Method for NH3 reforming

Abstract

The present invention relates to a process for NH3 reforming, the process comprising: (i) providing a reactor containing an NH3 reforming catalyst C1, the NH3 reforming catalyst 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 comprising NH3; (iii) feeding F1 into the reactor and contacting F1 with C1, wherein the reactor has a temperature of 100 DEG C or higher; obtaining a product gas stream P1 comprising H2O and an NH3 reforming catalyst C2; wherein the feed according to (ii) begins at the point in time t1; wherein at point in time t2, the molar ratio of H2O in P1 to H2O in F1 is greater than 1: 1, and wherein the difference between t2 and t1 is in the range of 5 s to 10 days.

Description

Technical Field

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

[0002] NH3 is seen as a future energy carrier that is able to chemically store large amounts of H2. Therefore, sustainable NH3 could potentially be produced on a large scale from renewable energy sources. Reforming NH3 on-site where H2 is required (see equation 1 below) could be the final step to complete the H2 value chain based on renewable electricity.

[0003]

[0004] In order to obtain H 2 directly at high pressures, in particular at pressures in the range from 10 to 50 bar absolute (bara), NH 3 reforming itself is very frequently also carried out at these pressures.

[0005] I. Lucentini et al., Ind. Eng. Chem. Res. [Industrial and Engineering Chemistry Research] 2021, 60, 18560-18611 and T. Le et al., Korean J. Chem. Eng. [Korean Journal of Chemical Engineering], 2021, 38(6), 1087-1103, respectively provide an overview of the catalysts used in ammonia decomposition.

[0006] X.-K. Li et al., Journal of Catalysis, 2005, 236, 181-189, specifically relates to the decomposition of ammonia over Ni and Ru catalysts.

[0007] Bell et al., Top Catal. [Catalysis Topics], 2016, 59, 1438-1457, relates to the decomposition of ammonia using non-precious metal catalysts, wherein Co-containing catalysts and Ni-containing catalysts are mainly discussed.

[0008] Fang et al. outlined the challenges and opportunities facing Ru-based catalysts for the synthesis and utilization of ammonia in ACS Catalysis 2022, 12, 3938-3954.

[0009] Typically, the spent NH3 reforming catalyst must be activated in a reducing gas prior to NH3 reforming. Conventionally, the NH3 reforming catalyst is activated with hydrogen as a reducing agent, which may be diluted with an inert gas, such as one or more of N2 or Ar. For example, WO 2023 / 111017 A1 relates to a method for ammonia reforming, in particular allowing reforming at relatively high pressures, which involves activating the catalyst with H2.

[0010] Therefore, there is a need to provide a relatively more convenient process, in particular by avoiding the additional step of preparing a specific reducing stream for reducing the spent catalyst. DETAILED DESCRIPTION

[0011] Therefore, the object of the present invention is to provide a method for NH3 reforming, so as to allow a convenient and resource-efficient method. Surprisingly, it has been found that a novel method for NH3 reforming can be provided, wherein the spent NH3 reforming catalyst is reduced in a gas stream comprising NH3. Therefore, it is found that by using NH3 feedstock as an activation reactant, a startup sequence or even an NH3 reforming plant can be promoted. The method of the present invention is generally applicable to any NH3 reforming catalyst that must be activated in a reducing gas.

[0012] Therefore, the present invention relates to a method for NH3 reforming, the method comprising

[0013] (i) providing a reactor containing an NH3 reforming catalyst C1, the NH3 reforming catalyst 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;

[0014] (ii) preparing a feed gas stream F1 comprising NH3;

[0015] (iii) feeding F1 prepared according to (ii) into a reactor and contacting F1 with an NH3 reforming catalyst C1, wherein the reactor has a temperature of 100°C or higher;

[0016] Obtaining a product gas stream P1 comprising H2O and an NH3 reforming catalyst C2;

[0017] wherein the feed according to (ii) is started at time t1;

[0018] Wherein at time point t2, the molar ratio of H2O(P1):H2O(F1) of H2O in the product gas stream P1 to H2O in the feed gas stream F1 is greater than 1:1, wherein the H2O in the product gas stream P1 and the H2O in the feed gas stream F1 are preferably determined according to DIN EN14790, more preferably according to Reference Example 1, wherein the difference between t2 and t1 is in the range of 5 s to 10 days.

[0019] In the context of the present invention, the difference between t2 and t1 may also be designated as Δt. Further, the difference Δt between t2 and t1 is calculated as Δt=t2-t1, where t2 is greater than t1.

[0020] Preferably, at time point t2, the molar ratio of H2O(P1):H2O(F1) of H2O in the product gas stream P1 to H2O in the feed gas stream F1 is 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.

[0021] Preferably, the difference between t2 and t1 is in the range of 5s to 9d, preferably in the range of 1min to 8d, more preferably in the range of 5min to 7d, more preferably in the range of 0.5h to 5d, more preferably in the range of 1h to 4d, more preferably in the range of 3h to 2d, more preferably in the range of 6h to 2d.

[0022] Preferably, the X-ray diffraction pattern of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows one or more crystalline phases of one or more oxides of M1, preferably determined according to Reference Example 2.

[0023] Preferably, the X-ray diffraction pattern of the NH3 reforming catalyst C2 obtained from (iii) shows one or more crystalline phases of the element M1, preferably determined according to Reference Example 2.

[0024] Preferably, the X-ray diffraction pattern of the NH3 reforming catalyst C2 obtained from (iii) does not show any crystalline phase of the oxide or oxides of M1, preferably determined according to Reference Example 2.

[0025] Preferably, M1 is selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu and a mixture of two or more thereof, more preferably selected from the group consisting of Ni, Co, Ru, Fe and a mixture thereof.

[0026] In the case where M1 is selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu and a mixture of two or more thereof, it is preferred that M1 includes Ni, preferably Ni.

[0027] In the case where M1 includes Ni, it is preferred that the XRD pattern of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a weight ratio of NiO crystalline phase to elemental Ni crystalline phase greater than 1:100, more 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, wherein the XRD pattern is preferably determined according to Reference Example 2.

[0028] In addition, in the case where M1 includes Ni, it is preferred that the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a first peak having a maximum value in the range of 100°C to 400°C, more preferably in the range of 120°C to 350°C, and more preferably in the range of 150°C to 250°C, wherein the TPR curve is preferably determined according to Reference Example 3.

[0029] In the case where the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a first peak having a maximum value in the range of 100°C to 400°C, it is preferred that the integral of the first peak provides a value in the range of 500 to 4000 μmol / g, more preferably in the range of 1500 to 3000 μmol / g, more preferably in the range of 2000 to 2500 μmol / g.

[0030] In addition, in the case where the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a first peak having a maximum value in the range of 100°C to 400°C, it is preferred that the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a second peak having a maximum value in the range of greater than 400°C to 900°C, more preferably in the range of 425°C to 850°C, and more preferably in the range of 450°C to 800°C, wherein the TPR curve is preferably determined according to Reference Example 3.

[0031] In the case where the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a second peak having a maximum value in the range of greater than 400°C to 900°C, it is preferred that the integral of the second peak provides a value in the range of 500 to 4500 μmol / g, more preferably in the range of 1500 to 3500 μmol / g, more preferably in the range of 2000 to 3000 μmol / g.

[0032] In addition, in the case where the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a first peak having a maximum value in the range of 100°C to 400°C, it is preferred that the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a third peak having a maximum value in the range of greater than 900°C to 1300°C, preferably in the range of 950°C to 1250°C, and more preferably in the range of 1000°C to 1200°C, wherein the TPR curve is preferably determined according to Reference Example 3.

[0033] In the case where the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a third peak having a maximum value in the range of greater than 900°C to 1300°C, it is preferred that the integral of the third peak provides a value in the range of 100 to 1500 μmol / g, more preferably in the range of 300 to 1250 μmol / g, more preferably in the range of 500 to 1000 μmol / g.

[0034] In the case where M1 is selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu and a mixture of two or more thereof, it is preferred that M1 includes Ru, more preferably Ru.

[0035] In the case where M1 includes Ru, more preferably Ru, it is preferred that the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a peak having a maximum value in the range of 100°C to 400°C, more preferably in the range of 120°C to 350°C, more preferably in the range of 150°C to 250°C, wherein the TPR curve is preferably determined according to Reference Example 3.

[0036] In the case where the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a peak having a maximum value in the range of 100°C to 400°C, it is preferred that the integral of the peak provides a value in the range of 1500 to 5000 μmol / g, more preferably in the range of 2500 to 4000 μmol / g, more preferably in the range of 3000 to 3500 μmol / g.

[0037] Preferably, the reactor provided in (i) has a length in the range of 0.5 m to 20 m, more preferably in the range of 1 m to 12 m.

[0038] Preferably, the reactor provided in (i) is operated in adiabatic mode.

[0039] Preferably, the reactor provided in (i) is heated directly, preferably flame-heated or electrically heated.

[0040] Preferably, the feed gas stream F1 prepared according to (ii) comprises 0 to 0.5 vol-%, more preferably 0 to 0.2 vol-%, more preferably 0 to 0.1 vol-%, more preferably 0 to 0.05 vol-%, more preferably 0 to 0.02 vol-%, more preferably 0 to 0.01 vol-%, more preferably 0 to 0.005 vol-%, more preferably 0 to 0.002 vol-%, more preferably 0 to 0.001 vol-% H2.

[0041] Preferably, the feed gas stream F1 prepared according to (ii) comprises 1 to 100 vol-%, more preferably 2 to 100 vol-%, more preferably 4 to 100 vol-%, more preferably 5 to 100 vol-%, more preferably 50 to 100 vol-%, more preferably 80 to 100 vol-%, more preferably 85 to 100 vol-%, more preferably 89.5 to 100 vol-%, preferably 94.5 to 100 vol-%, more preferably 99.0 to 100 vol-%, more preferably 99.5 to 100 vol-%, more preferably 99.6 to 100 vol-%, more preferably 99.7 to 100 vol-%, more preferably 99.8 to 100 vol-%, more preferably 99.9 to 100 vol-%, more preferably 99.95 to 100 vol-%, more preferably 99.98 to 100 vol-%, more preferably 99.99 to 100 vol-% NH3.

[0042] Preferably, the feed gas stream F1 prepared according to (ii) has an NH3 partial pressure in the range of 0.01 to 65 bar absolute, more preferably in the range of 0.05 to 45 bar absolute, more preferably in the range of 0.1 to 25 bar absolute, more preferably in the range of 0.5 to 15 bar absolute, more preferably in the range of 1 to 10 bar absolute.

[0043] Preferably, the feed gas stream F1 prepared according to (ii) comprises 0 to 1 vol-%, more preferably 0 to 0.8 vol-%, more preferably 0.0001 to 0.7 vol-%, more preferably 0.0001 to 0.6 vol-%, more preferably 0.03 to 0.5 vol-%, more preferably 0.05 to 0.4 vol-% H2O.

[0044] Preferably, the feed gas stream F1 prepared according to (ii) 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 inert gas, wherein the inert gas comprises, preferably consists of: one or more of Ar and N2, preferably N2.

[0045] Preferably, 99 to 100 vol.-%, preferably 99.9 to 100 vol.-%, more preferably 99.99 to 100 vol.-% of the feed gas stream F1 prepared according to (ii) consists of NH3, H2, optionally H2O and optionally an inert gas, wherein the inert gas comprises, preferably consists of: one or more of Ar and N2, preferably N2.

[0046] Preferably, according to (iii), a feed gas stream F1 prepared according to (ii) is fed to the reactor, the feed gas stream having a relative humidity of 100 to 15,000 h. -1 In the range of 500 to 10,000 h -1 In the range of 1000 to 5000 h -1 In the range of 2000 to 4750h -1 In the range of 3500 to 4500 h -1 Gas hourly space velocity in the range.

[0047] Preferably, the contacting according to (iii) is carried out at a pressure in the range of 1 to 65 bar absolute, more preferably 2 to 50 bar absolute, more preferably 4 to 35 bar absolute, more preferably 5 to 10 bar absolute.

[0048] Preferably, the contacting according to (iii) is carried out at a temperature in the range of 200 to 1000°C, more preferably 350 to 800°C, more preferably 450 to 650°C.

[0049] Preferably, the method further comprises

[0050] (iv) preparing a feed gas stream F2 comprising NH3;

[0051] (v) feeding the feed gas stream F2 prepared according to (iv) into the reactor and contacting the feed gas stream F2 with the NH3 reforming catalyst C2 obtained from (iii);

[0052] (vi) removing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2.

[0053] In case where the process further comprises (iv), (v) and (vi), it is preferred that the feed gas stream F2 prepared according to (iv) comprises 0 to 0.5 vol-%, more preferably 0 to 0.2 vol-%, more preferably 0 to 0.1 vol-%, more preferably 0 to 0.05 vol-%, more preferably 0 to 0.02 vol-%, more preferably 0 to 0.01 vol-%, more preferably 0 to 0.005 vol-%, more preferably 0 to 0.002 vol-%, more preferably 0 to 0.001 vol-% H2.

[0054] Additionally, in case wherein the process further comprises (iv), (v) and (vi), it is preferred that the feed gas stream F2 prepared according to (iv) comprises 1 to 100 vol-%, more preferably 2 to 100 vol-%, more preferably 4 to 100 vol-%, more preferably 5 to 100 vol-%, more preferably 50 to 100 vol-%, more preferably 80 to 100 vol-%, more preferably 85 to 100 vol-%, more preferably 89.5 to 100 vol-%, preferably 94.5 to 100 vol-%, more preferably 99.0 to 100 vol-%, more preferably 99.5 to 100 vol-%, more preferably 99.6 to 100 vol-%, more preferably 99.7 to 100 vol-% NH3.

[0055] Additionally, in case where the process further comprises (iv), (v) and (vi), it is preferred that the feed gas stream F2 prepared according to (iv) comprises 0 to 1 vol-%, more 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 HO.

[0056] Additionally, in cases where the process further comprises (iv), (v) and (vi), it is preferred that the feed gas stream F2 prepared according to (iv) 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, preferably consists of: one or more of Ar and N2, preferably N2.

[0057] Additionally, in cases where the process further comprises (iv), (v) and (vi), it is preferred that 99 to 100 vol-%, more preferably 99.9 to 100 vol-%, more preferably 99.99 to 100 vol-% of the feed gas stream F2 prepared according to (iv) consists of NH3, H2, optionally H2O and optionally an inert gas, wherein the inert gas comprises, preferably consists of: one or more of Ar and N2, preferably N2.

[0058] Additionally, in cases where the process further comprises (iv), (v) and (vi), it is preferred that the feed gas stream F2 prepared according to (iv) has the same chemical composition as the feed gas stream F1 prepared according to (ii).

[0059] In addition, in the case where the process further comprises (iv), (v) and (vi), it is preferred that the feed gas stream F2 prepared according to (iv) is fed into the reactor according to (v), the feed gas stream having a flow rate of 500 to 15,000 h -1 In the range of 1000 to 10,000 h -1 In the range of 2000 to 8000 hours, more preferably in the range of 2000 to 8000 hours -1 In the range of 3250 to 6000h, more preferably in the range of 3250 to 6000h -1 In the range of 3500 to 5000 h -1 Gas hourly space velocity in the range.

[0060] In addition, in cases where the method further comprises (iv), (v) and (vi), it is preferred that the contacting according to (v) is carried out at a pressure in the range of 10 to 65 bar absolute, preferably 20 to 55 bar absolute, more preferably 30 to 50 bar absolute, more preferably 35 to 45 bar absolute.

[0061] In addition, in the case where the method further comprises (iv), (v) and (vi), it is preferred that the contacting according to (v) is carried out at a temperature in the range of 200°C to 950°C, preferably 250°C to 800°C, more preferably 300°C to 700°C, more preferably 325°C to 600°C, more preferably 350°C to 550°C.

[0062] In addition, in the case where the method further includes (iv), (v) and (vi), it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises a metal M2, and the metal M2 is selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru and mixtures of two or more thereof, more preferably selected 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 selected from the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru and mixtures of two or more thereof, more preferably selected from the group consisting of K, Ba, Mo, Fe, Ru and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Ru and mixtures thereof, wherein M2 is more preferably Ru.

[0063] In the case where the NH3 reforming catalyst C1 contained in the reactor provided in (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, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises one or more of M1 and M2, preferably one or more support materials on which M1 and M2 are loaded, wherein 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 selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2 and mixtures of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2 and mixtures thereof, wherein the more preferred support material comprises Al2O3.

[0064] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (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 (i) further shows 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, and more preferably 40:60 to 50:50.

[0065] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (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 M2 comprises Fe or Co, preferably Fe or Co, and wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) 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, and more preferably 40:60 to 50:50.

[0066] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (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 M2 includes Ru, preferably Ru, and wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows 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.

[0067] According to the first alternative, and further in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (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 (i) further comprises Al and O.

[0068] In the case where the NH 3 reforming catalyst C1 contained in the reactor provided in (i) further contains Al and O, it is preferred that the NH 3 reforming catalyst C1 contained in the reactor provided in (i) contains Ni as the metal M1, wherein more preferably the metal M1 is Ni.

[0069] In the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) contains Ni as the metal M1, wherein the metal M1 is more preferably Ni, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) further contains Mg, wherein the Ni:Mg:Al molar ratio 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).

[0070] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ni as the metal M1, wherein more preferably the metal M1 is Ni, according to one alternative it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of Ni, Mg, Al and O.

[0071] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ni as metal M1, wherein more preferably the metal M1 is Ni, according to another alternative it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of M2, Ni, Mg, Al and O.

[0072] According to the second alternative, and further in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (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 (i) comprises Co as the metal M1, wherein more preferably the metal M1 is Co.

[0073] In the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) contains Co as the metal M1, wherein the metal M1 is more preferably Co, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) further contains La, wherein the Co:La:Al molar ratio 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).

[0074] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Co as metal M1, wherein more preferably the metal M1 is Co, according to one alternative it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of Co, La, Al and O.

[0075] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Co as metal M1, wherein more preferably the metal M1 is Co, according to another alternative it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of M2, Co, La, Al and O.

[0076] Preferably, the NH 3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of a shaped body.

[0077] In the case where the NH 3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of a shaped body, it is preferred that the shaped body is a tablet.

[0078] According to the first alternative, and in the case where the shaped body is a tablet, it is preferred that the tablet has a four-hole cross-section, more preferably a four-hole cross-section 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.

[0079] In the case where the tablet has a four-hole cross-section, more preferably a four-hole cross-section with a diameter in the range of 5 to 19 mm, it is preferred that the tablet is a calcined tablet, wherein the calcination is more preferably carried out in a gas atmosphere having a temperature in the range of 350°C to 450°C, more preferably in the range of 360°C to 440°C, more preferably in the range of 375°C to 425°C, more preferably in the range of 390°C to 410°C, wherein the gas atmosphere more preferably contains oxygen, more preferably one or more of oxygen, air or lean air, wherein the calcination is more preferably carried out for 0.5 to 20, more preferably 1 to 15 h, more preferably 2 to 10 h, more preferably 3 to 5 h.

[0080] In addition, in the case where the tablet has a four-hole cross-section, it is preferred that the tablet has a side compression strength 1 (SCS1) of at least 70N, more preferably in the range of 70 to 250N, and more preferably in the range of 70 to 130N determined as described in Reference Example 5, wherein the four cylindrical sections are respectively located in the area between the two grooves, wherein the side compression strength 1 is measured according to Reference Example 5 under the condition where the tablet stands on the two cylindrical sections on the sides of the groove.

[0081] In addition, in the case where the tablet has a four-hole cross-section, it is preferred that the tablet has a side compression strength 2 (SCS2) of at least 60N, more preferably in the range of 60 to 200N, more preferably in the range of 60 to 88N determined as described in Reference Example 5, wherein the four cylindrical sections are respectively located in the area between two grooves, wherein the side compression strength 2 is measured according to Reference Example 5 under the condition where the tablet stands on the cylindrical section.

[0082] In addition, in the case where the tablet has a four-hole cross-section, it is preferred that the tablet has a lateral compression strength 3 (SCS3) of at least 190N, more preferably in the range of 190 to 350N, more preferably in the range of 190 to 240N, as determined as described in Reference Example 5, wherein the four cylindrical segments are respectively located in the area between two grooves, wherein the lateral compression strength 3 is measured according to Reference Example 5 under the condition that the area of ​​the cylindrical segment is perpendicular to the direction of the force applied to the tablet.

[0083] According to the second alternative, and in the case where the shaped body is a tablet, it is preferred that 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, 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.

[0084] In the case where 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 preferred that the tablet is a calcined tablet, wherein the calcination has preferably been carried out in a gas atmosphere having a temperature in the range of 800°C to 1400°C, more preferably in the range of 875°C to 1275°C, more preferably in the range of 950°C to 1250°C, more preferably in the range of 1050°C to 1225°C, wherein the gas atmosphere more preferably contains oxygen, more preferably one or more of oxygen, air, or lean air, wherein the calcination is more preferably carried out for 0.5 to 20 h, more preferably 1 to 15 h, more preferably 2 to 10 h, more preferably 3 to 5 h.

[0085] In addition, in the case where 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 preferred that the tablet has a side compression strength 1 (SCS1) 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 determined as described in Reference Example 4, and the molded body is more preferably a tablet having a four-hole cross-section and having four grooves, wherein the four cylindrical sections are respectively located in the area between two grooves, wherein the side compression strength 1 is measured according to Reference Example 4 under the condition where the tablet stands on the two cylindrical sections on the sides of the groove.

[0086] In addition, in the case where 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 preferred that the tablet has a side compression strength 2 (SCS2) of at least 170N, more preferably at least 190N, more preferably in the range of 190 to 450N, more preferably in the range of 190 to 300N, more preferably in the range of 190 to 270N as determined as described in Reference Example 4, wherein the four cylindrical sections are respectively located in the area between two grooves, wherein the side compression strength 2 is measured according to Reference Example 4 under the condition where the tablet stands on the cylindrical section.

[0087] In addition, in the case where 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 preferred that the tablet has a side compression strength 3 (SCS3) 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 determined as described in Reference Example 4, wherein the four cylindrical sections are respectively located in the area between the two grooves, wherein the side compression strength 3 is preferably measured according to Reference Example 4 under the condition that the area of ​​the cylindrical section is perpendicular to the direction of the force applied to the tablet.

[0088] According to the above, in particular, specific and preferred embodiments relating to the case in which the NH3 reforming catalyst C1 contained in the reactor provided in (i) contains Ru, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) further contains one or more carrier materials, wherein Ru is loaded on the one or more carrier materials.

[0089] In the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises 1 wt.-% or less, more preferably 0.5 wt.-%, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, and more preferably 0.001 wt.-% or less of Ni and Co, calculated as the respective elements and based on 100 wt.-% of the NH3 reforming catalyst C1.

[0090] In addition, in the case where the NH reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred according to one alternative that the one or more support materials exhibit a 20 m 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, and more preferably 75 to 80 m 2 The BET surface area is preferably determined in accordance with ISO 9277:2010.

[0091] In addition, in the case where the NH reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred according to another alternative that the one or more support materials exhibit a 20 m 2 / g or more, more preferably greater than 20 to 150m 2 / g, more preferably 21 to 100m 2 / g, more preferably 22 to 70m 2 / g, more preferably 23 to 50m 2 / g, more preferably 24 to 40m 2 / g, and more preferably 25 to 35m 2 The BET surface area is preferably determined in accordance with ISO 9277:2010.

[0092] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred that the one or more support materials 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, and more preferably 0.8 to 0.85 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0093] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on one or more support materials, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) exhibits a relative humidity of 20 to 800 m 2 / g, more 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, and more preferably 70 to 75m 2 The BET surface area is preferably determined in accordance with ISO 9277:2010.

[0094] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) exhibits a pore volume in the range of 0.1 to 2 ml / g, more preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, and more preferably 0.3 to 0.35 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0095] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred that, calculated as element and based on 100 wt.-% of Ru contained in the NH3 reforming catalyst C1 contained in the reactor provided in (i), 90 to 100 wt.-%, more preferably 95 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of Ru is supported on the one or more support materials contained in the catalyst.

[0096] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more carrier materials, wherein Ru is loaded on the one or more carrier materials, it is preferred that Ru is loaded on the one or more carrier materials by impregnation technology using an aqueous solution of one or more ruthenium salts, wherein the one or more ruthenium salts more preferably include Ru(NO)(NO3)3, wherein Ru(NO)(NO3)3 is more preferably used as the one or more ruthenium salts.

[0097] In addition, in the case where the NH reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred that the one or more support materials are 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 and rare earth metals, including combinations of two or more thereof, more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd, including combinations of two or more thereof, more preferably selected from the group consisting of Al, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals and rare earth metals, including combinations of two or more thereof, more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd, including combinations of two or more thereof, more preferably selected from the group consisting of Al, Ti, Z r, Mg, Ca and La, including combinations of two or more thereof, more preferably selected from the group consisting of: Al, Zr and Mg, including combinations of two or more thereof, wherein more preferably one or more carrier materials comprise one or more metal oxides, the one or more metal oxides being selected from the group consisting of: Al2O3, ZrO2 and spinel, including mixtures of two or more thereof, preferably selected from the group consisting of: ZrO2 and spinel, including mixtures of two or more thereof, wherein more preferably one or more carrier materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2, wherein more preferably one or more carrier materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0098] In cases where one or more support materials include ZrO2, it is preferred that the ZrO2 contains 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 and cubic phases of ZrO2, including mixtures of two or three thereof.

[0099] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred that the one or more support materials are 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, and more preferably substantially free of alkaline earth metals.

[0100] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more carrier materials, wherein Ru is loaded on the one or more carrier materials, it is preferred that the one or more carrier materials are substantially free of Al2O3 and / or SiO2, more preferably substantially free of Al2O3 and SiO2, more preferably substantially free of Al and / or Si, and more preferably substantially free of Al and Si.

[0101] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred that the one or more support materials are substantially free of carbon nanotubes, more preferably substantially free of elemental carbon, and more preferably substantially free of carbon.

[0102] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more carrier materials, wherein Ru is loaded on the one or more carrier materials, it is preferred that the NH3 reforming catalyst C1 comprises Ru in an amount ranging from 0.1 to 15 wt.-%, more preferably from 1 to 10 wt.-%, more preferably from 2 to 8 wt.-%, more preferably from 3 to 6.5 wt.-%, more preferably from 4 to 6 wt.-%, and more preferably from 4.5 to 5.5 wt.-%, based on 100 wt.-% of the total amount of the one or more carrier materials.

[0103] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 consists of Ru and one or more support materials.

[0104] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is loaded on one or more support materials, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises one or more alkali metal and / or alkaline earth metal hydroxides, wherein one or more alkali metal and / or alkaline earth metal hydroxides are loaded on one or more support materials loaded with 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 and KOH, including mixtures of two or more thereof, more preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH and KOH, including mixtures of two or more thereof, more preferably selected from the group consisting of LiOH, NaOH and KOH, including mixtures of two or more thereof, wherein the more preferred catalyst further comprises KOH and / or LiOH, preferably KOH.

[0105] In the case where the NH3 reforming catalyst C1 contained in the reactor provided in (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 one or more Ru-loaded support materials, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises one or more alkali metal hydroxides in an amount ranging from 0.5 to 15 wt.-%, more preferably from 1 to 10 wt.-%, more preferably from 2 to 8 wt.-%, more preferably from 3 to 6.5 wt.-%, more preferably from 4 to 6 wt.-%, and more preferably from 4.5 to 5.5 wt.-%, based on 100 wt.-% of the total amount of the one or more support materials.

[0106] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (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 one or more Ru-loaded support materials, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of Ru, one or more alkali metal hydroxides and one or more support materials.

[0107] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more carrier materials, wherein Ru is loaded on the one or more carrier materials, it is preferred that the NH3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of a molded body and / or in the form of a powder, preferably in the form of a molded body, and more preferably in the form of an extrudate or a tablet.

[0108] In the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of extrudates, it is preferred that 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, and more preferably 2.5 to 3.5 mm.

[0109] In addition, in the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of an extrudate, it is preferred that the extrudate is separated and the NH3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of an extrudate of a separated sieved portion 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 to 700 μm, and more preferably 300 to 500 μm.

[0110] In the case where the NH3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of extrudates of separated sieved fractions in the range of 50 μm to 2.5 mm, it is preferred that the tablet has a four-hole cross section, more preferably a four-hole cross section and four four grooves.

[0111] The present invention is further illustrated by the following groups of embodiments and combinations of embodiments resulting from dependencies and back-references as indicated. In particular, it should be noted that in each case where a series of embodiments is mentioned, for example in the context of a term such as "a method as described in any one of embodiments 1 to 4", each embodiment in this series is intended to be disclosed explicitly to the skilled person, i.e. the wording of this term should be understood by the skilled person as synonymous with "a method as described in any one of embodiments 1, 2, 3 and 4".

[0112] Further, it is explicitly pointed out that the following set of embodiments is not a set of claims that determine the scope of protection, but represents a suitable structural part of the present description related to the general and preferred aspects of the present invention.

[0113] 1. A method for NH3 reforming, the method comprising

[0114] (i) providing a reactor containing an NH3 reforming catalyst C1, the NH3 reforming catalyst 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;

[0115] (ii) preparing a feed gas stream F1 comprising NH3;

[0116] (iii) feeding F1 prepared according to (ii) into the reactor and contacting F1 with the NH3 reforming catalyst C1, wherein the reactor has a temperature of 100°C or higher;

[0117] Obtaining a product gas stream P1 comprising H2O and an NH3 reforming catalyst C2;

[0118] wherein the feed according to (ii) is started at time t1;

[0119] Wherein at time point t2, the molar ratio H2O(P1):H2O(F1) of H2O in the product gas stream P1 to H2O in the feed gas stream F1 is greater than 1:1, wherein the H2O in the product gas stream P1 and the H2O in the feed gas stream F1 are preferably determined according to DIN EN 14790, more preferably according to Reference Example 1, wherein the difference between t2 and t1 is in the range of 5 s to 10 days.

[0120] 2. A method as described in Example 1, wherein at time point t2, the molar ratio of H2O(P1):H2O(F1) of H2O in the product gas stream P1 to H2O in the feed gas stream F1 is 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.

[0121] 3. A method as described in Example 1 or 2, wherein the difference between t2 and t1 is in the range of 5s to 9d, preferably in the range of 1min to 8d, more preferably in the range of 5min to 7d, more preferably in the range of 0.5h to 5d, more preferably in the range of 1h to 4d, more preferably in the range of 3h to 2d, more preferably in the range of 6h to 2d.

[0122] 4. A method as described in 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 (i) shows one or more crystalline phases of one or more oxides of M1, preferably determined according to Reference Example 2.

[0123] 5. The method as described in any one of embodiments 1 to 4, wherein the X-ray diffraction pattern of the NH3 reforming catalyst C2 obtained from (iii) shows one or more crystalline phases of element M1, preferably determined according to Reference Example 2.

[0124] 6. The method as described in any one of embodiments 1 to 5, wherein the X-ray diffraction pattern of the NH3 reforming catalyst C2 obtained from (iii) does not show any crystalline phase of one or more oxides of M1, preferably determined according to Reference Example 2.

[0125] 7. The method of any one of embodiments 1 to 6, wherein M1 is selected from the group consisting of Ru, Ni, Rh, Co, Ir, Fe, Pt, Cr, Pd, Cu, and a mixture of two or more thereof, preferably selected from the group consisting of Ni, Co, Ru, Fe, and a mixture thereof.

[0126] 8. The method of embodiment 7, wherein M1 comprises Ni, preferably Ni.

[0127] 9. A method as described in Example 8, wherein the XRD pattern of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a weight 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, wherein the XRD pattern is preferably determined according to Reference Example 2.

[0128] 10. A method as described in Example 8 or 9, wherein the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a first peak having a maximum value in the range of 100°C to 400°C, preferably in the range of 120°C to 350°C, more preferably in the range of 150°C to 250°C, wherein the TPR curve is preferably determined according to Reference Example 3.

[0129] 11. The method of embodiment 10, wherein the integration of the first peak provides a value 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.

[0130] 12. A method as described in Example 10 or 11, wherein the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a second peak having a maximum value in the range of greater than 400°C to 900°C, preferably in the range of 425°C to 850°C, more preferably in the range of 450°C to 800°C, wherein the TPR curve is preferably determined according to Reference Example 3.

[0131] 13. The method of embodiment 12, wherein the integration of the second peak provides a value 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.

[0132] 14. A method as described in any one of Examples 10 to 13, wherein the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a third peak having a maximum value in the range of greater 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, wherein the TPR curve is preferably determined according to Reference Example 3.

[0133] 15. The method of embodiment 14, wherein the integration of the third peak provides a value 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.

[0134] 16. The method of embodiment 7, wherein M1 comprises Ru, preferably Ru.

[0135] 17. A method as described in Example 16, wherein the TPR curve of the NH3 reforming catalyst C1 contained in the reactor provided in (i) shows a peak having a maximum value in the range of 100°C to 400°C, preferably in the range of 120°C to 350°C, more preferably in the range of 150°C to 250°C, wherein the TPR curve is preferably determined according to Reference Example 3.

[0136] 18. The method of embodiment 17, wherein the integration of the peak provides a value 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.

[0137] 19. The method of any one of embodiments 1 to 18, wherein the reactor provided in (i) has a length in the range of 0.5 to 20 m, preferably in the range of 1 to 12 m.

[0138] 20. The method of any one of embodiments 1 to 19, wherein the reactor provided in (i) is operated in an adiabatic mode.

[0139] 21. The method of any one of embodiments 1 to 20, wherein the reactor provided in (i) is directly heated, preferably flame heated or electrically heated.

[0140] 22. A process as described in any of Examples 1 to 21, wherein the feed gas stream F1 prepared according to (ii) comprises 0 to 0.5 volume-%, preferably 0 to 0.2 volume-%, more preferably 0 to 0.1 volume-%, more preferably 0 to 0.05 volume-%, more preferably 0 to 0.02 volume-%, more preferably 0 to 0.01 volume-%, more preferably 0 to 0.005 volume-%, more preferably 0 to 0.002 volume-%, more preferably 0 to 0.001 volume-% H2.

[0141] 23. The process of any one of embodiments 1 to 22, wherein the feed gas stream F1 prepared according to (ii) comprises 1 to 100 vol-%, preferably 2 to 100 vol-%, more preferably 4 to 100 vol-%, more preferably 5 to 100 vol-%, more preferably 50 to 100 vol-%, more preferably 80 to 100 vol-%, more preferably 85 to 100 vol-%, more preferably 89.5 to 100 vol-%, preferably 94.5 to 1 00 volume-%, more preferably 99.0 to 100 volume-%, more preferably 99.5 to 100 volume-%, more preferably 99.6 to 100 volume-%, more preferably 99.7 to 100 volume-%, more preferably 99.8 to 100 volume-%, more preferably 99.9 to 100 volume-%, more preferably 99.95 to 100 volume-%, more preferably 99.98 to 100 volume-%, more preferably 99.99 to 100 volume-% NH3.

[0142] 24. A process as described in any one of embodiments 1 to 23, wherein the feed gas stream F1 prepared according to (ii) has an NH3 partial pressure in the range of 0.01 to 65 bar absolute pressure, preferably in the range of 0.05 to 45 bar absolute pressure, more preferably in the range of 0.1 to 25 bar absolute pressure, more preferably in the range of 0.5 to 15 bar absolute pressure, more preferably in the range of 1 to 10 bar absolute pressure.

[0143] 25. The process of any one of embodiments 1 to 24, wherein the feed gas stream F1 prepared according to (ii) comprises 0 to 1 vol-%, preferably 0 to 0.8 vol-%, more preferably 0.0001 to 0.7 vol-%, more preferably 0.0001 to 0.6 vol-%, more preferably 0.03 to 0.5 vol-%, more preferably 0.05 to 0.4 vol-% H2O.

[0144] 26. A method as described in any of embodiments 1 to 25, wherein the feed gas stream F1 prepared according to (ii) contains 0 to 99 volume-%, preferably 98 volume-%, more preferably 0 to 96 volume-%, more preferably 0 to 95 volume-%, more preferably 0 to 50 volume-%, more preferably 0 to 30 volume-%, more preferably 0 to 20 volume-%, more preferably 0 to 10 volume-%, more preferably 0 to 5 volume-% of an inert gas, wherein the inert gas comprises, preferably consists of: one or more of Ar and N2, preferably N2.

[0145] 27. A method as described in any of Examples 1 to 26, wherein 99 to 100 volume-%, preferably 99.9 to 100 volume-%, more preferably 99.99 to 100 volume-% of the feed gas stream F1 prepared according to (ii) consists of NH3, H2, optionally H2O and optionally an inert gas, wherein the inert gas includes, preferably consists of: one or more of Ar and N2, preferably N2.

[0146] 28. The process of any one of embodiments 1 to 27, wherein the feed gas stream F1 prepared according to (ii) is fed to the reactor according to (iii), the feed gas stream having a flow rate of 100 to 15,000 h -1 In the range of 500 to 10,000 hours, preferably -1 In the range of 1000 to 5000 h -1 In the range of 2000 to 4750h -1 In the range of 3500 to 4500 h -1 Gas hourly space velocity in the range.

[0147] 29. The method of any one of embodiments 1 to 28, wherein the contacting according to (iii) is performed at a pressure in the range of 1 to 65 bar absolute, more preferably 2 to 50 bar absolute, more preferably 4 to 35 bar absolute, more preferably 5 to 10 bar absolute.

[0148] 30. The method of any one of embodiments 1 to 29, wherein the contacting according to (iii) is performed at a temperature in the range of 200°C to 1000°C, preferably 350°C to 800°C, more preferably 450°C to 650°C.

[0149] 31. The method of any one of embodiments 1 to 30, further comprising

[0150] (iv) preparing a feed gas stream F2 comprising NH3;

[0151] (v) feeding the feed gas stream F2 prepared according to (iv) into the reactor and contacting the feed gas stream F2 with the NH3 reforming catalyst C2 obtained from (iii);

[0152] (vi) removing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2.

[0153] 32. A method as described in Example 31, wherein the feed gas stream F2 prepared according to (iv) contains 0 to 0.5 volume-%, preferably 0 to 0.2 volume-%, more preferably 0 to 0.1 volume-%, more preferably 0 to 0.05 volume-%, more preferably 0 to 0.02 volume-%, more preferably 0 to 0.01 volume-%, more preferably 0 to 0.005 volume-%, more preferably 0 to 0.002 volume-%, more preferably 0 to 0.001 volume-% H2.

[0154] 33. A method as described in Example 31 or 32, wherein the feed gas stream F2 prepared according to (iv) contains 1 to 100 volume-%, more preferably 2 to 100 volume-%, more preferably 4 to 100 volume-%, more preferably 5 to 100 volume-%, more preferably 50 to 100 volume-%, more preferably 80 to 100 volume-%, more preferably 85 to 100 volume-%, more preferably 89.5 to 100 volume-%, preferably 94.5 to 100 volume-%, more preferably 99.0 to 100 volume-%, more preferably 99.5 to 100 volume-%, more preferably 99.6 to 100 volume-%, more preferably 99.7 to 100 volume-% NH3.

[0155] 34. A method as described in any of embodiments 31 to 33, wherein the feed gas stream F2 prepared according to (iv) contains 0 to 1 volume-%, preferably 0 to 0.8 volume-%, more preferably 0.0001 to 0.7 volume-%, more preferably 0.0001 to 0.5 volume-%, more preferably 0.0005 to 0.4 volume-%, more preferably 0.001 to 0.3 H2O.

[0156] 35. A method as described in any of Examples 31 to 34, wherein the feed gas stream F2 prepared according to (iv) contains 0 to 99 volume-%, preferably 98 volume-%, more preferably 0 to 96 volume-%, more preferably 0 to 95 volume-%, more preferably 0 to 50 volume-%, more preferably 0 to 30 volume-%, more preferably 0 to 20 volume-%, more preferably 0 to 10 volume-%, more preferably 0 to 5 volume-% of an inert gas, wherein the inert gas comprises, preferably consists of: one or more of Ar and N2, preferably N2.

[0157] 36. A method as described in any of Examples 31 to 35, wherein 99 to 100 volume-%, preferably 99.9 to 100 volume-%, more preferably 99.99 to 100 volume-% of the feed gas stream F2 prepared according to (iv) consists of NH3, H2, optionally H2O and optionally an inert gas, wherein the inert gas includes, preferably consists of: one or more of Ar and N2, preferably N2.

[0158] 37. The method of any one of embodiments 31 to 36, wherein the feed gas stream F2 prepared according to (iv) has the same chemical composition as the feed gas stream F1 prepared according to (ii).

[0159] 38. The process of any one of embodiments 31 to 37, wherein the feed gas stream F2 prepared according to (iv) is fed to the reactor according to (v), the feed gas stream having a flow rate of 500 to 15,000 h. -1 In the range of 1000 to 10,000 hours, preferably -1 In the range of 2000 to 8000 hours, more preferably in the range of 2000 to 8000 hours -1 In the range of 3250 to 6000h, more preferably in the range of 3250 to 6000h -1 In the range of 3500 to 5000 h -1 Gas hourly space velocity in the range.

[0160] 39. The method of any one of embodiments 31 to 38, wherein the contacting according to (v) is carried out at a pressure in the range of 10 to 65 bar absolute, more preferably 20 to 55 bar absolute, more preferably 30 to 50 bar absolute, more preferably 35 to 45 bar absolute.

[0161] 40. The method of any one of embodiments 31 to 39, wherein the contacting according to (v) is carried out at a temperature in the range of 200°C to 950°C, preferably 250°C to 800°C, preferably 300°C to 700°C, more preferably 325°C to 600°C, more preferably 350°C to 550°C.

[0162] 41. A method as described in any one of Examples 1 to 40, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises a metal M2, and the metal M2 is selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru and mixtures of two or more thereof, preferably selected 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 selected from the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru and mixtures of two or more thereof, more preferably selected from the group consisting of K, Ba, Mo, Fe, Ru and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Ru and mixtures thereof, wherein M2 is more preferably Ru.

[0163] 42. A method as described in Example 41, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises one or more of M1 and M2, preferably one or more carrier materials on which M1 and M2 are loaded, wherein the one or more carrier 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 selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2 and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2 and a mixture thereof, wherein more preferably the carrier material includes Al2O3.

[0164] 43. A method as described in Example 41 or 42, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) further shows 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, and more preferably 40:60 to 50:50.

[0165] 44. A method as described in any of Examples 41 to 43, wherein M2 comprises Fe or Co, preferably Fe or Co, and wherein the NH3 reforming catalyst C1 contained in the reactor provided in (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, and more preferably 40:60 to 50:50.

[0166] 45. A method as described in any of Embodiments 41 to 44, wherein M2 comprises Ru, preferably Ru, and wherein the NH3 reforming catalyst C1 contained in the reactor provided in (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, and more preferably 5:95 to 6:94.

[0167] 46. ​​The method as described in any one of embodiments 41 to 45, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises Al and O.

[0168] 47. The method as described in embodiment 46, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ni as the metal M1, wherein preferably the metal M1 is Ni.

[0169] 48. A method as described in Example 47, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises Mg, wherein the Ni:Mg:Al molar ratio 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).

[0170] 49. A method as described in Example 47 or 48, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of Ni, Mg, Al and O.

[0171] 50. A method as described in Example 47 or 48, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of M2, Ni, Mg, Al and O.

[0172] 51. The method as described in Example 46, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Co as the metal M1, wherein preferably the metal M1 is Co.

[0173] 52. A method as described in Example 52, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises La, wherein the Co:La:Al molar ratio 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).

[0174] 53. A method as described in Example 51 or 52, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of Co, La, Al and O.

[0175] 54. A method as described in Example 51 or 52, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of M2, Co, La, Al and O.

[0176] 55. The method according to any one of embodiments 1 to 54, wherein the NH 3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of a shaped body.

[0177] 56. The method of embodiment 55, wherein the shaped body is a tablet.

[0178] 57. A method as described in Example 56, wherein the tablet has a four-hole cross-section, preferably a four-hole cross-section having 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.

[0179] 58. A method as described in Example 57, wherein the tablet is a calcined tablet, wherein the calcination is preferably carried out in a gas atmosphere having a temperature in the range of 350°C to 450°C, more preferably in the range of 360°C to 440°C, more preferably in the range of 375°C to 425°C, more preferably in the range of 390°C to 410°C, wherein the gas atmosphere more preferably contains oxygen, more preferably one or more of oxygen, air, or lean air, wherein the calcination is more preferably carried out for 0.5 to 20 h, more preferably 1 to 15 h, more preferably 2 to 10 h, more preferably 3 to 5 h.

[0180] 59. A method as described in Example 57 or 58, wherein the tablet has a side compression strength 1 (SCS1) of at least 70N, preferably in the range of 70 to 250N, more preferably in the range of 70 to 130N determined as described in Reference Example 5, wherein the four cylindrical sections are respectively located in the area between the two grooves, wherein the side compression strength 1 is measured according to Reference Example 5 under the condition where the tablet stands on the two cylindrical sections on the sides of the groove.

[0181] 60. A method as described in any of Examples 57 to 59, wherein the tablet has a side compression strength 2 (SCS2) of at least 60 N, preferably in the range of 60 to 200 N, more preferably in the range of 60 to 88 N determined as described in Reference Example 5, wherein the four cylindrical sections are respectively located in the area between the two grooves, wherein the side compression strength 2 is measured according to Reference Example 5 under the condition where the tablet stands on the cylindrical sections.

[0182] 61. A method as described in any of embodiments 57 to 60, wherein the tablet has a lateral compression strength 3 (SCS3) of at least 190 N, preferably in the range of 190 to 350 N, more preferably in the range of 190 to 240 N determined as described in Reference Example 5, wherein the four cylindrical segments are respectively located in the area between the two grooves, wherein the lateral compression strength 3 is measured according to Reference Example 5 under the condition where the area of ​​the cylindrical segment is perpendicular to the direction of the force applied to the tablet.

[0183] 62. A method as described in Example 56, wherein the tablet has a four-hole cross-section, preferably a four-hole cross-section having 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.

[0184] 63. A method as described in Example 62, wherein the tablet is a calcined tablet, wherein the calcination is preferably carried out in a gas atmosphere having a temperature in the range of 800°C to 1400°C, more preferably in the range of 875°C to 1275°C, more preferably in the range of 950°C to 1250°C, more preferably in the range of 1050°C to 1225°C, wherein the gas atmosphere more preferably contains oxygen, more preferably one or more of oxygen, air, or lean air, wherein the calcination is more preferably carried out for 0.5 to 20 h, more preferably 1 to 15 h, more preferably 2 to 10 h, more preferably 3 to 5 h.

[0185] 64. A method as described in Example 62 or 63, wherein the tablet has a side compression strength 1 (SCS1) of at least 366N, preferably at least 400N, more preferably in the range of 400 to 800N, more preferably in the range of 400 to 600N, more preferably in the range of 400 to 570N determined as described in Reference Example 4, and the molded body is more preferably a tablet with a four-hole cross-section and four grooves, wherein the four cylindrical sections are respectively located in the area between two grooves, wherein the side compression strength 1 is measured according to Reference Example 4 under the condition where the tablet stands on the two cylindrical sections on the sides of the groove.

[0186] 65. A method as described in any of Examples 62 to 64, wherein the tablet has a side compression strength 2 (SCS2) 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 determined as described in Reference Example 4, wherein the four cylindrical sections are respectively located in the area between the two grooves, wherein the side compression strength 2 is measured according to Reference Example 4 under the condition where the tablet stands on the cylindrical sections.

[0187] 66. A method as described in any of Examples 62 to 65, wherein the tablet has a lateral compression strength 3 (SCS3) 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 determined as described in Reference Example 4, wherein the four cylindrical segments are respectively located in the area between the two grooves, wherein the lateral compression strength 3 is preferably measured according to Reference Example 4 under the condition that the area of ​​the cylindrical segment is perpendicular to the direction of the force applied to the tablet.

[0188] 67. The method of any one of embodiments 1 to 7 and 16 to 4066, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials.

[0189] 68. A method as described in Example 67, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) contains 1 wt.-% or less, preferably 0.5 wt.-%, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, and more preferably 0.001 wt.-% or less of Ni and Co, calculated as corresponding elements and based on 100 wt.-% of the NH3 reforming catalyst C1.

[0190] 69. The method of embodiment 67 or 68, wherein the one or more carrier materials exhibit 20 m 2 / g or higher, 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, and more preferably 75 to 80 m 2 The BET surface area is preferably determined in accordance with ISO 9277:2010.

[0191] 70. The method of embodiment 67 or 68, wherein the one or more support materials exhibit a 20 m 2 / g or higher, preferably greater than 20 to 150m 2 / g, more preferably 21 to 100m 2 / g, more preferably 22 to 70m 2 / g, more preferably 23 to 50m 2 / g, more preferably 24 to 40m 2 / g, and more preferably 25 to 35m 2 The BET surface area is preferably determined in accordance with ISO 9277:2010.

[0192] 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, and more preferably 0.8 to 0.85 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0193] 72. The method of any one of embodiments 67 to 71, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) exhibits a relative humidity of 20 to 800 m / s.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, and more preferably 70 to 75m 2 The BET surface area is preferably determined in accordance with ISO 9277:2010.

[0194] 73. A method as described in any one of Embodiments 67 to 72, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (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, and more preferably 0.3 to 0.35 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0195] 74. A method as described in any of Examples 67 to 73, calculated as element and based on 100 wt.-% of Ru contained in the NH3 reforming catalyst C1 contained in the reactor provided in (i), 90 to 100 wt.-%, preferably 95 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of Ru is loaded on the one or more support materials contained in the catalyst.

[0196] 75. A method as described in any one of Examples 67 to 74, wherein Ru is loaded 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 preferably include Ru(NO)(NO3)3, wherein Ru(NO)(NO3)3 is more preferably used as the one or more ruthenium salts.

[0197] 76. The method of any one of embodiments 67 to 75, wherein the one or more support materials are selected from the group consisting of metal oxides, wherein the metals of the metal oxides are preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals and rare earth metals, including combinations of two or more thereof, more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd, including combinations of two or more thereof, more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca and La, including combinations of two or more thereof, And more preferably selected from the group consisting of: Al, Zr and Mg, including combinations of two or more thereof, wherein more preferably the one or more carrier materials include one or more metal oxides, the one or more metal oxides are selected from the group consisting of: Al2O3, ZrO2 and spinel, including mixtures of two or more thereof, preferably selected from the group consisting of: ZrO2 and spinel, including mixtures of two or more thereof, wherein more preferably the one or more carrier materials include ZrO2 and / or MgAl2O4, preferably ZrO2, wherein more preferably the one or more carrier materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0198] 77. A method as described in Example 76, wherein ZrO2 contains 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 phase, tetragonal phase and cubic phase of ZrO2, including mixtures of two or three thereof.

[0199] 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 oxides, more preferably substantially free of Ca and / or Mg, more preferably substantially free of Ca and Mg, and more preferably substantially free of alkaline earth metals.

[0200] 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, and more preferably substantially free of Al and Si.

[0201] 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, and more preferably substantially free of carbon.

[0202] 81. A method as described in any of Examples 67 to 80, wherein the NH3 reforming catalyst C1 contains Ru in an amount ranging from 0.1 to 15 wt.-%, preferably 1 to 10 wt.-%, more preferably 2 to 8 wt.-%, more preferably 3 to 6.5 wt.-%, more preferably 4 to 6 wt.-%, and more preferably 4.5 to 5.5 wt.-%, based on 100 wt.-% of the total amount of the one or more carrier materials.

[0203] 82. A method as described in any of Examples 67 to 81, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 consists of Ru and the one or more support materials.

[0204] 83. A method as described in any one of Examples 67 to 82, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) further comprises one or more alkali metal and / or alkaline earth metal hydroxides, wherein the one or more alkali metal hydroxides and / or alkaline earth metal hydroxides are loaded on the one or more Ru-loaded support materials, wherein these alkali metal hydroxides and / or alkaline earth metal hydroxides are preferably selected from the group consisting of: Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH and KOH, including mixtures of two or more thereof, more preferably selected from the group consisting of: Mg(OH)2, Ca(OH)2, LiOH, NaOH and KOH, including mixtures of two or more thereof, more preferably selected from the group consisting of: LiOH, NaOH and KOH, including mixtures of two or more thereof, wherein more preferably the catalyst further comprises KOH and / or LiOH, preferably KOH.

[0205] 84. A method as described in Example 83, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) contains the one or more alkali metal hydroxides in an amount ranging from 0.5 to 15 wt.-%, preferably 1 to 10 wt.-%, more preferably 2 to 8 wt.-%, more preferably 3 to 6.5 wt.-%, more preferably 4 to 6 wt.-%, and more preferably 4.5 to 5.5 wt.-%, based on 100 wt.-% of the total amount of the one or more carrier materials.

[0206] 85. A method as described in Example 83 or 84, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the NH3 reforming catalyst C1 contained in the reactor provided in (i) consists of Ru, the one or more alkali metal hydroxides and the one or more support materials.

[0207] 86. A method as described in any one of Embodiments 67 to 85, wherein the NH3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of a molded body and / or in the form of a powder, preferably in the form of a molded body, and more preferably in the form of an extrudate or a tablet.

[0208] 87. The method of embodiment 86, wherein the extrudates have a diameter ranging from 0.5 to 10 mm, preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and more preferably 2.5 to 3.5 mm.

[0209] 88. A method as described in Example 86 or 87, wherein the extrudates are separated and the NH3 reforming catalyst C1 contained in the reactor provided in (i) is in the form of extrudates of separate sieved portions 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, and more preferably 300 μm to 500 μm.

[0210] 89. The method of embodiment 88, wherein the tablets have a four-hole cross-section, preferably a four-hole cross-section and four grooves. BRIEF DESCRIPTION OF THE DRAWINGS

[0211] Figure 1 : Shows the results of NH3 reforming on a Ni-containing catalyst. NH3 conversion is represented by % on the ordinate, and temperature is represented by °C on the abscissa. Diamonds (◆) indicate measurement points of catalysts activated in a H2 gas atmosphere, and triangles (▲) indicate measurement points of catalysts activated in a NH3 gas atmosphere.

[0212] Figure 2 : A side view of an arrangement for determining lateral pressure strength 1 (SCS1) is shown on the left, a side view of an arrangement for determining lateral pressure strength 2 (SCS2) is shown in the middle, and a side view of an arrangement for determining lateral pressure strength 3 (SCS3) is shown on the right.

[0213] Figure 3: shows a TPR graph of the passivated and partially reduced Ni-containing catalyst prepared according to Reference Example 6. On the abscissa, the temperature is represented in ° C., and on the ordinate, the intensity of the TCD signal is represented in arbitrary units.

[0214] Figure 4 : shows a TPR graph of a fully oxidized Ni-containing catalyst prepared according to Reference Example 7. On the abscissa, the temperature is represented in °C, and on the ordinate, the intensity of the TCD signal is represented in arbitrary units.

[0215] Figure 5 : shows a TPR graph of the Ni-containing catalyst prepared according to Reference Example 6 when analyzed after use in the test according to Example 9. On the abscissa, the temperature is represented in ° C., and on the ordinate, the intensity of the TCD signal is represented in arbitrary units.

[0216] Figure 6 : shows a TPR graph of the Ru-containing catalyst prepared according to Reference Example 8. On the abscissa, the temperature is represented in °C, and on the ordinate, the intensity of the TCD signal is represented in arbitrary units.

[0217] Experimental Section

[0218] The present invention is further illustrated by the following Reference Examples, Examples and Comparative Examples.

[0219] Reference Example 1: Determining Gas Stream Composition by FTIR

[0220] The gas stream composition, in particular the H2O content of the gas stream, was determined using Fourier transform infrared spectroscopy (FTIR). For this purpose, the device "IGS Analyzer" from Thermo Fisher Scientific was used, with the software "Omnic 9" being used for data evaluation.

[0221] Reference Example 2: Determination of X-ray Diffraction (XRD)

[0222] Powder X-ray diffraction (PXRD) data were collected using a diffractometer (D8 Advance II series, Bruker AXS GmbH) equipped with a LYNXEYE detector operated with a copper anode X-ray tube running at 40 kV and 40 mA. The geometry was Bragg-Brentano and air scattering was reduced using an air scattering shield.

[0223] Calculation of crystallinity: The crystallinity of the samples was determined using the software DIFFRAC.EVA provided by Bruker AXS, Karlsruhe, according to the method described on page 121 of the user manual. For the calculation, the default parameters were used.

[0224] Calculation of phase composition: The phase composition was calculated for the raw data using the modeling software DIFFRAC.TOPAS (DIFFRAC.TOPAS 6th edition, 2017 user manual, Bruker AXS, Karlsruhe). The diffraction pattern was simulated using the crystal structure of the determined phase, instrument parameters, and the grain size of the individual phases. In addition to the function modeling the background intensity, it was also fitted to the data.

[0225] For the case where oxidized or passivated NH3 reforming catalyst samples were analyzed, the samples were homogenized in a mortar and then pressed into a standard flat sample holder for Bragg-Brentano geometry data collection provided by Bruker AXS. The sample powder was compressed and flattened using a glass plate to achieve a flat surface. Data were collected from an angle range of 2° to 70° 2θ with a step size of 0.02° 2θ, while the variable divergence slit was set to an angle of 0.1°. The crystalline content describes the ratio of the intensity of the crystalline signal to the total scattered intensity. The passivation layer produces a fairly broad and almost amorphous signal in the XRD. This broad signal is very clearly different from the oxidized part of the fresh sample.

[0226] For the case where the reduced NH 3 reforming catalyst sample was analyzed, the sample was taken out of the reactor under an inert gas atmosphere and prepared for XRD analysis in a glove box under inert gas using a gas-tight sample carrier (e.g., a gas-tight sample holder or a sealed capillary).

[0227] Reference Example 3: Determination of Temperature Programmed Reduction (TPR)

[0228] use Autochem II performs temperature programmed reduction (TPR) measurements. As reducing gas mixture, 5% H2 in Ar was applied. Hydrogen consumption was monitored via a TCD detector and shown as reverse consumption. Therefore, hydrogen consumption is shown as a positive peak. The gas flow was adjusted to 50 ml / min. Hydrogen consumption was further integrated and given in μmol / g (catalyst) and was associated with a certain reduction event.

[0229] Reference Example 4: Determination of lateral pressure strength

[0230] Determine the lateral compression strength on the semi-automatic tablet testing system SotaxST-50WTDH. Measure the lateral compression strength at a constant speed of 0.05mm / s. The range of 0 to 800N can be tested. For each measurement, the direction of the sample is adjusted with a horizontal rotating table and fine adjustments are made manually. Further, several measurement parameters (if applicable) are adjusted, depending on the direction and characteristics of the sample, such as mass, height / thickness, diameter and rupture strength. The data obtained are evaluated with the scientific program q-doc prolab (version 4fsp2 (4.10)). Tablets with a four-hole cross-section are tested, in which three positions perpendicular to each other are detected, allowing the determination of lateral compression strength 1, lateral compression strength 2 and lateral compression strength 3. The relative standard deviation of compressive strength 1, 2 and 3 is 7.48%.

[0231] like Figure 2 As can be seen in the table, lateral compression strength 1 refers to the position of the tablet in the semi-automatic tablet testing system where the sample stands on two cylindrical sections on the sides of the groove on the rotating table, lateral compression strength 2 refers to the position where the sample stands on one cylindrical section on the rotating table, and lateral compression strength 3 refers to the position where the hole is parallel to the direction of the force applied to the sample during the test.

[0232] Reference Example 5: Determination of lateral pressure strength

[0233] The lateral compression strength was determined on a tablet testing system (Typ BZ2.5 / TS1S, Zwick). The lateral compression strength was measured using a punching tool. The lateral compression strength was recorded as soon as the sample broke. For each measurement, the orientation of the sample was adjusted manually on a horizontal platform. The punching tool was arranged to punch from above. Further, several measuring parameters were adjusted (if applicable), depending on the orientation and characteristics of the sample, such as mass, height / thickness, diameter and rupture strength. Tablets with a four-hole cross-section were tested, in which three positions perpendicular to each other were probed, allowing the determination of lateral compression strength 1, lateral compression strength 2 and lateral compression strength 3. Figure 2 As can be seen in the table, lateral compression strength 1 refers to the position of the tablet in the semi-automatic tablet testing system where the sample stands on two cylindrical sections on the sides of the groove on the rotating table, lateral compression strength 2 refers to the position where the sample stands on one cylindrical section on the rotating table, and lateral compression strength 3 refers to the position where the hole is parallel to the direction of the force applied to the sample during the test.

[0234] Reference Example 6: Preparation of a passivated partially reduced Ni-containing catalyst

[0235] A physical mixture of NiO (60 wt-%) and alumina powder is mixed with water and a binder (e.g., methylcellulose or bentonite) into an extrudable paste. The paste is extruded (1 / 8" diameter) and calcined at a moderate temperature below 300°C. The catalyst obtained is partially reduced and passivated under air. The partially reduced and passivated catalyst comprises a weight ratio of NiO to elemental Ni of 43:57, as determined according to Reference Example 2. The average crystallite size of Ni is 6.0 nm, and the average crystallite size of NiO is 2.5 nm.

[0236] The reduction of the passivation layer occurs at mild temperatures between 150°C and 220°C. The residual bulk NiO is reduced at higher temperatures between 400°C and 700°C.

[0237] The results of TPR are shown in Table 1 below, and TPR is plotted in Figure 3 middle.

[0238] Table 1: Results of TPR determined according to Reference Example 3.

[0239]

[0240] In addition, the Ni-containing catalyst was analyzed after use in the test according to Example 9. Since 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 in the following Table 2. Further, the used catalyst included a weight 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.

[0241] Table 2: Results of TPR determined according to Reference Example 3.

[0242]

[0243] As from Figure 5 The results shown in Table 2 are Figure 3 Compared with the results in Table 1, it can be concluded that 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 is applied shows a strong peak below 400°C, indicating that passivation of metallic Ni occurs when the catalyst is transferred from the reactor to the analysis.

[0244] Reference Example 7: Preparation of a fully oxidized Ni-containing catalyst

[0245] A Ni-containing NH 3 reforming catalyst was prepared according to the method described in Example E1 of WO 2013 / 068905 A1.

[0246] An aqueous solution of nickel nitrate (14 wt-% Ni concentration) was mixed with hydrotalcite and an appropriate amount of water to prepare an extrudable paste. The paste was extruded in the next step. The subsequent heat treatment of the obtained extrudate was the same as in Example 1 (Example E1 of WO 2013 / 068905A1).

[0247] The nickel content of the calcined extrudates was 15.5 wt-%, the magnesium content was 14.0 wt-% and the aluminum content was 29.5 wt-%.

[0248] In the TPR determined according to Reference Example 3, it was observed that the first reduction event of the fully oxidized Ni-containing catalyst started at 400° C. and continued to 1000° C. and above. The results of the TPR are shown in Table 3 below, and the TPR is plotted in Figure 4 middle.

[0249] Table 3: Results of TPR determined according to Reference Example 3.

[0250]

[0251] Reference Example 8: Preparation of Ru (5 wt.-%) and KOH (5 wt.-%; corresponding to 3.5 wt.-% K) supported on MgAl2O4 spinel

[0252] A hydrotalcite precursor (Pural MG30 from Sasol) was calcined at a temperature in the range of 850° C. to 980° C. and for a duration in the range of 1 to 3 h and then used as a support. 93 g of the support in the form of a shaped body was impregnated with 27 g of a Ru(NO)(NO3)3 solution (19.7 wt.-% Ru in solution). After drying at 180° C. for 4 h, the Ru-containing shaped body was impregnated with 5.105 g of K(OH). The resulting material was then dried at 120° C. for 2 h and calcined at 500° C. for 2 h under synthetic air consisting of 21 vol.-% O2 and 79 vol.-% N2.

[0253] The Ru-containing catalyst obtained was analyzed by TPR according to Reference Example 3. The results are shown in Figure 6 and Table 4 below.

[0254] Table 4: Results of TPR determined according to Reference Example 3.

[0255]

[0256] Example 9: NH3 reforming test

[0257] To illustrate the method of the present invention, a Ni-containing NH3 reforming catalyst in the form of an extrudate was prepared according to Reference Example 6. The catalyst was used in an NH3 reforming method. In one run, the catalyst was activated at a temperature of up to 400° C. at a heating rate of 2° C. / min at a pressure of 20 bar absolute. At 400° C., the temperature was maintained for 1 h. The activation scheme was carried out in a gas stream comprising NH3 with a partial pressure of 1 bar absolute and diluted with Ar, followed by NH3 reforming. For comparison reasons, the NH3 reforming method was carried out in another run using the catalyst, which was conventionally activated in a gas stream comprising 5 volume-% H2 in Ar.

[0258] In order to achieve the desired NH3 reforming conditions, a specific temperature regime is applied.

[0259] Then with 4000h -1 NH3 reforming was carried out in a gas stream consisting essentially of NH3 with a gas hourly space velocity (GHSV) of 1.5 GHSV, wherein the NH3 reforming was carried out at a pressure of 40 bar absolute. 5000 ppm volume fraction of H2O was added to the pure NH3 feed stream before feeding into the reactor. The catalyst was tested between 350°C and 550°C. The activity of the catalyst activated in different gas atmospheres was determined. The results are shown in Table 5 below.

[0260] Table 5: NH3 conversion results of Ni-based catalysts activated in different reducing atmospheres.

[0261]

[0262] As can be concluded from the results of NH3 reforming, it was found that activating the NH3 reforming catalyst in a gas stream containing NH3 is a method suitable for forming a very active catalyst and simplifies the activation and start-up sequence of a typical NH3 reforming process. Thus, it was found that activation under a gas stream containing NH3 was successful even at high pressure, and the NH3 reforming catalyst showed the same activity level as conventional activation.

[0263] Prior Art Cited:

[0264] -I. Lucentini et al., Ind. Eng. Chem. Res., 2021, 60, 18560-18611

[0265] -T.Le et al., Korean J.Chem.Eng., 2021, 38(6), 1087-1103

[0266] -Bell et al., Top Catal., 2016, 59, 1438-1457

[0267] -X.-K.Li et al., Journal of Catalysis, 2005, 236, 181-189

[0268] -H. Fang et al., ACS Catalysis, 2022, 12, 3938-3954

Claims

1. A method for NH3 reforming, the method comprising (i) providing a reactor containing an NH3 reforming catalyst C1, the NH3 reforming catalyst 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 comprising NH3; (iii) feeding F1 prepared according to (ii) into the reactor and contacting F1 with the NH3 reforming catalyst C1, wherein the reactor has a temperature of 100°C or higher; Obtaining a product gas stream P1 comprising H2O and an NH3 reforming catalyst C2; in Starting the feed according to (ii) at time t1; Wherein at time point t2, the molar ratio H2O(P1):H2O(F1) of H2O in the product gas stream P1 to H2O in the feed gas stream F1 is greater than 1:1, wherein the difference between t2 and t1 is in the range of 5 s to 10 days.

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

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

4. The method according to 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 a mixture of two or more thereof.

5. The method according to any one of claims 1 to 4, wherein: The feed gas stream F1 prepared according to (ii) comprises 0 to 0.5 vol-% H2.

6. The method according to any one of claims 1 to 5, wherein: The feed gas stream F1 prepared according to (ii) comprises 1 to 100 vol-% NH 3 .

7. The method according to any one of claims 1 to 6, wherein: The feed gas stream F1 prepared according to (ii) has an NH3 partial pressure in the range from 0.01 to 65 bar absolute.

8. The method according to any one of claims 1 to 7, wherein: The feed gas stream F1 prepared according to (ii) comprises 0 to 1 vol-% H2O.

9. The method according to any one of claims 1 to 8, wherein: 99 to 100 vol-% of the feed gas stream F1 prepared according to (ii) consists of NH3, H2, optionally H2O and optionally an inert gas, wherein the inert gas comprises one or more of Ar and N2.

10. The method according to any one of claims 1 to 9, wherein: According to (iii), the feed gas stream F1 prepared according to (ii) is fed into the reactor, the feed gas stream having a flow rate of 100 to 15,000 h -1 Gas hourly space velocity in the range.

11. The method according to any one of claims 1 to 10, wherein: The contacting according to (iii) is carried out at a pressure in the range of 1 to 65 bar absolute.

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

13. The method of any one of claims 1 to 12, further comprising (iv) preparing a feed gas stream F2 comprising NH3; (v) feeding the feed gas stream F2 prepared according to (iv) into the reactor and contacting the feed gas stream F2 with the NH3 reforming catalyst C2 obtained from (iii); (vi) removing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2.

14. The method of claim 13, wherein: The feed gas stream F2 prepared according to (iv) comprises 1 to 100 vol-% NH3.

15. The method according to claim 13 or 14, wherein: 99 to 100 vol-% of the feed gas stream F2 prepared according to (iv) consists of NH3, H2, optionally H2O and optionally an inert gas, wherein the inert gas comprises one or more of Ar and N2.

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