NH3 reforming method

Abstract

The present invention relates to a method for NH reforming, the method comprising the steps of: (i) providing a reactor containing an NH reforming catalyst C1, the NH reforming catalyst C1 comprising a metal M1 selected from the group consisting of groups 6 to 11 of the periodic table, and mixtures of two or more thereof; (ii) preparing a feed gas stream F1 containing NH; and (iii) feeding F1 prepared according to step (ii) to the reactor and contacting F1 with the NH reforming catalyst C1 to obtain a product gas stream P1 comprising HO and the NH reforming catalyst C2, wherein the reactor has a temperature of 100°C or higher; the feeding according to step (ii) is initiated at time t1; and at time t2, the HO(P1):HO(F1) molar ratio of the HO in the product gas stream P1 to the HO in the feed gas stream F1 exceeds 1:1, and the difference between t2 and t1 is in the range of 5 seconds to 10 days.

Description

[Technical Field]

[0001] The present invention relates to a method for reforming NH3 using an NH3 reforming catalyst, the method comprising the step of reducing said catalyst in a gas stream comprising NH3. [Background technology]

[0002] NH3 is considered the energy vector of the future, capable of chemically storing significant amounts of H2. Therefore, sustainable NH3 may be produced on a large scale from renewable energy sources. On-site reforming of NH3 where H2 is required (see Equation 1 below) may be the final step in closing the renewable electricity-based H2 value chain. (1) 2NH3 ⇔ N2 + 3H2 To directly utilize H2 at high pressures, especially at pressures of 10-50 bara, the reforming of NH3 itself is very often carried out at these pressures.

[0003] I. Lucentini et al., Eng. Chem. Res. 2021, 60, 18560-18611 and T. Le et al., Korean J. Chem. Eng., 2021, 38(6), 1087-1103 each provide an overview of catalysts used for the decomposition of ammonia.

[0004] X.-K. Li et al., Journal of Catalysis, 2005, 236, 181-189, is particularly concerned with the decomposition of ammonia over Ni and Ru catalysts.

[0005] Bell et al., Top Catal., 2016, 59, 1438-1457, relates to the decomposition of ammonia using non-noble metal catalysts, where catalysts containing mainly Co and Ni are discussed.

[0006] Fang et al., in ACS Catalysis 2022, 12, 3938-3954, outline the challenges and potential of Ru-based catalysts for ammonia synthesis and utilization.

[0007] Typically used NH reforming catalysts must be activated in a reducing gas prior to NH reforming. Conventionally, NH reforming catalysts are activated using hydrogen as a reducing agent, which may be diluted with one or more inert gases, such as N or Ar. For example, WO 2023 / 111017 A1 relates to a method for reforming ammonia, including activation of the catalyst with H, which allows reforming at particularly relatively high pressures.

[0008] Therefore, there was a need to provide a relatively simple process, particularly by avoiding the additional step of preparing a specific reduction stream for reducing spent catalyst. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] WO 2023 / 111017 A1 [Non-patent literature]

[0010] [Non-Patent Document 1] I. Lucentini et al., Eng. Chem. Res. 2021, 60, 18560-18611 [Non-patent document 2] T. Le et al., Korean J. Chem. Eng., 2021, 38(6), 1087-1103 [Non-patent document 3] X.-K. Li et al., Journal of Catalysis, 2005, 236, 181-189 [Non-patent document 4] Bell et al., Top Catal., 2016, 59, 1438-1457 [Non-patent document 5] Fang et al., ACS Catalysis 2022, 12, 3938-3954 Summary of the Invention [Problem to be solved by the invention]

[0011] It was therefore an object of the present invention to provide a method for NH3 reforming that allows for a simple and resource-efficient process. [Means for solving the problem]

[0012] Surprisingly, it has been found that a novel process for NH3 reforming can be provided, in which the used NH3 reforming catalyst is reduced in a gas stream containing NH3. It has therefore been found that the application of NH3 feedstock as an activation reactant facilitates the start-up sequence, or alternatively, an NH3 reforming plant. The process of the present invention is generally applicable to NH3 reforming catalysts that must be activated in a reducing gas.

[0013] Accordingly, the present invention relates to a method for NH3 reforming, said method comprising the following steps: (i) providing a reactor containing an NH3 reforming catalyst C1 comprising a metal M1 selected from the group consisting of Groups 6 to 11 of the Periodic Table (including mixtures of two or more thereof); (ii) preparing a feed gas stream F1 containing NH3; (iii) feeding F1 prepared according to step (ii) into a reactor and contacting F1 with an NH3 reforming catalyst C1 to obtain a product gas stream P1 comprising H2O and an NH3 reforming catalyst C2, wherein the reactor has a temperature of 100°C or greater; Including, The supply according to step (ii) is started at time t1; At time t2, the molar ratio H2O(P1):H2O(F1) of the H2O in product gas stream P1 to the H2O in feed gas stream F1 exceeds 1:1, and the H2O in product gas stream P1 and the H2O in feed gas stream F1 are preferably determined according to DIN EN 14790, more preferably according to Reference Example 1, and the difference between t2 and t1 is in the range of 5 seconds to 10 days.

[0014] In the context of the present invention, the difference between t2 and t1 may also be designated as Δt. Furthermore, the difference between t2 and t1 Δt is calculated as Δt=t2−t1, where t2 is greater than t1. [Brief explanation of the drawings]

[0015] [Figure 1] Figure 1 shows the results of NH3 reforming using a Ni-containing catalyst. The NH3 conversion is shown in % on the vertical axis, and the temperature in °C on the horizontal axis. Diamonds (◆) indicate measurement points for the catalyst activated in an H2 gas atmosphere, and triangles (▲) indicate measurement points for the catalyst activated in an NH3 gas atmosphere. [Figure 2] Figure 2 shows a side view of the arrangement for determining Side Crushing Strength 1 (SCS1) on the left, a side view of the arrangement for determining Side Crushing Strength 2 (SCS2) in the middle, and a side view of the arrangement for determining Side Crushing Strength 3 (SCS3) on the right. [Figure 3] 3 shows the TPR diagram of the passivated and partially reduced Ni-containing catalyst prepared according to Reference Example 6. The horizontal axis shows the temperature in ° C., and the vertical axis shows the intensity of the TCD signal in arbitrary units. [Figure 4] 4 shows the TPR diagram of the fully oxidized Ni-containing catalyst prepared according to Reference Example 7. The horizontal axis shows the temperature in ° C., and the vertical axis shows the intensity of the TCD signal in arbitrary units. [Figure 5] 5 shows a TPR diagram of the Ni-containing catalyst prepared according to Reference Example 6 when analyzed after being used in the test according to Example 9. The horizontal axis shows the temperature in ° C., and the vertical axis shows the intensity of the TCD signal in arbitrary units. [Figure 6] 6 shows the TPR diagram of the Ru-containing catalyst prepared according to Reference Example 8. The horizontal axis shows the temperature in ° C., and the vertical axis shows the intensity of the TCD signal in arbitrary units. DETAILED DESCRIPTION OF THE INVENTION

[0016] At time t2, the molar ratio of H2O in product gas stream P1 to H2O in feed gas stream F1, H2O(P1):H2O(F1), is preferably in the range of 1.0001:1 to 25:1, more preferably in the range of 1.0005:1 to 15:1, more preferably in the range of 1.001:1 to 10:1, more preferably in the range of 1.005:1 to 5:1, more preferably in the range of 1.01:1 to 4:1, more preferably in the range of 1.05:1 to 3:1, more preferably in the range of 1.1:1 to 2:1.

[0017] The difference between t2 and t1 is preferably in the range of 5 seconds to 9 days, preferably in the range of 1 minute to 8 days, more preferably in the range of 5 minutes to 7 days, more preferably in the range of 0.5 hours to 5 days, more preferably in the range of 1 hour to 4 days, more preferably in the range of 3 hours to 2 days, more preferably in the range of 6 hours to 2 days.

[0018] Preferably, the X-ray diffraction pattern of the NH3 reforming catalyst C1 contained in the reactor provided in step (i), preferably determined according to Reference Example 2, shows one or more crystalline phases of one or more oxides of M1.

[0019] Preferably, the X-ray diffraction pattern of the NH3 reforming catalyst C2 obtained from step (iii), preferably determined according to Reference Example 2, shows one or more crystalline phases of element M1.

[0020] Preferably, the X-ray diffraction pattern of the NH3 reforming catalyst C2 obtained from step (iii), preferably determined according to Reference Example 2, does not show any crystalline phase of one or more oxides of M1.

[0021] M1 is preferably selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu, and mixtures of two or more thereof, more preferably from the group consisting of Ni, Co, Ru, Fe, and mixtures thereof.

[0022] When M1 is selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu, and mixtures of two or more thereof, preferably M1 comprises Ni, and preferably is Ni.

[0023] When M1 comprises Ni, the XRD pattern of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably exhibits a mass ratio of NiO crystalline phase to elemental Ni crystalline phase of more than 1:100, more preferably more than 1:10, more preferably in the range of 1:10 to 100:1, more preferably in the range of 1:10 to 10:1, wherein the XRD pattern is preferably determined according to Reference Example 2.

[0024] Furthermore, when M1 contains Ni, the PR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably exhibits a first peak having a maximum value in the range of 100 to 400 °C, more preferably in the range of 120 to 350 °C, more preferably in the range of 150 to 250 °C, where the TPR profile is preferably determined according to Reference Example 3.

[0025] When the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) shows a first peak having a maximum value in the range of 100 to 400 °C, the integrated value of the first peak is preferably in the range of 500 to 4000 μmol / g, more preferably in the range of 1500 to 3000 μmol / g, and more preferably in the range of 2000 to 2500 μmol / g.

[0026] Furthermore, when the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) shows a first peak having a maximum value in the range of 100 to 400°C, the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably shows a second peak having a maximum value in the range of more than 400°C to 900°C, more preferably in the range of 425°C to 850°C, more preferably in the range of 450°C to 800°C, where the TPR profile is preferably determined according to Reference Example 3.

[0027] When the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) shows a second peak having a maximum value in the range of more than 400°C to 900°C, the integrated value of the second peak is in the range of 500 to 4500 μmol / g, more preferably in the range of 1500 to 3500 μmol / g, and more preferably in the range of 2000 to 3000 μmol / g.

[0028] Furthermore, when the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) shows a first peak having a maximum value in the range of 100 to 400°C, the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably shows a third peak having a maximum value in the range of more than 900°C to 1300°C, preferably in the range of 950°C to 1250°C, more preferably in the range of 1000°C to 1200°C, where the TPR profile is preferably determined according to Reference Example 3.

[0029] When the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) shows a third peak having a maximum value in the range of more than 900°C to 1300°C, the integrated value of the third peak is preferably in the range of 100 to 1500 μmol / g, more preferably in the range of 300 to 1250 μmol / g, and more preferably in the range of 500 to 1000 μmol / g.

[0030] When M1 is selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu, and mixtures of two or more thereof, M1 preferably comprises Ru, and more preferably is Ru.

[0031] When M1 comprises Ru, more preferably is Ru, the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably exhibits a peak having a maximum value in the range of 100 to 400 °C, more preferably in the range of 120 to 350 °C, more preferably in the range of 150 to 250 °C, wherein the TPR profile is preferably determined according to Reference Example 3.

[0032] When the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) shows a peak having a maximum value in the range of 100 to 400 °C, the integral value of the peak is preferably in the range of 1500 to 5000 μmol / g, more preferably in the range of 2500 to 4000 μmol / g, and more preferably in the range of 3000 to 3500 μmol / g.

[0033] The reactor provided in step (i) preferably has a length in the range of 0.5 to 20 m, more preferably in the range of 1 to 12 m.

[0034] Preferably, the reactor provided in step (i) is operated in an adiabatic mode.

[0035] The reactor provided in step (i) is preferably directly heated, preferably flame heated or electrically heated.

[0036] The feed gas stream F1 prepared according to step (ii) preferably comprises 0-0.5% by volume of H2, more preferably 0-0.2% by volume, more preferably 0-0.1% by volume, more preferably 0-0.05% by volume, more preferably 0-0.02% by volume, more preferably 0-0.01% by volume, more preferably 0-0.005% by volume, more preferably 0-0.002% by volume, more preferably 0-0.001% by volume of H2.

[0037] The feed gas stream F1 prepared according to step (ii) preferably comprises 1 to 100% by volume, more preferably 2 to 100% by volume, more preferably 4 to 100% by volume, more preferably 5 to 100% by volume, more preferably 50 to 100% by volume, more preferably 80 to 100% by volume, more preferably 85 to 100% by volume, more preferably 89.5 to 100% by volume, preferably 94.5 to 100% by volume, more preferably 99.0 to 100% by volume, more preferably 99.5 to 100% by volume, more preferably 99.6 to 100% by volume, more preferably 99.7 to 100% by volume, more preferably 99.8 to 100% by volume, more preferably 99.9 to 100% by volume, more preferably 99.95 to 100% by volume, more preferably 99.98 to 100% by volume, more preferably 99.99 to 100% by volume of NH3.

[0038] The feed gas stream F1 prepared according to step (ii) preferably has an NH3 partial pressure in the range of 0.01 to 65 bara, more preferably in the range of 0.05 to 45 bara, more preferably in the range of 0.1 to 25 bara, more preferably in the range of 0.5 to 15 bara, more preferably in the range of 1 to 10 bara.

[0039] The feed gas stream F1 prepared according to step (ii) preferably comprises 0-1 vol. %, more preferably 0-0.8 vol. %, more preferably 0.0001-0.7 vol. %, more preferably 0.0001-0.6 vol. %, more preferably 0.03-0.5 vol. %, more preferably 0.05-0.4 vol. % HO.

[0040] The feed gas stream F1 prepared according to step (ii) preferably comprises 0 to 99 vol%, more preferably 98 vol%, more preferably 0 to 96 vol%, more preferably 0 to 95 vol%, more preferably 0 to 50 vol%, more preferably 0 to 30 vol%, more preferably 0 to 20 vol%, more preferably 0 to 10 vol%, more preferably 0 to 5 vol% of an inert gas, wherein the inert gas comprises one or more of Ar and N2, preferably N2, and preferably consists of one or more of Ar and N2, preferably N2.

[0041] Preferably, 99 to 100% by volume, preferably 99.9 to 100% by volume, more preferably 99.99 to 100% by volume, of the feed gas stream F1 prepared according to step (ii) consists of NH3, H2, optionally H2O, and optionally an inert gas, wherein the inert gas comprises one or more of Ar and N2, preferably N2, preferably consists of one or more of Ar and N2, preferably N2.

[0042] The feed gas stream F1 prepared according to step (ii) is preferably heated to a temperature of 100 to 15,000 h -1 range, more preferably 500 to 10,000 h -1 range, more preferably 1000 to 5000 h -1 range, more preferably 2000 to 4750 h -1 range, more preferably 3500 to 4500 h -1 to the reactor according to step (iii) at a gas hourly space velocity in the range of

[0043] The contacting in step (iii) is preferably carried out at a pressure in the range of 1 to 65 bara, more preferably 2 to 50 bara, more preferably 4 to 35 bara, more preferably 5 to 10 bara.

[0044] The contact in step (iii) is carried out at a temperature in the range of preferably 200 to 1000°C, more preferably 350 to 800°C, more preferably 450 to 650°C.

[0045] Preferably, the method comprises the steps of: (iv) preparing a feed gas stream F2 comprising NH3; (v) feeding the feed gas stream F2 prepared according to step (iv) into a reactor and contacting the feed gas stream F2 with the NH3 reforming catalyst C2 obtained from step (iii); (vi) removing an effluent gas stream comprising H2 and N2 from the reactor; Further includes:

[0046] If the method further comprises steps (iv), (v) and (vi), the feed gas stream F2 prepared according to step (iv) preferably comprises 0-0.5% by volume of H2, more preferably 0-0.2% by volume, more preferably 0-0.1% by volume, more preferably 0-0.05% by volume, more preferably 0-0.02% by volume, more preferably 0-0.01% by volume, more preferably 0-0.005% by volume, more preferably 0-0.002% by volume, more preferably 0-0.001% by volume of H2.

[0047] Furthermore, when the method further comprises steps (iv), (v) and (vi), the feed gas stream F2 prepared according to step (iv) preferably comprises 1 to 100% by volume, more preferably 2 to 100% by volume, more preferably 4 to 100% by volume, more preferably 5 to 100% by volume, more preferably 50 to 100% by volume, more preferably 80 to 100% by volume, more preferably 85 to 100% by volume, more preferably 89.5 to 100% by volume, preferably 94.5 to 100% by volume, more preferably 99.0 to 100% by volume, more preferably 99.5 to 100% by volume, more preferably 99.6 to 100% by volume, more preferably 99.7 to 100% by volume of NH3.

[0048] Furthermore, when the method further comprises steps (iv), (v) and (vi), the feed gas stream F2 prepared according to step (iv) preferably comprises 0-1 vol.%, more preferably 0-0.8 vol.%, more preferably 0.0001-0.7 vol.%, more preferably 0.0001-0.5 vol.%, more preferably 0.0005-0.4 vol.%, more preferably 0.001-0.3 vol.% HO.

[0049] Furthermore, when the method further comprises steps (iv), (v) and (vi), the feed gas stream F2 prepared according to step (iv) preferably comprises 0 to 99 vol%, more preferably 98 vol%, more preferably 0 to 96 vol%, more preferably 0 to 95 vol%, more preferably 0 to 50 vol%, more preferably 0 to 30 vol%, more preferably 0 to 20 vol%, more preferably 0 to 10 vol%, more preferably 0 to 5 vol% of an inert gas, wherein the inert gas comprises one or more of Ar and N2, preferably N2, and preferably consists of one or more of Ar and N2, preferably N2.

[0050] Furthermore, when the method further comprises steps (iv), (v) and (vi), preferably 99 to 100% by volume, more preferably 99.9 to 100% by volume, more preferably 99.99 to 100% by volume of the feed gas stream F2 prepared according to step (iv) consists of NH3, H2, optionally H2O, and optionally an inert gas, wherein the inert gas comprises one or more of Ar and N2, preferably N2, and preferably consists of one or more of Ar and N2, preferably N2.

[0051] Furthermore, if the method further comprises steps (iv), (v) and (vi), preferably the feed gas stream F2 prepared according to step (iv) has the same chemical composition as the feed gas stream F1 prepared according to step (ii).

[0052] Furthermore, if the method further comprises steps (iv), (v) and (vi), the feed gas stream F2 prepared according to step (iv) is preferably oxidized for 500 to 15,000 h -1 range, more preferably 1000 to 10000 h -1 range, more preferably 2000 to 8000 h -1 range, more preferably 3250 to 6000 h -1 range, more preferably 3500 to 5000 h -1 The gas is fed to the reactor according to step (v) at a gas hourly space velocity in the range of

[0053] Furthermore, when the method further comprises steps (iv), (v) and (vi), the contacting according to step (v) is preferably carried out at a pressure in the range of 10 to 65 bara, preferably 20 to 55 bara, more preferably 30 to 50 bara, more preferably 35 to 45 bara.

[0054] Furthermore, when the method further comprises steps (iv), (v) and (vi), the contacting in step (v) is preferably carried out at a temperature in the range of 200 to 950°C, preferably 250 to 800°C, more preferably 300 to 700°C, more preferably 325 to 600°C, more preferably 350 to 550°C.

[0055] If the method further comprises steps (iv), (v) and (vi), the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably from the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably from the group consisting of K, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably from the group consisting of Fe, Ru, and mixtures thereof, wherein more preferably M2 is Ru.

[0056] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and a mixture of two or more thereof, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises one or more support materials on which M1 and M2, preferably one or more of M1 and M2, are supported, wherein the one or more support materials are preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and a mixture of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, ZrO2, CeO2, and a mixture of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, and a mixture thereof, and more preferably the support material comprises Al2O3.

[0057] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and a mixture of two or more thereof, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, preferably 0.5:99.5 to 75:25, more preferably 1:99 to 70:30, more preferably 5:95 to 65:35, more preferably 15:85 to 60:40, more preferably 30:70 to 55:45, more preferably 40:60 to 50:50.

[0058] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and a mixture of two or more thereof, M2 preferably comprises Fe or Co, and is preferably Fe or Co, and the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably exhibits an M2:M1 atomic ratio in the range of 1:99 to 80:20, more preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, more preferably 40:60 to 50:50.

[0059] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and a mixture of two or more thereof, M2 preferably comprises, and is preferably Ru, and the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably exhibits an M2:M1 atomic ratio in the range of 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.

[0060] According to a first alternative embodiment, further, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and mixtures of two or more thereof, preferably the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises Al and O.

[0061] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further contains Al and O, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in step (i) contains Ni as the metal M1, and more preferably the metal M1 is Ni.

[0062] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) contains Ni as the metal M1, more preferably when the metal M1 is Ni, it is preferable that the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further contains Mg, and in this case, the molar ratio of Ni:Mg:Al is more 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).

[0063] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) contains Ni as the metal M1, more preferably when the metal M1 is Ni, according to one alternative embodiment, preferably 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, more preferably 99.9 to 100 mass% of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of Ni, Mg, Al and O.

[0064] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ni as the metal M1, more preferably when the metal M1 is Ni, according to a further alternative embodiment, preferably 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, more preferably 99.9 to 100 mass% of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of M2, Ni, Mg, Al and O.

[0065] According to a second alternative embodiment, further, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and mixtures of two or more thereof, preferably the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Co as the metal M1, more preferably the metal M1 is Co.

[0066] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) contains Co as the metal M1, more preferably when the metal M1 is Co, it is preferable that the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further contains La, wherein the molar ratio of Co:La:Al is more 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).

[0067] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) contains Co as the metal M1, more preferably when the metal M1 is Co, according to one alternative embodiment, preferably 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, more preferably 99.9 to 100 mass% of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of Co, La, Al and O.

[0068] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Co as the metal M1, more preferably the metal M1 is Co, according to a further alternative embodiment, preferably 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, more preferably 99.9 to 100 mass% of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of M2, Co, La, Al and O.

[0069] The NH3 reforming catalyst C1 contained in the reactor provided in step (i) is preferably in the form of extrusions.

[0070] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is in the form of a molding, the molding is preferably a tablet.

[0071] According to a first alternative embodiment, when the molding is a tablet, the tablet preferably has a four-hole cross section, more preferably a diameter in the range of 5 to 19 mm, more preferably in the range of 8 to 18 mm, more preferably in the range of 16.7 to 16.8 mm, and a height in the range of 7 to 11 mm, preferably in the range of 9.5 to 10.5 mm, more preferably in the range of 9.7 to 10.0 mm.

[0072] When the tablet has a four-hole cross section, more preferably a four-hole cross section having a diameter in the range of 5 to 19 mm, it is preferable that the tablet is a sintered tablet, and here, the sintering is preferably carried out in a gas atmosphere having a temperature in the range of 350 to 450°C, more preferably in the range of 360 to 440°C, more preferably in the range of 375 to 425°C, more preferably in the range of 390 to 410°C, the gas atmosphere more preferably containing oxygen, more preferably one or more of oxygen, air, and diluted air, and the sintering is preferably carried out for 0.5 to 20 hours, more preferably 1 to 15 hours, more preferably 2 to 10 hours, more preferably 3 to 5 hours.

[0073] Furthermore, when the tablet has a four-hole cross section, the tablet preferably has a side crushing strength 1 (SCS1) determined according to Reference Example 5 of at least 70 N, more preferably in the range of 70 to 250 N, more preferably in the range of 70 to 130 N, wherein four cylindrical segments are arranged in each region between two flutes, and the side crushing strength 1 is measured according to Reference Example 5 with the tablet standing on the two cylindrical segments sandwiched between the flutes.

[0074] Furthermore, when the tablet has a four-hole cross section, the tablet preferably has a side crushing strength 2 (SCS2) determined according to Reference Example 5 of at least 60 N, more preferably in the range of 60 to 200 N, more preferably in the range of 60 to 88 N, where four cylindrical segments are arranged in each region between two flutes, and the side crushing strength 2 is measured according to Reference Example 5 with the tablet standing on the two cylindrical segments sandwiched between the flutes.

[0075] Furthermore, when the tablet has a four-hole cross section, the tablet preferably has a side crushing strength 3 (SCS3) determined in accordance with Reference Example 5 of at least 190 N, more preferably in the range of 190 to 350 N, more preferably in the range of 190 to 240 N, wherein four cylindrical segments are arranged in each region between two flutes, and the side crushing strength 3 is measured in accordance with Reference Example 5 with the region of the cylindrical segments perpendicular to the direction of the force applied to the tablet.

[0076] According to a second alternative embodiment, when the molded product is a tablet, the tablet preferably has a four-hole cross section, more preferably a diameter in the range of 10 to 18 mm, more preferably in the range of 13.5 to 16.0 mm, more preferably in the range of 14.0 to 15.5 mm, and a height in the range of 5 to 11 mm, more preferably in the range of 7.5 to 9.4 mm, more preferably in the range of 8.2 to 9.0 mm.

[0077] When the tablet has a four-hole cross section, more preferably a four-hole cross section with a diameter in the range of 10 to 18 mm, it is preferable that the tablet is a sintered tablet, wherein the sintering is carried out in a gas atmosphere having a temperature preferably in the range of 800 to 1400°C, more preferably in the range of 875 to 1275°C, more preferably in the range of 950 to 1250°C, more preferably in the range of 1050 to 1225°C, the gas atmosphere more preferably containing oxygen, more preferably one or more of oxygen, air, and diluted air, and the sintering is preferably carried out for 0.5 to 20 hours, more preferably 1 to 15 hours, more preferably 2 to 10 hours, more preferably 3 to 5 hours.

[0078] Furthermore, when the tablet has a four-hole cross-section, more preferably a four-hole cross-section with a diameter in the range of 10 to 18 mm, the tablet preferably has a side crushing strength 1 (SCS1) determined according to Reference Example 4 of at least 366 N, more preferably at least 400 N, more preferably in the range of 400 to 800 N, more preferably in the range of 400 to 600 N, more preferably in the range of 400 to 570 N, and the molded product more preferably has a four-hole cross-section and is a tablet having four flutes, with four cylindrical segments arranged in each region between two flutes, and the side crushing strength 1 is measured according to Reference Example 4 with the tablet standing on the two cylindrical segments sandwiched between the flutes.

[0079] Furthermore, when the tablet has a four-hole cross-section, more preferably a four-hole cross-section with a diameter in the range of 10 to 18 mm, the tablet preferably has a lateral crushing strength 2 (SCS2) determined according to Reference Example 4 of at least 170 N, more preferably at least 190 N, more preferably in the range of 190 to 450 N, more preferably in the range of 190 to 300 N, more preferably in the range of 190 to 270 N, wherein four cylindrical segments are arranged in each region between two flutes, and the lateral crushing strength 2 is measured according to Reference Example 4 with the tablet standing on the cylindrical segments.

[0080] Furthermore, when the tablet has a four-hole cross section, more preferably a four-hole cross section with a diameter in the range of 10 to 18 mm, the tablet preferably has a side crushing strength 3 (SCS3) determined according to Reference Example 4 of at least 345 N, more preferably at least 500 N, more preferably in the range of 500 to 950 N, more preferably in the range of 500 to 800 N, more preferably in the range of 500 to 770 N, wherein four cylindrical segments are arranged in each region between two flutes, and the side crushing strength 3 is preferably measured according to Reference Example 4 with the region of the cylindrical segments perpendicular to the direction of the force applied to the tablet.

[0081] According to certain preferred embodiments described above, particularly in relation to the case where the NH3-reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru, preferably, the NH3-reforming catalyst C1 contained in the reactor provided in step (i) further comprises one or more support materials, wherein Ru is supported on the one or more support materials.

[0082] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably comprises at most 1% by mass of Ni and Co, respectively, calculated based on 100% by mass of the NH3 reforming catalyst C1, more preferably at most 0.5% by mass, more preferably at most 0.1% by mass, more preferably at most 0.05% by mass, more preferably at most 0.01% by mass, more preferably at most 0.005% by mass, more preferably at most 0.001% by mass.

[0083] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, according to one alternative embodiment, the one or more support materials preferably have a molecular weight of 2000 or more. 2 / g or more, more preferably 30 to 800m 2 / g, more preferably 40 to 500m 2 / g, more preferably 50 to 300m 2 / g, more preferably 60 to 200m 2 / g, more preferably 70 to 100m 2 / g, more preferably 75-80m 2 / g, where the BET surface area is preferably determined according to ISO 9277:2010.

[0084] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, according to a further alternative embodiment, the one or more support materials preferably have a molecular weight of 2000 or more. 2 / g or more, more preferably 20 to 150m 2 / g, more preferably 21 to 100m 2 / g, more preferably 22 to 70 m 2 / g, more preferably 23 to 50m 2 / g, more preferably 24 to 40 m 2 / g, more preferably 25 to 35m 2 / g, where the BET surface area is preferably determined according to ISO 9277:2010.

[0085] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, the one or more support materials preferably exhibit a pore volume in the range of 0.2 to 3 ml / g, more 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, wherein the pore volume is preferably determined in accordance with ISO 15901-2:2022.

[0086] Furthermore, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and when Ru is supported on one or more support materials, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is preferably 20 to 800 m 2 / g, more preferably 30 to 500m2 / g, more preferably 40 to 300m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, more preferably 70-75m 2 / g, where the BET surface area is preferably determined according to ISO 9277:2010.

[0087] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably exhibits a pore volume in the range of 0.1-2 ml / g, more preferably 0.15-1.2 ml / g, more preferably 0.2-0.8 ml / g, more preferably 0.25-0.5 ml / g, more preferably 0.3-0.35 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0088] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) contains Ru and one or more support materials, and Ru is supported on one or more support materials, preferably 90 to 100 mass%, more preferably 95 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass%, of Ru, as an element, calculated based on 100 mass% of Ru contained in the NH3 reforming catalyst C1 contained in the reactor provided in step (i), is supported on one or more support materials contained in the catalyst.

[0089] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, it is preferred that Ru is supported on the one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, wherein the one or more ruthenium salts more preferably comprise Ru(NO)(NO3)3, and more preferably Ru(NO)(NO3)3 is adopted as the one or more ruthenium salts.

[0090] Furthermore, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and when Ru is supported on one or more support materials, the one or more support materials are preferably selected from the group consisting of metal oxides, wherein the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, rare earth metals, and combinations of two or more thereof, more preferably Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, Nd, and combinations of two or more thereof, more preferably Al, Ti, Zr, Mg, C more preferably from the group consisting of Al, Zr, Mg, and 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, spinel, and mixtures of two or more thereof, preferably from the group consisting of ZrO2, spinel, and 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 consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0091] When the one or more support materials comprise ZrO2, it is preferred that the ZrO2 comprises one or more crystalline phases and / or is amorphous, wherein the one or more crystalline phases of ZrO2 are selected from the group consisting of monoclinic, tetragonal, cubic phases of ZrO2, and mixtures of two or three thereof.

[0092] Furthermore, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and when Ru is supported on one or more support materials, the one or more support materials are preferably substantially free of CaO and / or MgO, more preferably substantially free of CaO and MgO, more preferably substantially free of alkaline earth metal oxides, more preferably substantially free of Ca and / or Mg, more preferably substantially free of Ca and Mg, more preferably substantially free of alkaline earth metals.

[0093] Furthermore, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and when Ru is supported on one or more support materials, the one or more support materials are preferably substantially free of Al2O3 and / or SiO2, more preferably substantially free of Al2O3 and SiO2, more preferably substantially free of Al and / or Si, more preferably substantially free of Al and Si.

[0094] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, the one or more support materials are preferably substantially free of carbon nanotubes, more preferably substantially free of elemental carbon, and even more preferably substantially free of carbon.

[0095] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, the NH3 reforming catalyst C1 preferably comprises Ru in an amount in the range of 0.1 to 15 mass%, more preferably 1 to 10 mass%, more preferably 2 to 8 mass%, more preferably 3 to 6.5 mass%, more preferably 4 to 6 mass%, and more preferably 4.5 to 5.5 mass%, based on 100 mass% of the total amount of the one or more support materials.

[0096] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, preferably 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, more preferably 99.9 to 100 mass% of the NH3 reforming catalyst C1 consists of Ru and one or more support materials.

[0097] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises one or more alkali metal and / or alkaline earth metal hydroxides, and the one or more alkali metal and / or alkaline earth metal hydroxides are supported on the one or more support materials that support Ru, wherein the alkali metal and / or alkaline earth metal hydroxide is more preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH, KOH, and mixtures of two or more thereof, more preferably from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH, KOH, and mixtures of two or more thereof, more preferably from the group consisting of LiOH, NaOH, KOH, and mixtures of two or more thereof, and more preferably the catalyst further comprises KOH and / or LiOH, preferably KOH.

[0098] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises one or more alkali metal and / or alkaline earth metal hydroxides, and the one or more alkali metal and / or alkaline earth metal hydroxides are supported on one or more support materials supporting Ru, the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably comprises the one or more alkali metal hydroxides in an amount in the range of 0.5 to 15 mass%, more preferably 1 to 10 mass%, more preferably 2 to 8 mass%, more preferably 3 to 6.5 mass%, more preferably 4 to 6 mass%, more preferably 4.5 to 5.5 mass%, based on 100 mass% of the total amount of the one or more support materials.

[0099] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further contains one or more alkali metal and / or alkaline earth metal hydroxides, and the one or more alkali metal and / or alkaline earth metal hydroxides are supported on one or more support materials supporting Ru, preferably 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, more preferably 99.9 to 100 mass% of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of Ru, one or more alkali metal hydroxides, and one or more support materials.

[0100] Furthermore, when the NH3-reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on one or more support materials, the NH3-reforming catalyst C1 contained in the reactor provided in step (i) is preferably in the form of a molding and / or powder, preferably in the form of a molding, more preferably in the form of an extrudate or a tablet.

[0101] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is in the form of extrudates, the extrudates have a diameter in the range of 0.5 to 10 mm, more preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

[0102] Furthermore, when the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is in the form of extrudates, it is preferred that the extrudates are divided, and the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is in the form of extrudates with a divided sieve fraction in the range of 50 μm to 2.5 mm, more preferably 100 μm to 1.5 mm, more preferably 200 μm to 1 mm, more preferably 250 μm to 700 μm, more preferably 300 μm to 500 μm.

[0103] When the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is in the form of extrudates of a dividing sieve fraction in the range of 50 μm to 2.5 mm, the tablets preferably have a four-hole cross section, more preferably a four-hole cross section and four flutes.

[0104] The present invention is further described by the following series of embodiments and combinations of embodiments resulting from the dependencies and backward references as indicated. In particular, in each instance where a range of embodiments is mentioned, it should be noted that in the context of a term such as "the method according to any one of embodiments 1 to 4," it is meant that all embodiments within this range are expressly disclosed to those skilled in the art, that is, the expression of this term means that it is understood by those skilled in the art to be synonymous with "the method according to any one of embodiments 1, 2, 3, and 4."

[0105] Furthermore, it should be expressly noted that the following series of embodiments represent a suitably structured part of the description directed to general and preferred aspects of the present invention, rather than the claims which determine the scope of protection.

[0106] 1. A method for NH3 reforming, comprising the steps of: (i) providing a reactor containing an NH3 reforming catalyst C1 comprising a metal M1 selected from the group consisting of Groups 6 to 11 of the periodic table, and mixtures of two or more thereof; (ii) preparing a feed gas stream F1 containing NH3; (iii) feeding F1 prepared according to step (ii) into a reactor and contacting F1 with the NH3 reforming catalyst C1 to obtain a product gas stream P1 comprising H2O and the NH3 reforming catalyst C2, wherein the reactor has a temperature of 100°C or greater; Including, The supply according to step (ii) is started at time t1; 1. A method according to claim 1, wherein at time t2, the molar ratio H2O(P1):H2O(F1) of the H2O in product gas stream P1 to the H2O in feed gas stream F1 exceeds 1:1, the H2O in product gas stream P1 and the H2O in feed gas stream F1 being preferably determined according to DIN EN 14790, more preferably according to Reference Example 1, and the difference between t2 and t1 is in the range of 5 seconds to 10 days.

[0107] 2. The method of embodiment 1, wherein at time t2, the molar ratio of HO in product gas stream P1 to HO in feed gas stream F1, HO(P1):HO(F1), is in the range of 1.0001:1 to 25:1, preferably in the range of 1.0005:1 to 15:1, more preferably in the range of 1.001:1 to 10:1, more preferably in the range of 1.005:1 to 5:1, more preferably in the range of 1.01:1 to 4:1, more preferably in the range of 1.05:1 to 3:1, more preferably in the range of 1.1:1 to 2:1.

[0108] 3. The method according to embodiment 1 or 2, wherein the difference between t2 and t1 is in the range of 5 seconds to 9 days, preferably in the range of 1 minute to 8 days, more preferably in the range of 5 minutes to 7 days, more preferably in the range of 0.5 hours to 5 days, more preferably in the range of 1 hour to 4 days, more preferably in the range of 3 hours to 2 days, more preferably in the range of 6 hours to 2 days.

[0109] 4. The method according to any one of embodiments 1 to 3, wherein the X-ray diffraction pattern of the NH3 reforming catalyst C1 contained in the reactor provided in step (i), preferably determined according to Reference Example 2, shows one or more crystalline phases of one or more oxides of M1.

[0110] 5. The method according to any one of embodiments 1 to 4, wherein the X-ray diffraction pattern of the NH3 reforming catalyst C2 obtained from step (iii), preferably determined according to Reference Example 2, shows one or more crystalline phases of element M1.

[0111] 6. The method according to any one of embodiments 1 to 5, wherein the X-ray diffraction pattern of the NH3 reforming catalyst C2 obtained from step (iii), preferably determined according to Reference Example 2, does not show any crystalline phase of one or more oxides of M1.

[0112] 7. The method of any one of the preceding claims, wherein M1 is selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu, and mixtures of two or more thereof, preferably Ni, Co, Ru, Fe, and mixtures thereof.

[0113] 8. The method of any one of embodiments 1 to 7, wherein M1 comprises Ni, preferably Ni.

[0114] 9. The method according to embodiment 8, wherein the XRD pattern of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) exhibits a mass ratio of NiO crystalline phase to elemental Ni crystalline phase greater than 1:100, preferably greater than 1:10, more preferably in the range of 1:10 to 100:1, more preferably in the range of 1:10 to 10:1, and the XRD pattern is preferably determined according to Reference Example 2.

[0115] 10. The method according to embodiment 8 or 9, wherein the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) shows a first peak having a maximum value in the range of 100 to 400 °C, preferably in the range of 120 to 350 °C, more preferably in the range of 150 to 250 °C, and the TPR profile is preferably determined according to Reference Example 3.

[0116] 11. The method according to embodiment 10, wherein the integral value of the first peak is in the range of 500 to 4000 μmol / g, preferably in the range of 1500 to 3000 μmol / g, more preferably in the range of 2000 to 2500 μmol / g.

[0117] 12. The method according to embodiment 10 or 11, wherein the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) preferably exhibits a second peak having a maximum value in the range of more than 400°C to 900°C, more preferably in the range of 425°C to 850°C, more preferably in the range of 450°C to 800°C, and the TPR profile is preferably determined according to Reference Example 3.

[0118] 13. The method according to embodiment 12, wherein the integral value of the second peak is in the range of 500 to 4500 μmol / g, preferably in the range of 1500 to 3500 μmol / g, more preferably in the range of 2000 to 3000 μmol / g.

[0119] 14. The method according to any one of embodiments 10 to 13, wherein the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) exhibits a third peak having a maximum value in the range of more than 900 °C to 1300 °C, preferably in the range of 950 °C to 1250 °C, more preferably in the range of 1000 °C to 1200 °C, and the TPR profile is preferably determined according to Reference Example 3.

[0120] 15. The method according to embodiment 14, wherein the integral value of the third peak is in the range of 100 to 1500 μmol / g, preferably in the range of 300 to 1250 μmol / g, more preferably in the range of 500 to 1000 μmol / g.

[0121] 16. The method of embodiment 7, wherein M1 comprises Ru, preferably Ru.

[0122] 17. The method according to embodiment 16, wherein the TPR profile of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) shows a peak having a maximum value in the range of 100 to 400 °C, preferably in the range of 120 to 350 °C, more preferably in the range of 150 to 250 °C, and the TPR profile is preferably determined according to Reference Example 3.

[0123] 18. The method according to embodiment 17, wherein the integral value of the peak is in the range of 1500 to 5000 μmol / g, preferably in the range of 2500 to 4000 μmol / g, more preferably in the range of 3000 to 3500 μmol / g.

[0124] 19. The process according to any one of the preceding embodiments, wherein the reactor provided in step (i) has a length in the range of 0.5 to 20 m, preferably in the range of 1 to 12 m.

[0125] 20. The method of any one of the preceding embodiments, wherein the reactor provided in step (i) is operated in an adiabatic mode.

[0126] 21. The method of any one of the preceding embodiments, wherein the reactor provided in step (i) is directly heated, preferably flame heated or electrically heated.

[0127] 22. The method of any one of the preceding claims, wherein the feed gas stream F1 prepared according to step (ii) comprises 0-0.5% by volume, preferably 0-0.2% by volume, more preferably 0-0.1% by volume, more preferably 0-0.05% by volume, more preferably 0-0.02% by volume, more preferably 0-0.01% by volume, more preferably 0-0.005% by volume, more preferably 0-0.002% by volume, more preferably 0-0.001% by volume of H2.

[0128] 23. The method according to any one of the preceding embodiments, wherein the feed gas stream F1 prepared according to step (ii) comprises 1 to 100% by volume, preferably 2 to 100% by volume, more preferably 4 to 100% by volume, more preferably 5 to 100% by volume, more preferably 50 to 100% by volume, more preferably 80 to 100% by volume, more preferably 85 to 100% by volume, more preferably 89.5 to 100% by volume, preferably 94.5 to 100% by volume, more preferably 99.0 to 100% by volume, more preferably 99.5 to 100% by volume, more preferably 99.6 to 100% by volume, more preferably 99.7 to 100% by volume, more preferably 99.8 to 100% by volume, more preferably 99.9 to 100% by volume, more preferably 99.95 to 100% by volume, more preferably 99.98 to 100% by volume, more preferably 99.99 to 100% by volume of NH3.

[0129] 24. The method of any one of the preceding embodiments, wherein the feed gas stream F1 prepared according to step (ii) has an NH3 partial pressure in the range of 0.01 to 65 bara, preferably in the range of 0.05 to 45 bara, more preferably in the range of 0.1 to 25 bara, more preferably in the range of 0.5 to 15 bara, more preferably in the range of 1 to 10 bara.

[0130] 25. The method of any one of the preceding embodiments, wherein the feed gas stream F1 prepared according to step (ii) comprises 0-1 vol.%, preferably 0-0.8 vol.%, more preferably 0.0001-0.7 vol.%, more preferably 0.0001-0.6 vol.%, more preferably 0.03-0.5 vol.%, more preferably 0.05-0.4 vol.% HO.

[0131] 26. The method of any one of the preceding embodiments, wherein the feed gas stream F1 prepared according to step (ii) comprises 0 to 99% by volume, preferably 98% by volume, more preferably 0 to 96% by volume, more preferably 0 to 95% by volume, more preferably 0 to 50% by volume, more preferably 0 to 30% by volume, more preferably 0 to 20% by volume, more preferably 0 to 10% by volume, more preferably 0 to 5% by volume of an inert gas, wherein the inert gas comprises one or more of Ar and N2, preferably N2, and preferably consists of one or more of Ar and N2, preferably N2.

[0132] 27. The method of any one of the preceding embodiments, wherein 99 to 100% by volume, preferably 99.9 to 100% by volume, more preferably 99.99 to 100% by volume, of the feed gas stream F1 prepared according to step (ii) consists of NH3, H2, optionally H2O, and optionally an inert gas, wherein the inert gas comprises one or more of Ar and N2, preferably N2, and preferably consists of one or more of Ar and N2, preferably N2.

[0133] 28. The feed gas stream F1 prepared according to step (ii) is heated for 100 to 15,000 h -1 range, more preferably 500 to 10,000 h -1 range, more preferably 1000 to 5000 h -1 range, more preferably 2000 to 4750 h -1 range, more preferably 3500 to 4500 h -1 28. The method of any one of the preceding embodiments, wherein the gas is fed to the reactor according to step (iii) at a gas hourly space velocity in the range of

[0134] 29. The process of any one of embodiments 1 to 28, wherein the contacting according to step (iii) is carried out at a pressure in the range of 1 to 65 bara, preferably 2 to 50 bara, more preferably 4 to 35 bara, more preferably 5 to 10 bara.

[0135] 30. The method of any one of embodiments 1 to 29, wherein the contacting according to step (iii) is carried out at a temperature in the range of 200 to 1000°C, preferably 350 to 800°C, more preferably 450 to 650°C.

[0136] 31. The following steps: (iv) preparing a feed gas stream F2 comprising NH3; (v) feeding the feed gas stream F2 prepared according to step (iv) into the reactor and contacting the feed gas stream F2 with the NH3 reforming catalyst C2 obtained from step (iii); (vi) removing an effluent gas stream comprising H2 and N2 from the reactor; 31. The method of any one of embodiments 1 to 30, further comprising:

[0137] 32. The method of embodiment 31, wherein the feed gas stream F2 prepared according to step (iv) comprises 0-0.5% by volume, preferably 0-0.2% by volume, more preferably 0-0.1% by volume, more preferably 0-0.05% by volume, more preferably 0-0.02% by volume, more preferably 0-0.01% by volume, more preferably 0-0.005% by volume, more preferably 0-0.002% by volume, more preferably 0-0.001% by volume of H2.

[0138] 33. The method of embodiment 31 or 32, wherein the feed gas stream F2 prepared according to step (iv) comprises 1 to 100% by volume, preferably 2 to 100% by volume, more preferably 4 to 100% by volume, more preferably 5 to 100% by volume, more preferably 50 to 100% by volume, more preferably 80 to 100% by volume, more preferably 85 to 100% by volume, more preferably 89.5 to 100% by volume, preferably 94.5 to 100% by volume, more preferably 99.0 to 100% by volume, more preferably 99.5 to 100% by volume, more preferably 99.6 to 100% by volume, more preferably 99.7 to 100% by volume of NH3.

[0139] 34. The method of any one of embodiments 31 to 33, wherein the feed gas stream F2 prepared according to step (iv) comprises 0 to 1 vol.%, preferably 0 to 0.8 vol.%, more preferably 0.0001 to 0.7 vol.%, more preferably 0.0001 to 0.5 vol.%, more preferably 0.0005 to 0.4 vol.%, more preferably 0.001 to 0.3 vol.% H2O.

[0140] 35. The method of any one of embodiments 31 to 34, wherein the feed gas stream F2 prepared according to step (iv) comprises 0 to 99% by volume, preferably 98% by volume, more preferably 0 to 96% by volume, more preferably 0 to 95% by volume, more preferably 0 to 50% by volume, more preferably 0 to 30% by volume, more preferably 0 to 20% by volume, more preferably 0 to 10% by volume, more preferably 0 to 5% by volume of an inert gas, wherein the inert gas comprises one or more of Ar and N2, preferably N2, and preferably consists of one or more of Ar and N2, preferably N2.

[0141] 36. The method of any one of embodiments 31 to 35, wherein 99 to 100% by volume, preferably 99.9 to 100% by volume, more preferably 99.99 to 100% by volume, of the feed gas stream F2 prepared according to step (iv) consists of NH3, H2, optionally H2O, and optionally an inert gas, wherein the inert gas comprises one or more of Ar and N2, preferably N2, and preferably consists of one or more of Ar and N2, preferably N2.

[0142] 37. The method of any one of embodiments 31 to 36, wherein the feed gas stream F2 prepared according to step (iv) has the same chemical composition as the feed gas stream F1 prepared according to step (ii).

[0143] 38. The feed gas stream F2 prepared according to step (iv) is heated for 500 to 15,000 h -1 range, preferably 1000 to 10000h -1 range, more preferably 2000 to 8000 h -1 range, more preferably 3250 to 6000 h -1range, more preferably 3500 to 5000 h -1 38. The method of any one of embodiments 31 to 37, wherein the gas is fed to the reactor in accordance with step (v) at a gas hourly space velocity in the range of

[0144] 39. The method of any one of embodiments 31 to 38, wherein the contacting according to step (v) is carried out at a pressure in the range of 10 to 65 bara, preferably 20 to 55 bara, more preferably 30 to 50 bara, more preferably 35 to 45 bara.

[0145] 40. The method of any one of embodiments 31 to 39, wherein the contacting according to step (v) is carried out at a temperature in the range of 200 to 950°C, preferably 250 to 800°C, more preferably 300 to 700°C, more preferably 325 to 600°C, more preferably 350 to 550°C.

[0146] 41. The method according to any one of the preceding embodiments, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and mixtures of two or more thereof, preferably from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably from the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably from the group consisting of K, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably from the group consisting of Fe, Ru, and mixtures thereof; more preferably M2 is Ru.

[0147] 42. The method of embodiment 41, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises one or more support materials on which one or more of M1 and M2, preferably M1 and M2, are supported, and the one or more support materials are 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 Al2O3.

[0148] 43. The method of embodiment 41 or 42, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, preferably 0.5:99.5 to 75:25, more preferably 1:99 to 70:30, more preferably 5:95 to 65:35, more preferably 15:85 to 60:40, more preferably 30:70 to 55:45, more preferably 40:60 to 50:50.

[0149] 44. The method of any one of embodiments 41 to 43, wherein M2 comprises Fe or Co, preferably is Fe or Co, and the NH3 reforming catalyst C1 contained in the reactor provided in step (i) exhibits an M2:M1 atomic ratio in the range of 1:99 to 80:20, preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, more preferably 40:60 to 50:50.

[0150] 45. The method of any one of embodiments 41 to 44, wherein M2 comprises Ru, preferably is Ru, and the NH3 reforming catalyst C1 contained in the reactor provided in step (i) exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 30:70, 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.

[0151] 46. ​​The method of any one of embodiments 41 to 45, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises Al and O.

[0152] 47. The method of embodiment 46, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ni as metal M1, preferably, metal M1 is Ni.

[0153] 48. The method of embodiment 47, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises 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).

[0154] 49. The method according to embodiment 47 or 48, wherein 95 to 100% by mass, preferably 97 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, more preferably 99.5 to 100% by mass, more preferably 99.9 to 100% by mass of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of Ni, Mg, Al and O.

[0155] 50. The method of embodiment 47 or 48, wherein 95 to 100% by mass, preferably 97 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, more preferably 99.5 to 100% by mass, more preferably 99.9 to 100% by mass of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of M2, Ni, Mg, Al and O.

[0156] 51. The method of embodiment 46, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Co as metal M1, preferably, metal M1 is Co.

[0157] 52. The method according to embodiment 52, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) further comprises 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).

[0158] 53. The method of embodiment 51 or 52, wherein 95 to 100% by mass, preferably 97 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, more preferably 99.5 to 100% by mass, more preferably 99.9 to 100% by mass of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of Co, La, Al and O.

[0159] 54. The method of embodiment 51 or 52, wherein 95 to 100% by mass, preferably 97 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, more preferably 99.5 to 100% by mass, more preferably 99.9 to 100% by mass of the NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of M2, Co, La, Al and O.

[0160] 55. The method of any one of embodiments 1 to 54, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is in the form of a molding.

[0161] 56. The method of embodiment 55, wherein the molded product is a tablet.

[0162] 57. The method according to embodiment 56, wherein the tablet has a four-hole cross section, preferably with a diameter in the range of 5 to 19 mm, more preferably in the range of 8 to 18 mm, more preferably in the range of 16.7 to 16.8 mm, and a height in the range of 7 to 11 mm, preferably in the range of 9.5 to 10.5 mm, more preferably in the range of 9.7 to 10.0 mm.

[0163] 58. The method of embodiment 57, wherein the tablet is a calcined tablet, and wherein calcination is carried out in a gas atmosphere having a temperature preferably in the range of 350 to 450°C, more preferably in the range of 360 to 440°C, more preferably in the range of 375 to 425°C, more preferably in the range of 390 to 410°C, and wherein the gas atmosphere preferably contains oxygen, and more preferably is one or more of oxygen, air, and diluted air, and wherein calcination is carried out for more preferably 0.5 to 20 hours, more preferably 1 to 15 hours, more preferably 2 to 10 hours, more preferably 3 to 5 hours.

[0164] 59. The method of embodiment 57 or 58, wherein the tablet has a side crushing strength 1 (SCS1) determined according to Reference Example 5 of at least 70 N, preferably in the range of 70 to 250 N, more preferably in the range of 70 to 130 N, and wherein four cylindrical segments are placed in each region between two flutes, and the side crushing strength 1 is measured according to Reference Example 5 with the tablet standing on the two cylindrical segments sandwiched between the flutes.

[0165] 60. The method according to any one of embodiments 57 to 59, wherein the tablet has a side crushing strength 2 (SCS2) determined according to Reference Example 5 of at least 60 N, preferably in the range of 60 to 200 N, more preferably in the range of 60 to 88 N, and wherein four cylindrical segments are placed in each region between two flutes, and the side crushing strength 2 is measured according to Reference Example 5 with the tablet standing on the two cylindrical segments sandwiched between the flutes.

[0166] 61. The method of any one of embodiments 57 to 60, wherein the tablet has a side crushing strength 3 (SCS3) determined according to Reference Example 5 of at least 190 N, preferably in the range of 190 to 350 N, more preferably in the range of 190 to 240 N, and wherein four cylindrical segments are placed in each region between two flutes, and the side crushing strength 3 is measured according to Reference Example 5 with the region of the cylindrical segments perpendicular to the direction of the force applied to the tablet.

[0167] 62. The method according to embodiment 56, wherein the tablet has a four-hole cross section, preferably with a diameter in the range of 10 to 18 mm, more preferably in the range of 13.5 to 16.0 mm, more preferably in the range of 14.0 to 15.5 mm, and a height in the range of 5 to 11 mm, more preferably in the range of 7.5 to 9.4 mm, more preferably in the range of 8.2 to 9.0 mm.

[0168] 63. The method of embodiment 62, wherein the tablet is a calcined tablet, and wherein calcination is carried out in a gas atmosphere having a temperature preferably in the range of 800 to 1400°C, more preferably in the range of 875 to 1275°C, more preferably in the range of 950 to 1250°C, more preferably in the range of 1050 to 1225°C, and wherein the gas atmosphere preferably contains oxygen, and more preferably is one or more of oxygen, air, or lean air, and wherein calcination is carried out for more preferably 0.5 to 20 hours, more preferably 1 to 15 hours, more preferably 2 to 10 hours, more preferably 3 to 5 hours.

[0169] 64. The method of embodiment 62 or 63, wherein the tablet has a side crushing strength 1 (SCS1) determined according to Reference Example 4 of at least 366 N, preferably at least 400 N, more preferably in the range of 400 to 800 N, more preferably in the range of 400 to 600 N, more preferably in the range of 400 to 570 N, and the molded product is more preferably a tablet having a four-hole cross section and four flutes, four cylindrical segments being arranged in each region between two flutes, and the side crushing strength 1 is measured according to Reference Example 4 with the tablet standing on the two cylindrical segments sandwiched between the flutes.

[0170] 65. The method according to any one of embodiments 62 to 64, wherein the tablet has a side crushing strength 2 (SCS2) determined according to Reference Example 4 of at least 170 N, preferably at least 190 N, more preferably in the range of 190 to 450 N, more preferably in the range of 190 to 300 N, more preferably in the range of 190 to 270 N, wherein four cylindrical segments are arranged in each region between two flutes, and wherein the side crushing strength 2 is measured according to Reference Example 4 with the tablet standing on the cylindrical segments.

[0171] 66. The method of any one of embodiments 62 to 65, wherein the tablet has a side crushing strength 3 (SCS3) determined according to Reference Example 4 of at least 345 N, preferably at least 500 N, more preferably in the range of 500 to 950 N, more preferably in the range of 500 to 800 N, more preferably in the range of 500 to 770 N, and wherein four cylindrical segments are arranged in each region between two flutes, and the side crushing strength 3 is preferably measured according to Reference Example 4 with the regions of the cylindrical segments perpendicular to the direction of the force applied to the tablet.

[0172] 67. The method of embodiments 1 to 7, 16 to 40 and 66, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises Ru and one or more support materials, and Ru is supported on the one or more support materials.

[0173] 68. The method of embodiment 67, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises, as the respective elements, at most 1% by weight, preferably at most 0.5% by weight, more preferably at most 0.1% by weight, more preferably at most 0.05% by weight, more preferably at most 0.01% by weight, more preferably at most 0.005% by weight, more preferably at most 0.001% by weight, and more preferably at most 0.001% by weight of Ni and Co, calculated based on 100% by weight of the NH3 reforming catalyst C1.

[0174] 69. The one or more carrier materials are 20 m 2 / g or more, preferably 30 to 800m 2 / g, more preferably 40 to 500m 2 / g, more preferably 50 to 300m 2 / g, more preferably 60 to 200m 2 / g, more preferably 70 to 100m 2 / g, more preferably 75-80m 2 69. The method of embodiment 67 or 68, wherein the hydroxybenzoate exhibits a BET surface area in the range of / g, the BET surface area preferably being determined according to ISO 9277:2010.

[0175] 70. The one or more carrier materials are 20 m 2 / g or more, preferably 20 to 150m 2 / g, more preferably 21 to 100m 2 / g, more preferably 22 to 70 m 2 / g, more preferably 23 to 50m 2 / g, more preferably 24 to 40 m 2 / g, more preferably 25 to 35m 2 69. The method of embodiment 67 or 68, wherein the hydroxybenzoate exhibits a BET surface area in the range of / g, the BET surface area preferably being determined according to ISO 9277:2010.

[0176] 71. The method of any one of embodiments 67 to 70, 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, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0177] 72. The NH3 reforming catalyst C1 contained in the reactor provided in step (i) is 20 to 800 m 2 / g, preferably 30 to 500m 2 / g, more preferably 40 to 300m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, more preferably 70-75m 2 72. The method according to any one of embodiments 67 to 71, wherein the crystalline silica exhibits a BET surface area in the range of / g, the BET surface area being preferably determined according to ISO 9277:2010.

[0178] 73. The method of any one of embodiments 67 to 72, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) exhibits 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, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0179] 74. The method of any one of embodiments 67 to 73, wherein, as element, 90 to 100 mass %, preferably 95 to 100 mass %, more preferably 99 to 100 mass %, more preferably 99.5 to 100 mass %, more preferably 99.9 to 100 mass %, of Ru is supported on the one or more support materials contained in the catalyst, calculated based on 100 mass % of Ru contained in the NH3 reforming catalyst C1 contained in the reactor provided in step (i).

[0180] 75. The method according to any one of embodiments 67 to 74, wherein Ru is supported on said one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, said one or more ruthenium salts preferably comprising Ru(NO)(NO3)3, more preferably Ru(NO)(NO3)3 is employed as said one or more ruthenium salts.

[0181] 76. The one or more support materials are selected from the group consisting of metal oxides, and the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, rare earth metals, and combinations of two or more thereof, more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, Nd, and combinations of two or more thereof, more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca, La, and combinations of two or more thereof, more preferably selected from the group consisting of Al, Zr, Mg, and combinations of two or more thereof. and a combination thereof; more preferably the one or more support materials comprise one or more metal oxides selected from the group consisting of Al2O3, ZrO2, spinel, and mixtures of two or more thereof, preferably from the group consisting of ZrO2, spinel, and 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 consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0182] 77. The method of embodiment 76, wherein the ZrO2 comprises one or more crystalline phases and / or is amorphous, and the one or more crystalline phases of ZrO2 are selected from the group consisting of a monoclinic phase, a tetragonal phase, a cubic phase of ZrO2, and mixtures of two or three thereof.

[0183] 78. The method of any one of embodiments 67 to 77, wherein the one or more support materials are substantially free of CaO and / or MgO, preferably substantially free of CaO and MgO, more preferably substantially free of alkaline earth metal oxides, more preferably substantially free of Ca and / or Mg, more preferably substantially free of Ca and Mg, more preferably substantially free of alkaline earth metals.

[0184] 79. The method of any one of embodiments 67 to 78, wherein the one or more support materials are substantially free of Al2O3 and / or SiO2, preferably substantially free of Al2O3 and SiO2, more preferably substantially free of Al and / or Si, more preferably substantially free of Al and Si.

[0185] 80. The method of any one of embodiments 67 to 79, wherein the one or more support materials are substantially free of carbon nanotubes, preferably substantially free of elemental carbon, more preferably substantially free of carbon.

[0186] 81. The method of any one of embodiments 67 to 80, wherein the NH3-reforming catalyst C1 comprises Ru in an amount ranging from 0.1 to 15% by weight, preferably from 1 to 10% by weight, more preferably from 2 to 8% by weight, more preferably from 3 to 6.5% by weight, more preferably from 4 to 6% by weight, more preferably from 4.5 to 5.5% by weight, based on 100% by weight of the total amount of the one or more support materials.

[0187] 82. The method of any one of embodiments 67 to 81, 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 NH3 reforming catalyst C1 consists of Ru and the one or more support materials.

[0188] 83. The method of any one of embodiments 67 to 82, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) 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 supported on the one or more support materials supporting Ru, and wherein the alkali metal and / or alkaline earth metal hydroxide is preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH, KOH, and mixtures of two or more thereof, more preferably from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH, KOH, and mixtures of two or more thereof, more preferably from the group consisting of LiOH, NaOH, KOH, and mixtures of two or more thereof, and more preferably the catalyst further comprises KOH and / or LiOH, preferably KOH.

[0189] 84. The method of embodiment 83, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) comprises the one or more alkali metal hydroxides in an amount ranging from 0.5 to 15% by weight, preferably from 1 to 10% by weight, more preferably from 2 to 8% by weight, more preferably from 3 to 6.5% by weight, more preferably from 4 to 6% by weight, more preferably from 4.5 to 5.5% by weight, based on 100% by weight of the total amount of the one or more support materials.

[0190] 85. The method of embodiment 83 or 84, 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 NH3 reforming catalyst C1 contained in the reactor provided in step (i) consists of Ru, the one or more alkali metal hydroxides, and the one or more support materials.

[0191] 86. The method according to any one of embodiments 67 to 85, wherein the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is in the form of a molding and / or in the form of a powder, preferably in the form of a molding, more preferably in the form of an extrudate or a tablet.

[0192] 87. The method of embodiment 86, wherein the extrudate has a diameter in the range of 0.5 to 10 mm, preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

[0193] 88. The method of embodiment 86 or 87, wherein the extrudates are split and the NH3 reforming catalyst C1 contained in the reactor provided in step (i) is in the form of extrudates with a split sieve fraction in the range of 50 μm to 2.5 mm, preferably 100 μm to 1.5 mm, more preferably 200 μm to 1 mm, more preferably 250 μm to 700 μm, more preferably 300 μm to 500 μm.

[0194] 89. The method according to embodiment 88, wherein the tablet has a four-hole cross section, preferably a four-hole cross section and four flutes. [Example]

[0195] Experimental Section The present invention will be further illustrated by the following Reference Examples, Examples and Comparative Examples.

[0196] Reference Example 1: Determining gas stream composition by FTIR Fourier transform infrared spectroscopy (FTIR) was used to determine the gas stream composition, in particular the HO content in the gas stream. For this purpose, the ThermoFisher Scientific "IGS Analyzer" instrument was used, and the "Omnic 9" software was used for data evaluation.

[0197] Reference Example 2: X-ray diffraction (XRD) determination Powder X-ray diffraction (PXRD) data were collected using a diffractometer (D8 Advance Series II, Bruker AXS GmbH) equipped with a LYNXEYE detector operated with a copper anode X-ray tube at 40 kV and 40 mA, Bragg-Brentano geometry, and an air scattering shield was used to reduce air scattering.

[0198] Crystallinity calculation: The crystallinity of the samples was determined using the software DIFFRAC.EVA from Bruker AXS GmbH, Karlsruhe, according to the method described in the user manual, page 121. Default parameters were used for the calculation.

[0199] Calculation of phase composition: Phase compositions were calculated for the raw data using the modeling software DIFFRAC.TOPAS provided by Bruker AXS GmbH (DIFFRAC.TOPAS Version 6 User Manual, 2017, Bruker AXS GmbH, Karlsruhe). The identified phase crystal structures, instrumental parameters, and crystallite sizes of the individual phases were used to simulate diffraction patterns, which were then fitted to the data in addition to a function modeling the background intensity.

[0200] When analyzing oxidized or passivated NH3 reforming catalyst samples, the samples were homogenized in a mortar and pressed into a standard flat sample holder for Bragg-Brentano geometry data collection provided by Bruker AXS GmbH. A flat surface was achieved by compressing and flattening the sample powder using a glass plate. The variable divergence slit angle was set to 0.1°, and data were collected from an angular range of 2 to 70° 2θ with a step size of 0.02° 2θ. The crystalline content represents the intensity of the crystalline signal relative to the total scattered intensity. The passivated layer yielded a fairly broad, nearly amorphous signal in the XRD. This broad signal was clearly different from the oxidized portion of the fresh sample.

[0201] When analyzing the reduced NH3 reforming catalyst samples, the samples were removed from the reactor under an inert gas atmosphere and prepared for XRD analysis using an airtight sample carrier, such as an airtight sample holder or a sealed capillary, in a glove box under inert gas.

[0202] Reference Example 3: Determination of Temperature Programmed Reduction (TPR) Temperature programmed reduction (TPR) determinations were performed using a Micromeritics® Autochem II. 5% H2 in Ar was used as the reducing gas. Hydrogen consumption was monitored with a TCD detector and presented as a reverse consumption. Hydrogen consumption is therefore presented as a positive peak. The gas flow was adjusted to 50 ml / min. Hydrogen consumption was further integrated and presented in μmol / g catalyst and related to a specific reduction event.

[0203] Reference Example 4: Determination of side crushing strength Side crushing strength was determined using a semi-automated tablet testing system, the Sotax ST-50 WTDH. Side crushing strength was measured at a constant speed of 0.05 mm / s. Tests were performed over a range of 0 to 800 N. For each measurement, the sample orientation was adjusted using a horizontal rotary table, with fine adjustments made manually. Additionally, several measurement parameters, such as mass, height / thickness, diameter, and breaking strength, were adjusted depending on the sample orientation and properties, if applicable. The resulting data were evaluated using the scientific program Q-DOC ProLab (version 4fsp2 (4.10)). Tablets with a four-hole cross section were tested, and probe measurements were performed at three mutually perpendicular positions to determine Side Crushing Strength 1, Side Crushing Strength 2, and Side Crushing Strength 3. The relative standard deviation for Crushing Strengths 1, 2, and 3 was 7.48%.

[0204] As can be seen in Figure 2, side crushing strength 1 refers to the position of the tablet in the semi-automatic tablet testing system where the sample stands on two cylindrical segments sandwiched by flutes on the rotating table, side crushing strength 2 refers to the position where the sample stands on one cylindrical segment on the rotating table, and side crushing strength 3 refers to the position where the hole is parallel to the direction of the force applied to the sample during the test.

[0205] Reference Example 5: Determination of side crushing strength Side crushing strength was determined using a tablet testing system (Typ BZ2.5 / TS1S, Zwick). Side crushing strength was measured using a punching tool. The side crushing strength was recorded when the sample broke. For each measurement, the sample was manually oriented on a horizontal table. The punching tool was positioned to punch from above. Additionally, several measurement parameters were adjusted depending on the sample orientation and properties, such as mass, height / thickness, diameter, and breaking strength. Tablets with a four-hole cross section were tested, and probe measurements were performed at three mutually perpendicular positions to determine side crushing strengths 1, 2, and 3. As can be seen in Figure 2, side crushing strength 1 refers to the position of the tablet in the semi-automatic tablet testing system where the sample stands on two cylindrical segments sandwiched between flutes on the rotating table. Side crushing strength 2 refers to the position where the sample stands on one cylindrical segment on the rotating table. Side crushing strength 3 refers to the position where the holes are parallel to the direction of the force applied to the sample during testing.

[0206] Reference Example 6: Preparation of passivated partially reduced Ni-containing catalyst A physical mixture of NiO (60% by weight) and alumina powder was mixed with water and a binder (e.g., methylcellulose or bentonite) to form an extrudable paste. This paste was extruded (1 / 8 inch diameter) and calcined at a moderate temperature below 300°C. The resulting catalyst was partially reduced and passivated in air. The partially reduced and passivated catalyst had a NiO to elemental Ni mass ratio of 43:57, as determined according to Reference Example 2. The average crystallite size of Ni was 6.0 nm, and the average crystallite size of NiO was 2.5 nm.

[0207] Reduction of the passivation layer occurs at mild temperatures between 150 and 220°C. Higher temperatures between 400 and 700°C reduce the remaining bulk NiO.

[0208] The TPR results are shown in Table 1 below and the TPR diagram is shown in Figure 3.

[0209] [Table 1]

[0210] Furthermore, the Ni-containing catalyst was analyzed after use according to the test in Example 9. Because the catalyst was not kept under an inert gas atmosphere after being removed from the reactor, partial oxidation occurred in air. The results are shown in Figure 5 and Table 2 below. Furthermore, the catalyst used had a mass ratio of NiO to elemental Ni of 30:70, as determined according to Reference Example 2. The average crystallite size of Ni was 12 nm, and the average crystallite size of NiO was 2 nm.

[0211] [Table 2]

[0212] As can be seen from the results shown in FIG. 5 and Table 2 in comparison with the results in FIG. 3 and Table 1, the Ni-containing catalyst prepared according to Reference Example 6 and then used in the catalytic test in which the method of the present invention was applied showed a strong peak below 400° C., indicating that passivation of metallic Ni occurred when the catalyst was transferred from the reactor to the analysis.

[0213] Reference Example 7: Preparation of fully oxidized Ni-containing catalyst A Ni-containing NH3 reforming catalyst was prepared according to the process described in Example E1 of WO 2013 / 068905 A1.

[0214] An aqueous nickel nitrate solution (Ni concentration 14% by mass) was mixed with hydrotalcite and an appropriate amount of water to prepare an extrudable paste. This paste was extruded in the following steps. The subsequent heat treatment of the obtained extrudate was the same as in Example 1 (Example E1 of WO 2013 / 068905 A1).

[0215] The calcined extrudates had a nickel content of 15.5 wt %, a magnesium content of 14.0 wt % and an aluminium content of 29.5 wt %.

[0216] In the TPR determined according to Reference Example 3, the first reduction event of the fully oxidized Ni-containing catalyst was observed to begin at 400° C. and continue up to above 1000° C. The TPR results are shown in Table 3 below, and the TPR diagram is shown in FIG.

[0217] [Table 3]

[0218] Reference Example 8: Preparation of MgAlO spinel supported Ru (5 wt%) and KOH (5 wt%, equivalent to 3.5 wt% K) A hydrotalcite precursor (Pural MG30 from Sasol) was calcined at temperatures ranging from 850 to 980°C for times ranging from 1 to 3 hours and then used as a support. A 93 g extrusion of the support was impregnated with 27 g of Ru(NO)(NO3)3 solution (19.7 wt% Ru in the solution). After drying at 180°C for 4 hours, the Ru-containing extrusion was impregnated with 5.105 g of K(OH). The resulting material was then dried at 120°C for 2 hours and subsequently calcined at 500°C for 2 hours under synthetic air consisting of 21% O2 and 79% N2 by volume.

[0219] The resulting Ru-containing catalyst was analyzed by TPR according to Reference Example 3. The results are shown in Figure 6 and Table 4 below.

[0220] [Table 4]

[0221] Reference Example 9: NH3 reforming test To illustrate the method of the present invention, a Ni-containing NH reforming catalyst was prepared in the form of extrudates according to Reference Example 6. The catalyst was used in an NH reforming process. In one run, the catalyst was activated at a pressure of 20 bara and a heating rate of 2°C / min to a temperature of 400°C. This activation protocol was carried out in a gas stream diluted with Ar with an NH partial pressure of 1 bara before NH reforming. For comparison, an NH reforming process was also carried out using the catalyst previously activated in a gas stream containing 5% by volume of H in Ar.

[0222] A specific temperature protocol was applied to reach the desired NH3 reforming conditions.

[0223] NH3 reforming is 4000h -1 The reaction was carried out in a gas stream consisting essentially of NH3 with a gas hourly space velocity (GHSV) of 1000 psi, and the NH3 reforming was carried out at a pressure of 40 bara. The pure NH3 feed stream was doped with 5000 ppm-volume H2O before being fed to the reactor. The catalysts were tested at temperatures between 350 and 550°C. The activity of the catalysts activated in different gas atmospheres was determined. The results are shown in Table 5 below.

[0224] [Table 5]

[0225] As can be seen from the NH3 reforming results, activating the NH3 reforming catalyst in a gas stream containing NH3 is a suitable method for producing highly active catalysts and simplifies the activation and start-up sequence of a typical NH3 reforming process. Thus, activation in a gas stream containing NH3, even at high pressure, was successful, and the NH3 reforming catalyst exhibited the same activity level as conventionally activated catalysts.

[0226] References: - I. Lucentini et al., Eng. Chem. Res. 2021, 60, 18560-18611 - T.Le et al., Korean J.Chem.Eng.,2021,38(6),1087-1103 - Bell et al., Top Catal., 2016, 59, 1438-1457 - X.-K. Li et al., Journal of Catalysis, 2005, 236, 181-189 - Fang et al., ACS Catalysis 2022,12,3938-3954

Claims

1. NH ３ A method for modification comprising the steps of: (i) NH containing a metal M1 selected from the group consisting of Groups 6 to 11 of the periodic table, and mixtures of two or more thereof ３ providing a reactor containing a reforming catalyst C1; (ii) NH ３ preparing a feed gas stream F1 containing (iii) feeding F1 prepared according to step (ii) into the reactor, and converting F1 into the NH ３ contacting the reforming catalyst C1 with H ２ O and NH ３ obtaining a product gas stream P1 comprising a reforming catalyst C2, the reactor having a temperature of 100° C. or higher; Including, The supply according to step (ii) is started at time t1; At time t2, H in the product gas stream P1 ２ O and H in the feed gas stream F1 ２ Sex with O ２ O(P1):H ２ The method wherein the O(F1) molar ratio is greater than 1:1 and the difference between t2 and t1 is in the range of 5 seconds to 10 days.

2. The NH contained in the reactor provided in step (i) ３ 2. The method of claim 1, wherein the X-ray diffraction pattern of the reforming catalyst C1 exhibits one or more crystalline phases of one or more oxides of M1.

3. The NH obtained from step (iii) ３ 3. The catalyst according to claim 1 or 2, wherein the X-ray diffraction pattern of the modified catalyst C2 shows one or more crystalline phases of the element M1.

4. 4. The method of any one of claims 1 to 3, wherein M1 is selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu, and mixtures of two or more thereof.

5. The feed gas stream F1 prepared according to step (ii) contains 0 to 0.5% by volume of H ２ 5. The catalyst of claim 1, comprising:

6. The feed gas stream F1 prepared according to step (ii) contains 1 to 100% by volume of NH ３ 6. The catalyst of claim 1, comprising:

7. The feed gas stream F1 prepared according to step (ii) contains NH ３ 7. The catalyst of claim 1 having a partial pressure.

8. The feed gas stream F1 prepared according to step (ii) contains 0 to 1% by volume of H ２ The method of claim 1 , further comprising:

9. 99-100% by volume of said feed gas stream F1 prepared according to step (ii) is NH ３ , H ２ , optionally H ２ O, and optionally an inert gas, wherein the inert gas is Ar and N ２ 9. The method of claim 1, comprising one or more of the following:

10. The feed gas stream F1 prepared according to step (ii) is －１ 10. The process of claim 1, wherein the gas is supplied to the reactor according to step (iii) at a gas hourly space velocity in the range of

11. 11. The process according to any one of claims 1 to 10, wherein the contacting according to step (iii) is carried out at a pressure in the range of from 1 to 65 bara.

12. 12. The process of any one of claims 1 to 11, wherein the contacting according to step (iii) is carried out at a temperature in the range of 200 to 1000°C.

13. The following process: (iv) NH ３ preparing a feed gas stream F2 comprising: (v) feeding the feed gas stream F2 prepared according to step (iv) into the reactor and rinsing the feed gas stream F2 with the NH ３ contacting with a reforming catalyst C2; and (vi) removing from the reactor ２ and N ２ removing an effluent gas stream comprising 13. The method of any one of claims 1 to 12, further comprising:

14. The feed gas stream F2 prepared according to step (iv) contains 1 to 100% by volume of NH ３ 14. The method of claim 13, comprising:

15. 99-100% by volume of the feed gas stream F2 prepared according to step (iv) is NH ３ , H ２ , optionally H ２ O, and optionally an inert gas, wherein the inert gas is Ar and N ２ 15. The method of claim 13 or 14, comprising one or more of:

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