample of the obtained 5 wt% Ru on ZrO2 extrudates was subjected to impregnation with KOH solution. To this effect, 5 g of the obtained extrudates were split to form fractions ranging from 315 to 500 microns, which were then impregnated by incipient wetness impregnation method with 0.25 g of KOH dissolved in 1.65 ml of water. The sample was then dried at 120°C and then calcined at 500°C for 2 hours under inert atmosphere.

[0081] As shown in FIG. 2, the T50 light-off temperature of the Ru-containing catalyst of Example 1, measured according to Reference Example 1, was 375° C.

[0082] Comparative Example 1: Production Unit Containing Four Non-Zoned Reactors

[0083] 1.1 Manufacturing Equipment Assembly A production apparatus including four reactors, each reactor being filled with the Ni-containing catalyst according to Example 3, was provided.

[0084] 1.2 Simulation of catalytic activity According to Reference Example 2, the reforming of NH3 was carried out for the adiabatic reactor cascade at a pressure of 5 bara and for 3000 h for the first reactor. -1 at an initial GHSV (1.2.1) of 1000 sq. m., and at a pressure of 20 bara and 3000 h for the first reactor. -1 The reactors were simulated with an initial GHSV (1.2.2) of 1000° C. The initial temperature was set at 750° C. for each reactor in both simulations. The results for the simulated reforming of NH3 are shown in Figures 4-5 and Tables 1-2 below.

[0085] 1.2.1 Simulation at 5 bara pressure Table 1 Inlet and outlet stream temperatures and NH3 conversion values ​​at 5 bara for four reactors packed with Ni-containing catalyst

[0086] [Table 1]

[0087] As can be inferred from the results shown in Table 1, a maximum conversion of 94.7% of NH3 is possible in the four reactors packed with Ni-containing catalyst.

[0088] 1.2.2 Simulation at 20 bara pressure Table 2 Inlet and outlet stream temperatures and NH3 conversion values ​​at 20 bara for four reactors packed with Ni-containing catalyst

[0089] [Table 2]

[0090] As can be inferred from the results shown in Table 2, a maximum conversion of 87.3% of NH3 is possible with the four reactors filled with Ni-containing catalyst. When comparing the results shown in Figures 4 and 5, it can be seen that the equilibrium conversion possible at higher pressures shifted to lower values ​​and that the conversion also decreased. In particular, the NH3 conversion after the fourth reactor was measured at 87.3% at 20 bara, lower than for reforming at 5 bara, where a conversion of 94.7% was measured.

[0091] Comparative Example 2: Production Unit Containing Four Non-Zoned Reactors 2.1 Manufacturing Equipment Assembly A production apparatus including four reactors, each reactor being filled with the Ru-containing catalyst according to Example 4, was provided.

[0092] 2.2 Simulation of catalytic activity According to Reference Example 2, the reforming of NH3 was carried out for the adiabatic reactor cascade at a pressure of 5 bara and for 3000 h for the first reactor. -1 The reactors were simulated with an initial GHSV of 100° C. The initial temperature was set to 600° C. for each reactor in the simulation. The results for the simulated reforming of NH3 are shown in FIG. 6 and Table 3 below. Table 3 Inlet and outlet stream temperatures and NH3 conversion values ​​at 5 bara for four reactors packed with Ru-containing catalyst

[0093] [Table 3]

[0094] As can be inferred from the results shown in Table 3, a maximum conversion of 99.2% of NH3 is possible in the four reactors packed with Ru-containing catalyst. Furthermore, it can be seen from Figure 6 that the third reactor reaches an equilibrium conversion of 92.2% at 348.6 °C.

[0095] In general, the Ru-containing catalysts showed higher NH3 conversion per reactor than the Ni-containing catalysts, but the reaction temperature was also shifted by 150° C. lower, especially for the inlet temperature from 750° C. to 600° C.

[0096] Example 3: Production apparatus containing one zoned reactor and three non-zoned reactors 3.1 Manufacturing Equipment Assembly A production apparatus including four reactors was provided. The third reactor in the direction of the NH3 feed flow was filled with the Ni-containing catalyst according to Reference Example 3 in the upstream reaction zone and the Ru-containing catalyst according to Reference Example 4 in the downstream reaction zone to obtain a zoned reactor. The volume ratio of the reaction zone containing the Ni-containing catalyst to the reaction zone containing the Ru-containing catalyst was 1:1. The other reactors were filled with the Ni-containing catalyst according to Reference Example 3.

[0097] 3.2 Simulation of catalytic activity According to Reference Example 2, the reforming of NH3 was carried out for the adiabatic reactor cascade at a pressure of 5 bara and for 3000 h for the first reactor. -1 At an initial GHSV (3.2.1), a pressure of 20 bara and 3000 h for the first reactor -1 at an initial GHSV (3.2.2) of 10000 h for the first reactor at a pressure of 20 bara and -1 The reactors were simulated with an initial GHSV (3.2.3) of 1000°C. The initial temperature was set to 750°C for each reactor in all three simulations. The results for the simulated reforming of NH3 are shown in Figures 7-9 and Tables 4-6 below, respectively.

[0098] 3.2.1 Pressure of 5 bara and 3000 h for the first reactor -1 Simulation with GHSV Table 4: The third reactor was zoned, with inlet and outlet stream temperatures and NH3 conversion values ​​at 5 bara for the four reactors. The upstream reaction zone of the third reactor is designated as reactor 3.1 and the downstream reaction zone as reactor 3.2.

[0099] [Table 4]

[0100] As can be inferred from the results shown in Table 4, the zoned, third reactor leads to a higher conversion. In particular, a conversion of 94.3% was measured after the third reactor, while a conversion of 76.3% was measured after the third reactor for the production unit according to Comparative Example 1 (whereby the same conditions, in particular the same pressure, were applied). In addition, the NH3 conversion after the fourth reactor was significantly improved. In particular, a conversion of 99.8% was measured after the fourth reactor, while a conversion of 94.7% was measured after the fourth reactor for the production unit according to Comparative Example 1. As can be seen from the results shown in FIG. 7, the conversion was measured to be 53.9% at the reactor inlet and 94.3% at the reactor outlet, meaning that more than 40% of the total conversion in the production unit was achieved by the third reactor alone. In contrast, the third reactor of the production unit according to Comparative Example 1 only achieved about 22% of the total conversion in the production unit.

[0101] 3.2.2 Pressure of 20 bara and 3000 h for the first reactor -1 Simulation with initial GHSV Table 5: The third reactor was zoned, with inlet and outlet stream temperatures and NH3 conversion values ​​at 20 bara for the four reactors. The upstream reaction zone of the third reactor is designated as reactor 3.1 and the downstream reaction zone as reactor 3.2.

[0102] [Table 5]

[0103] As can be inferred from the results shown in Table 5, the zoned, third reactor leads to a higher conversion. In particular, a conversion of 86.9% was measured after the third reactor, while a conversion of 70.0% was measured after the third reactor for the production unit according to Comparative Example 1 (whereby the same conditions, in particular the same pressure, were applied). In addition, the NH3 conversion after the fourth reactor was significantly improved. In particular, a conversion of 98.4% was measured after the fourth reactor, while a conversion of 87.3% was measured after the fourth reactor for the production unit according to Comparative Example 1. As can be seen from the results shown in FIG. 8, the conversion was measured to be 49.7% at the reactor inlet and 86.9% at the reactor outlet, meaning that more than 37% of the total conversion in the production unit was achieved by the third reactor alone. In contrast, the third reactor of the production unit according to Comparative Example 1 only achieved about 22% of the total conversion in the production unit.

[0104] 3.2.3 Pressure of 20 bara and 9000 h for the first reactor -1 Simulation with GHSV Table 6: The third reactor was zoned, with inlet and outlet stream temperatures and NH3 conversion values ​​at 20 bara for the four reactors. The upstream reaction zone of the third reactor is designated as reactor 3.1 and the downstream reaction zone as reactor 3.2.

[0105] [Table 6]

[0106] As can be inferred from the results shown in Table 6, the zoned, third reactor leads to higher conversion. In particular, a conversion of 76.5% was measured after the third reactor (12431 h -1 was applied), while a conversion rate of 70.0% was measured after the third reactor for the production unit according to Comparative Example 1 (4490 h -1GHSV was applied). Furthermore, the NH3 conversion after the fourth reactor was slightly lower than for the production plant according to Comparative Example 1, but the GHSV was higher in comparison. In particular, a conversion of 86.1% was measured after the fourth reactor (15883 h -1 GHSV was applied), while a conversion of 87.3% was measured after the fourth reactor for the production unit according to Comparative Example 1 (5100 h -1 GHSV of 10 ...

[0107] Example 4: Production apparatus containing one zoned reactor and three non-zoned reactors 4.1 Manufacturing Equipment Assembly A production apparatus was provided that included four reactors. The third reactor in the direction of the NH3 feed stream was filled with the Ni-containing catalyst according to Reference Example 3 in the upstream reaction zone and the Ru-containing catalyst according to Reference Example 4 in the downstream reaction zone. The volume ratio of the reaction zone containing the Ni-containing catalyst to the reaction zone containing the Ru-containing catalyst was varied as detailed in Table 7 below. The other reactors were filled with the Ni-containing catalyst according to Reference Example 3.

[0108] 4.2 Simulation of catalytic activity According to Reference Example 2, the reforming of NH3 was carried out for the adiabatic reactor cascade at a pressure of 20 bara and for 3000 h for the first reactor. -1 The initial GHSV was 3000h for the first reactor. -1 The reactors were simulated with an initial GHSV of 1000° C. The initial temperature was set to 750° C. for each reactor in all simulations. The results for the simulated reforming of NH3 are shown in Table 7 below. Table 7: The third reactor was zoned; temperatures of the inlet and outlet streams and NH3 conversion values ​​at 20 bara of the third and fourth reactors.

[0109] [Table 7]

[0110] As can be gathered from the results shown in Table 7, a volume ratio of 25:75 of the reaction zone containing the Ru-containing catalyst to the reaction zone containing the Ni-containing catalyst in the third reactor leads to a high conversion rate of 98.4% after the fourth reactor. Even the implementation of a reaction zone containing only 1% by volume of the Ru-containing catalyst already shows a significant conversion increase after the third reactor. In particular, a conversion rate of 75.1% was measured after the third reactor, while a conversion rate of 70.0% was measured after the third reactor for the production device according to Comparative Example 1 at 20 bara.

[0111] Example 5: A production system containing three reactors, two of which are zoned 5.1 Manufacturing Equipment Assembly A production apparatus including three reactors was provided. The first and second reactors in the direction of NH3 feed flow were respectively filled with Ni-containing catalyst according to Reference Example 3 in the upstream reaction zone and Ru-containing catalyst according to Reference Example 4 in the downstream reaction zone to obtain a two-zone reactor. The volume ratio of the reaction zone containing Ni-containing catalyst to the reaction zone containing Ru-containing catalyst was 1:1 for both reactors. The third reactor was filled with Ni-containing catalyst according to Reference Example 3.

[0112] 5.2 Simulation of catalytic activity According to Reference Example 2, the reforming of NH3 was carried out for the adiabatic reactor cascade at a pressure of 20 bara and for 3000 h for the first reactor. -1 The reactors were simulated with an initial GHSV of 1000 sq. m. The initial temperature was set at 750° C. for each reactor. The results for the simulated reforming of NH3 are shown in FIG. 10 and Table 8 below, respectively. Table 8: The inlet and outlet stream temperatures and NH3 conversion values ​​at 20 bara for the three reactors, with the first and second reactors zoned. The upstream reaction zone of the reactor is designated as reactor x.1 and the downstream reaction zone as reactor x.2.

[0113] [Table 8]

[0114] As can be gathered from the results shown in Table 8, the implementation of two zoned reactors in the production plant leads to a relatively higher conversion after two reactor stages. In particular, a conversion of 83.6% was measured after the second reactor, while a conversion of 49.7% was measured after the second reactor for the production plant according to Comparative Example 1. Thus, the implementation of a third reactor in the production plant is sufficient to reach the equilibrium conversion, in particular a conversion of 98.3% at 615.7° C. as shown in FIG. 10, so that the implementation of a fourth reactor is discarded. [Brief description of the drawings]

[0115] [Figure 1] FIG. 1 shows a schematic diagram of a zoned reactor (1) having two zones. The reactor inlet (2) is separated from the reactor outlet (3) by the reactor axial length L. An inlet reaction zone (4) is located adjacent to the reactor inlet and an outlet reaction zone (5) is located adjacent to the reactor outlet. [Diagram 2] 1 shows the results of measuring the T50 light-off temperature according to Reference Example 1 for the Ni-containing catalyst according to Reference Example 3 and the Ru-containing catalyst according to Reference Example 4. The equilibrium conversion is shown by the thick solid line. The arrows and dotted lines indicate classification as high-temperature or low-temperature active catalysts, where a catalyst that shows 50% NH3 conversion at a temperature of 450°C or less can be classified as a low-temperature active catalyst, and a catalyst that shows 50% NH3 conversion at a temperature of more than 450°C can be classified as a high-temperature active catalyst. [Diagram 3]3A and 3B show parity plots of simulated and experimental values ​​for the partial pressures of NH3, N2, and H2 for the Ru-containing catalyst according to Reference Example 4 (FIG. 3A) and for the Ni-containing catalyst according to Reference Example 3 (FIG. 3B), respectively. [Figure 4] 4 shows the NH3 conversion as a function of temperature at 5 bara, simulated for a production unit according to Comparative Example 1. The temperature is shown on the abscissa in ° C. and the conversion is shown on the ordinate in %. [Diagram 5] 4 shows the NH3 conversion as a function of temperature at 20 bara, simulated for a production unit according to Comparative Example 1. The temperature is shown on the abscissa in ° C. and the conversion is shown on the ordinate in %. [Figure 6] 4 shows the NH3 conversion as a function of temperature at 5 bara, simulated for a production unit according to Comparative Example 2. The temperature is shown on the abscissa in ° C. and the conversion is shown on the ordinate in %. [Figure 7] 1 shows the NH3 conversion as a function of temperature at an initial GHSV of 5 bara and 3000 h-1 simulated for a production unit according to Example 3. Temperature is shown on the abscissa in °C and conversion is shown on the ordinate in %. [Figure 8] 1 shows the NH3 conversion as a function of temperature at an initial GHSV of 20 bara and 3000 h-1 simulated for a production unit according to Example 3. Temperature is shown on the abscissa in ° C. and conversion is shown on the ordinate in %. [Figure 9] 1 shows the NH3 conversion as a function of temperature at an initial GHSV of 20 bara and 9000 h-1 simulated for a production unit according to Example 3. Temperature is shown on the abscissa in ° C. and conversion is shown on the ordinate in %. [Figure 10] 4 shows the NH3 conversion as a function of temperature at 20 bara, simulated for a production unit according to Example 5. Temperature is shown on the abscissa in ° C. and conversion is shown on the ordinate in %.

[0116] References: - U.S. Patent Application Publication No. 2020 / 0062590 A1 - International Publication No. 2013 / 004649 A1 Brochure - S.Osborne et al.,Nitrogen+Syngas,373,September-October 2021,p.44-50

Claims

1. A zone-divided reactor for the reforming of NH3 to N2 and H2, wherein the reactor is an adiabatic reactor, and the reactor comprises a reactor inlet and a reactor outlet separated by an axial length L of the reactor, and n reaction zones (n being an integer between 2 and 5) arranged in sequence and extending from the reactor inlet to the reactor outlet along the axial length L of the reactor, wherein the length of each of the n reaction zones in the axial direction constitutes a small portion of the length L of the reactor, the sum of the lengths of all the reaction zones in the axial direction is less than or equal to L, and each of the n reaction zones independently contains one or more catalyst components, and the inlet reaction zone adjacent to the reactor inlet is... A reactor having a light-off temperature T50 for the reforming of NH3 to N2 and H2 that is higher than each of the one or more subsequent reaction zones downstream of the reactor outlet, an outlet reaction zone adjacent to the reactor outlet having a light-off temperature T50 for the reforming of NH3 to N2 and H2 that is lower than each of the one or more preceding reaction zones upstream of it, and each of the optional intermediate reaction zones between the inlet and outlet reaction zones having a light-off temperature T50 for the reforming of NH3 to N2 and H2 that is lower than each of the one or more preceding reaction zones upstream of it and higher than each of the one or more subsequent reaction zones downstream of it, wherein the T50 light-off temperature is determined according to Reference Example 1.

2. The reactor according to claim 1, wherein the inlet reaction zone exhibits a T50 light-off temperature exceeding 450°C.

3. The reactor according to claim 1, wherein the outlet reaction zone exhibits a T50 light-off temperature of 450°C or lower.

4. The reactor according to claim 1, wherein n is an integer in the range of 2 to 5.

5. The reactor according to claim 1, wherein each of the reaction zones independently has a length in the range of 0.01 L / n to 1.99 L / n.

6. The reactor according to claim 1, wherein one or more catalyst components contained in each of the n reaction zones are independently selected from the group consisting of Ni-containing catalysts, Fe-containing catalysts, Co-containing catalysts, Ru-containing catalysts, and mixtures thereof.

7. The reactor according to claim 6, wherein the one or more Co-containing catalysts and / or the one or more Ni-containing catalysts include a mixture of two or more of them, and further comprises a metal M selected from the group consisting of alkali metals, alkaline earth metals, Mo, and Fe.

8. The reactor according to claim 6, wherein the one or more Ni-containing catalysts contain Ni in an amount ranging from 5% to 25% by weight, based on 100% by weight of the total weight of the one or more Ni-containing catalysts.

9. The reactor according to claim 6, wherein the one or more Ru-containing catalyst contains Ru in an amount ranging from 0.5 to 15% by weight, based on 100% by weight of the total weight of the one or more carrier materials.

10. The reactor according to claim 6, wherein the one or more Ru-containing catalysts further comprises one or more alkali metal and / or alkaline earth metal hydroxides.

11. The reactor according to claim 1, wherein the one or more catalyst components are in the form of a molded article and / or in the form of a powder.

12. N ２ and H ２ NH to ３ A manufacturing apparatus for modifying a material, wherein the manufacturing apparatus includes k adiabatic reactors, each including a reactor inlet and a reactor outlet, at least one of the reactors is a zone-divided reactor as described in claim 1, k is an integer in the range of 1 to 6, and the reactors are arranged sequentially along the reaction flow. A manufacturing apparatus in which heating components are arranged upstream of each of the k reactors.

13. The manufacturing apparatus according to claim 12, wherein one identical heating device is located upstream of each of the k reactors.

14. N ２ and H ２ NH to ３ A method for modifying the said method, (i) the step of providing the zone division reactor according to claim 1, (ii) NH ３ The steps include providing a supply gas flow containing; (iii) A step of supplying the supply gas flow provided in (iii) into the reactor according to claim 1 provided in (i), wherein the supply is performed at a pressure of the supply gas flow in the range of 1 to 80 bara and at a temperature of the supply gas flow in the range of 175 to 825°C; (iv) removing the product gas stream from the reactor provided in (i) or from the production apparatus, wherein the product gas stream contains N ２ and H ２ ; and Methods that include...

15. N ２ and H ２ NH to ３ Use of the reactor described in claim 1 or the manufacturing apparatus described in claim 12 for the modification of the product.

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