Ni-based catalysts for NH3 reforming applications

Abstract

The present invention relates to a catalyst comprising Ni, Ru, and a promoter metal M1, wherein the catalyst exhibits a Ru:Ni mass ratio in the range of 0.0001:1 to 0.5:1, the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, and mixtures of two or more thereof, and the catalyst further comprises one or more support materials on which Ni, Ru, and the promoter metal M1 are respectively supported. Furthermore, the present invention relates to a method for preparing the catalyst comprising Ni, Ru, and the promoter metal M1, and to the catalyst obtainable according to said method, and to a method for reforming ammonia using the catalyst of the present invention.

Description

[Technical Field]

[0001] The present invention relates to an ammonia reforming catalyst, a method for producing the same, and an ammonia reforming method using the same. [Background technology]

[0002] NH3 is considered the energy vector of the future, capable of chemically storing significant amounts of H2. Therefore, sustainable NH3 may be produced on a large scale from renewable energy sources. On-site reforming of NH3 where H2 is required (see Equation 1 below) may be the final step to close the renewable electricity-based H2 value chain. (1) 2NH3 ⇔ N2 + 3H2 I. Lucentini et al., Eng. Chem. Res. 2021, 60, 18560-18611 and T. Le et al., Korean J. Chem. Eng., 2021, 38(6), 1087-1103 each provide an overview of catalysts used for the decomposition of ammonia.

[0003] X.-K. Li et al., Journal of Catalysis, 2005, 236, 181-189, is particularly concerned with the decomposition of ammonia over Ni and Ru catalysts.

[0004] Bell et al., Top Catal., 2016, 59, 1438-1457, relates to the decomposition of ammonia using non-noble metal catalysts, where catalysts containing mainly Co and Ni are discussed. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] I. Lucentini et al., Eng. Chem. Res. 2021, 60, 18560-18611 [Non-patent document 2] T. Le et al., Korean J. Chem. Eng., 2021, 38(6), 1087-1103 [Non-patent document 3] X.-K. Li et al., Journal of Catalysis, 2005, 236, 181-189 [Non-patent document 4] Bell et al., Top Catal., 2016, 59, 1438-1457 Summary of the Invention [Problem to be solved by the invention]

[0006] Despite the development of numerous catalysts for ammonia decomposition, there remains a need for more effective catalysts, particularly those that can convert ammonia to hydrogen and nitrogen at low temperatures and decompose ammonia with high efficiency. [Means for solving the problem]

[0007] Therefore, it has been surprisingly discovered that the use of relatively small amounts of Ru in a K-promoted Ni-based catalyst can provide unexpectedly high conversions at low temperatures when used for ammonia decomposition. In particular, a very strong synergistic effect between Ru, Ni, and K has been unexpectedly discovered in the catalytic decomposition of ammonia, and only small amounts of Ru are required to obtain a highly efficient catalyst.

[0008] Accordingly, the present invention relates to a catalyst comprising Ni, Ru, and a promoter metal M1, wherein the catalyst exhibits a Ru:Ni mass ratio in the range of 0.0001:1 to 0.5:1, the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, and mixtures of two or more thereof, and the catalyst further comprises one or more support materials on which the Ni, Ru, and the promoter metal M1 are respectively supported. [Brief explanation of the drawings]

[0009] [Figure 1]Figure 1 shows the results of NH reforming over the extruded catalysts at a GHSV of 4,000 h, p(NH) = 20 bara, and 5,000 ppm-vol HO co-feed. The extruded catalysts were tested at temperatures between 300 and 650 °C. Results are shown for 15 wt. % Ni supported on MgO / Al2O3 mixed oxide without (Catalyst 2) and with 0.1 and 0.5 wt. % Ru promoter (Catalyst 3), as well as for the latter Ru-promoted catalyst further promoted with 3.5 wt. % K according to Example 4 of the present invention. [Figure 2] Figure 2 shows the results of NH reforming using the tableted catalysts at a GHSV of 4,000 h-1, p(NH3) = 30 bara, and 5,000 ppm-vol HO cofeed. The tableted catalysts were tested at temperatures between 300 and 650 °C. Results are shown for 15 wt. % Ni supported on MgO / Al2O3 mixed oxide without (Catalyst 2) and with 0.5 wt. % Ru promoter (Catalyst 3), as well as for the latter Ru-promoted catalyst further promoted with 3.5 wt. % K according to Example 4 of the present invention. For comparison, a catalyst with 15 wt. % Ni and 3.5 wt. % KOH without Ru (Catalyst 5) is also shown. [Figure 3] Figure 3 shows the XRD pattern of the catalyst of Example 2, where it is clearly seen that the Mg,Al-spinel structure forms part of the support material. The diffractogram contains the line pattern of MgAl2O4 (lines without asterisks) and the line pattern of cubic MgNiO2 (lines with asterisks). DETAILED DESCRIPTION OF THE INVENTION

[0010] Preferably, the catalyst exhibits a Ru:Ni mass ratio in the range of 0.001:1 to 0.9:1, more preferably 0.005:1 to 0.5:1, more preferably 0.01:1 to 0.1:1, more preferably 0.02:1 to 0.05:1, more preferably 0.025:1 to 0.035:1.

[0011] Preferably, the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, and mixtures of two or more thereof, more preferably from the group consisting of Li, K, Na, Cs, and mixtures of two or more thereof, more preferably from the group consisting of Li, K, Na, and mixtures of two or more thereof, more preferably the promoter metal M1 is Li, K, or Li and K, more preferably the promoter metal M1 is K, more preferably the promoter metal M1 consists of Li, K, or Li and K, more preferably the promoter metal M1 consists of K.

[0012] Preferably, the catalyst exhibits a Ni:M1 atomic ratio in the range of 0.1:1 to 30:1, more preferably 0.5:1 to 20:1, more preferably 1:1 to 15:1, more preferably 1.5:1 to 10:1, more preferably 2:1 to 6:1, more preferably 2.5:1 to 4:1, more preferably 2.7:1 to 3.5:1, more preferably 2.9:1 to 3:1.

[0013] Preferably, the one or more support materials are selected from the group consisting of metal oxides, wherein the metal of the metal oxide is more preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, rare earth metals, and combinations of two or more thereof, more preferably from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, Nd, and combinations of two or more thereof, more preferably from the group consisting of Al, Ti, Zr, Mg, Ca, La, and combinations of two or more thereof, more preferably from the group consisting of Al, Zr, Mg, and combinations of two or more thereof, and more preferably Alternatively, the one or more support materials comprise one or more metal oxides selected from the group consisting of Al2O3, ZrO2, spinel, and mixtures of two or more thereof, preferably from the group consisting of ZrO2, spinel, and mixtures of two or more thereof, more preferably from the group consisting of ZrO2, NiMgO2, MgAl2O4, and mixtures of two or more thereof; more preferably, the one or more support materials comprise MgAl2O4, preferably NiMgO2 and MgAl2O4; more preferably, the one or more support materials consist of MgAl2O4, or NiMgO2 and MgAl2O4, preferably NiMgO2 and MgAl2O4.

[0014] Preferably, based on 100% by mass of Ni and Ru contained in the catalyst, 90% by mass to 100% by mass of Ni and Ru calculated as each element is supported on one or more support materials contained in the catalyst, more preferably 95% by mass to 100% by mass, more preferably 99% by mass to 100% by mass, more preferably 99.5% by mass to 100% by mass, and more preferably 99.9% by mass to 100% by mass.

[0015] Preferably, based on 100% by mass of Ni, Ru, and promoter metal M1 contained in the catalyst, 90% by mass to 100% by mass, more preferably 95% by mass to 100% by mass, more preferably 99% by mass to 100% by mass, more preferably 99.5% by mass to 100% by mass, and more preferably 99.9% by mass to 100% by mass of Ni, Ru, and promoter metal M1, calculated as each element, are supported on one or more support materials contained in the catalyst.

[0016] Preferably, the catalyst contains Ni in an amount in the range of 1 to 75 mass %, more preferably 3 to 60 mass %, more preferably 5 to 40 mass %, more preferably 10 to 25 mass %, more preferably 12 to 18 mass %, more preferably 14 to 16 mass %, calculated as the element based on 100 mass % of the catalyst.

[0017] Preferably, the catalyst contains Ru in an amount in the range of 0.01 to 5 mass %, more preferably 0.05 to 2.5 mass %, more preferably 0.1 to 1.5 mass %, more preferably 0.2 to 1 mass %, more preferably 0.3 to 0.8 mass %, more preferably 0.4 to 0.6 mass %, calculated as the element, based on 100 mass % of the catalyst.

[0018] Preferably, the catalyst comprises the promoter metal M1 in an amount in the range of 0.05 to 25% by mass, more preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, more preferably 2 to 5% by mass, more preferably 3 to 4% by mass, calculated as the element, based on 100% by mass of the catalyst.

[0019] Preferably, 95 to 100% by mass of the catalyst consists of Ni, Ru, a promoter metal M1, and one or more support materials, and Ni, Ru, and the promoter metal M1 may each be present as an element, an oxide, and / or a salt, more preferably 97 to 100% by mass, more preferably 98 to 100% by mass, more preferably 99 to 100% by mass, more preferably 99.5 to 100% by mass, more preferably 99.9 to 100% by mass.

[0020] Preferably, the catalyst contains one or more promoter metals M1 as hydroxides, bicarbonates and / or carbonates, more preferably as hydroxides and / or bicarbonates, more preferably as hydroxides, and more preferably the promoter metal M1 is contained in the catalyst as its hydroxide salt.

[0021] Preferably, Ru is supported on one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, more preferably wherein the one or more ruthenium salts comprise Ru(NO)(NO3)3, and more preferably Ru(NO)(NO3)3 is employed as the one or more ruthenium salts.

[0022] Preferably, the catalyst is in the form of moldings, extrudates and / or powders, more preferably in the form of moldings or extrudates, more preferably in the form of moldings.

[0023] When the catalyst is in the form of extrudates, the extrudates preferably have a diameter in the range of 0.5 to 10 mm, more preferably 1 to 7 mm, even more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, even more preferably 2.5 to 3.5 mm.

[0024] When the catalyst is in the form of a molding, the molding preferably has a diameter in the range of 1 to 20 mm, more preferably 1 to 15 mm.

[0025] When the catalyst is in the form of a molding, it is preferred that the molding has a quadrilateral shape. In the sense of this patent application, the term quadrilateral preferably refers to the shape as depicted in Figure 1 of WO 2020 / 157202 A1.

[0026] The present invention also relates to a method for preparing a catalyst comprising Ni, Ru and a promoter metal M1, preferably a catalyst comprising Ni, Ru and a promoter metal M1 according to any one of the specific preferred embodiments of the present invention, wherein the method comprises the following steps: (1) preparing a mixture comprising one or more Ni sources, one or more support materials and / or one or more precursors thereof, and water; (2) molding the mixture obtained in step (1); (3) firing the molded body obtained in step (2); (4) impregnating the calcined compact obtained in step (3) with an aqueous solution of one or more Ru salts; (5) firing the impregnated compact obtained in step (4); (6) impregnating the fired compact obtained in step (5) with an aqueous solution of one or more salts of a promoter metal M1, wherein the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, and mixtures of two or more thereof; (7) firing the impregnated molded body obtained in step (6); Includes:

[0027] In step (1), it is preferred that the one or more Ni sources comprise one or more Ni salts, wherein the anion of the one or more Ni salts is more preferably selected from the group consisting of halide, carbonate, hydrogencarbonate, sulfate, hydrogensulfate, hydroxide, nitrate, phosphate, hydrogenphosphate, dihydrogenphosphate, acetate, and a combination of two or more thereof, more preferably from the group consisting of chloride, bromide, fluoride, hydrogencarbonate, hydrogensulfate, nitrate, dihydrogenphosphate, acetate, and a combination of two or more thereof, more preferably from the group consisting of chloride, fluoride, nitrate, acetate, and a combination of two or more thereof; More preferably, the anion of the one or more Ni salts is chloride and / or nitrate, preferably nitrate, more preferably the one or more Ni sources comprises nickel(II) nitrate, more preferably the one or more Ni sources is nickel(II) nitrate.

[0028] In step (1), when the one or more Ni sources comprise one or more Ni salts, the one or more Ni sources are preferably provided as an aqueous solution of one or more nickel salts.

[0029] In step (1), 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 more preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, rare earth metals, and combinations of two or more thereof, more preferably from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, Nd, and combinations of two or more thereof, more preferably from the group consisting of Al, Ti, Zr, Mg, Ca, La, and combinations of two or more thereof, more preferably from the group consisting of Al, Zr, Mg, and combinations of two or more thereof. More preferably, the one or more support materials comprise one or more metal oxides selected from the group consisting of Al2O3, ZrO2, spinel, and mixtures of two or more thereof, preferably from the group consisting of ZrO2, spinel, and mixtures of two or more thereof, more preferably from the group consisting of ZrO2, NiMgO2, MgAl2O4, and mixtures of two or more thereof; more preferably, the one or more support materials comprise MgAl2O4, preferably NiMgO2 and MgAl2O4; more preferably, the one or more support materials consist of MgAl2O4, or NiMgO2 and MgAl2O4, preferably NiMgO2 and MgAl2O4.

[0030] In step (1), it is preferred that the one or more precursors of the one or more support materials comprise hydrotalcite, and more preferably the one or more precursors of the one or more support materials are hydrotalcite.

[0031] Preferably, step (1) comprises preparing a mixture comprising one or more Ni sources, one or more precursors of one or more support materials, and water; more preferably, step (1) consists of preparing a mixture comprising one or more Ni sources, one or more precursors of one or more support materials, and water.

[0032] Preferably, in step (2), shaping is achieved by molding or extruding the mixture obtained in step (1), more preferably by extrusion.

[0033] The calcination in step (3) is carried out at a temperature in the range of preferably 500 to 1,150°C, more preferably 700 to 1,100°C, more preferably 850 to 1,050°C, more preferably 950 to 1,050°C.

[0034] The calcination in step (3) is preferably carried out for a duration in the range of 0.5 to 9 hours, more preferably 1.5 to 6 hours, and more preferably 2 to 3 hours.

[0035] In step (4), the anion of the one or more Ru salts is preferably selected from the group consisting of halide, carbonate, hydrogencarbonate, sulfate, hydrogensulfate, hydroxide, nitrate, phosphate, hydrogenphosphate, dihydrogenphosphate, acetate, and combinations of two or more thereof, more preferably from the group consisting of chloride, bromide, fluoride, hydrogencarbonate, hydrogensulfate, nitrate, dihydrogenphosphate, acetate, and combinations of two or more thereof, more preferably from the group consisting of chloride, fluoride, nitrate, acetate, and combinations of two or more thereof; more preferably, the anion of the one or more Ru salts is chloride and / or nitrate, preferably nitrate; More preferably, the one or more Ru salts comprise Ru(NO)(NO3)3, and more preferably, the one or more Ru salts is Ru(NO)(NO3)3.

[0036] The impregnation in steps (4) and (6), independently of each other, is preferably accomplished by incipient wetness.

[0037] The firing in steps (5) and (7) is carried out independently at a temperature in the range of preferably 100 to 800°C, more preferably 350 to 700°C, more preferably 400 to 600°C, more preferably 450 to 550°C.

[0038] The calcinations in steps (5) and (7) are carried out independently of each other for a duration in the range of preferably 1 to 9 hours, more preferably 1.5 to 6 hours, more preferably 2 to 3 hours.

[0039] Preferably, in step (6), the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, and combinations of two or more thereof, preferably from the group consisting of Li, K, Na, Cs, and combinations of two or more thereof, more preferably from the group consisting of Li, K, Na, and combinations of two or more thereof, more preferably the promoter metal M1 is Li, K, or Li and K, more preferably the promoter metal M1 is K, more preferably the promoter metal M1 consists of Li, K, or Li and K, more preferably the promoter metal M1 consists of K.

[0040] Preferably, in step (6), the one or more salts of the promoter metal M1 are selected from the group consisting of hydroxides, carboxylates, carbonates, and combinations of two or more thereof; more preferably, the one or more salts of the promoter metal M1 are hydroxides and / or carboxylates, preferably hydroxides; more preferably, the one or more salts of the promoter metal M1 in step (6) are hydroxides.

[0041] The present invention also relates to a catalyst comprising Ni, Ru and a promoter metal M1, which is obtained or obtainable according to a method according to any one of the particular preferred embodiments of the method of the present invention, preferably according to any one of the particular preferred embodiments of the present invention.

[0042] The present invention also relates to a method for producing a method for manufacturing a semiconductor device, comprising the steps of: (i) providing a reactor containing a catalyst according to any one of the particular preferred embodiments of the present invention; (ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in step (ii) into the reactor provided in step (i) to contact the feed gas stream with the catalyst; (iv) removing an effluent gas stream comprising H2 and N2 from the reactor; The present invention relates to a method for reforming ammonia, comprising:

[0043] The contacting in step (iii) is preferably carried out at a pressure in the range of 1 to 100 bara, more preferably 10 to 75 bara, more preferably 15 to 40 bara, more preferably 18 to 35 bara, more preferably 20 to 28 bara, more preferably 20 to 25 bara.

[0044] The contact in step (iii) is carried out at a temperature in the range of 300 to 1,100°C, more preferably 450 to 1,000°C, preferably 500 to 900°C, more preferably 500 to 800°C, more preferably 500 to 600°C.

[0045] The feed gas stream prepared in step (ii) preferably comprises 1 to 100% by volume of NH3, more preferably 3 to 99.99% by volume, more preferably 5 to 99.95% by volume, more preferably 10 to 99.9% by volume, more preferably 20 to 99.8% by volume, more preferably 30 to 99.7% by volume, more preferably 40 to 99.6% by volume, more preferably 50 to 99.5% by volume.

[0046] The feed gas stream prepared in step (ii) preferably comprises 0-50 vol. % N2, more preferably 0.01-30 vol. %, more preferably 0.03-15 vol. %, more preferably 0.05-5 vol. %, more preferably 0.1-1 vol. %, more preferably 0.12-0.5 vol. %, more preferably 0.14-0.16 vol. % N2.

[0047] The feed gas stream prepared in step (ii) preferably comprises 0-75 vol% H, more preferably 0-60 vol%, more preferably 0-50 vol%, more preferably 0-40 vol%, more preferably 0-35 vol%, more preferably 0-30 vol% H.

[0048] The feed gas stream prepared in step (ii) preferably comprises 100 to 50,000 ppmv, more preferably 200 to 30,000 ppmv, more preferably 500 to 25,000 ppmv, more preferably 1,000 to 20,000 ppmv, more preferably 3,000 to 15,000 ppmv, more preferably 5,000 to 10,000 ppmv of HO.

[0049] The total amount of NH3, N2 and H2 contained in the feed gas stream prepared in step (ii) is preferably in the range of 90 to 100% by mass, preferably 95 to 99.95% by volume, more preferably 98 to 99.9% by volume, more preferably 99 to 99.85% by volume, more preferably 99.7 to 99.8% by volume.

[0050] The feed stream is preferably 500 to 40,000 h -1 , more preferably 700 to 20,000 h -1 , more preferably 800 to 16,000 h -1 , more preferably 900 to 10,000 hours -1 , more preferably 1,000 to 8,000 hours -1 The gas is fed to the reactor at a gas hourly space velocity in the range of 0.1 to 1.0.

[0051] After step (i) and before step (iii), the catalyst contained in the reactor provided in step (i) is reduced, preferably in an atmosphere comprising hydrogen and / or NH3, more preferably hydrogen.

[0052] If, after step (i) and before step (iii), the catalyst contained in the reactor provided in step (i) is reduced in an atmosphere comprising hydrogen and / or NH3, the reduction is preferably carried out at a temperature in the range of 450 to 1050°C, more preferably 500 to 950°C, more preferably 600 to 920°C, more preferably 600 to 890°C, more preferably 600 to 870°C, more preferably 600 to 700°C.

[0053] When the catalyst contained in the reactor provided in step (i) is reduced in an atmosphere containing hydrogen and / or NH3 after step (i) and before step (iii), the reduction is carried out in an atmosphere containing preferably 1 to 99 vol%, more preferably 3 to 90 vol%, more preferably 5 to 80 vol%, more preferably 6 to 50 vol%, more preferably 7 to 30 vol%, more preferably 8 to 20 vol%, more preferably 9 to 15 vol% H2. Furthermore, independently therefrom, the atmosphere preferably contains 1 to 99 vol%, more preferably 5 to 95 vol%, more preferably 10 to 90 vol%, more preferably 30 to 70 vol%, more preferably 45 to 55 vol% of an inert gas.

[0054] When the atmosphere contains 1 to 99% by volume of an inert gas, the inert gas preferably contains one or more gases selected from the group consisting of a rare gas, CO2, and nitrogen gas, more preferably from the group consisting of He, Ar, Ne, N2, and CO2, more preferably the inert gas contains CO2, N2, or CO2 and N2, more preferably the inert gas contains N2, and more preferably the inert gas is N2.

[0055] According to the present invention, preferably the process of the present invention is for the reforming of ammonia and hydrocarbons, wherein the feed gas stream prepared in step (ii) further comprises one or more hydrocarbons, and one or more of CO and HO, and the effluent gas stream removed in step (iv) further comprises CO.

[0056] Where the process of the present invention is for the reforming of ammonia and hydrocarbons, preferably the feed gas stream prepared in step (ii) further comprises CO and one or more hydrocarbons, and more preferably the feed gas stream comprises no more than 5% by volume of HO, more preferably no more than 3% by volume, more preferably no more than 1% by volume, more preferably no more than 0.5% by volume, more preferably no more than 0.1% by volume, more preferably no more than 0.05% by volume, more preferably no more than 0.01% by volume of HO.

[0057] Where the process of the invention is for the reforming of ammonia and hydrocarbons, it is instead preferred that the feed gas stream prepared in step (ii) further comprises HO and one or more hydrocarbons, wherein the feed gas stream preferably comprises 5% by volume or less of CO, more preferably 3% by volume or less, even more preferably 1% by volume or less, more preferably 0.5% by volume or less, even more preferably 0.1% by volume or less, more preferably 0.05% by volume or less, even more preferably 0.01% by volume or less of CO.

[0058] Where the process of the present invention is for the reforming of ammonia and hydrocarbons, also alternatively preferably, the feed gas stream prepared in step (ii) further comprises CO2, H2O and one or more hydrocarbons.

[0059] When the process of the present invention is for reforming ammonia and hydrocarbons, the one or more hydrocarbons are preferably selected from the group consisting of alkanes and mixtures thereof, more preferably C1 to C10 alkanes and mixtures thereof, more preferably C3 to C9 alkanes and mixtures thereof, more preferably C4 to C8 alkanes and mixtures thereof, more preferably C5 to C7 alkanes and mixtures thereof, more preferably C6 alkanes and mixtures thereof.

[0060] Furthermore, independently, the contacting is preferably carried out at a pressure in the range of greater than 10 bara to 50 bara, more preferably 12 to 45 bara, more preferably 15 to 40 bara, more preferably 18 to 35 bara, more preferably 20 to 30 bara.

[0061] Furthermore, independently thereof, the feed gas stream prepared in step (ii) preferably comprises 0.1 to 75 vol. %, more preferably 0.3 to 60 vol. %, more preferably 0.5 to 50 vol. %, more preferably 0.8 to 40 vol. %, more preferably 1 to 30 vol. % NH3.

[0062] Furthermore, independently thereof, the feed gas stream prepared in step (ii) preferably comprises 10 to 70% by volume, more preferably 12 to 60% by volume, more preferably 15 to 50% by volume of one or more hydrocarbons.

[0063] Furthermore, independently thereof, the feed gas stream prepared in step (ii) preferably comprises 0 to 75 vol.%, more preferably 0.5 to 70 vol.%, more preferably 1 to 68 vol.%, more preferably 3 to 66 vol.%, more preferably 5 to 64 vol.%, more preferably 8 to 62 vol.%, more preferably 10 to 60 vol.% HO.

[0064] Furthermore, independently thereof, the feed gas stream prepared in step (ii) preferably comprises 0 to 60% by volume CO2, more preferably 1 to 58% by volume, more preferably 3 to 56% by volume, more preferably 5 to 54% by volume, more preferably 8 to 52% by volume, more preferably 10 to 50% by volume CO2.

[0065] Additionally, independently, the feed stream preferably exhibits a HO:C molar ratio of HO to carbon contained in the one or more hydrocarbons in the range of from 0 to 4, more preferably from 0.1 to 3, more preferably from 0.3 to 2.5, more preferably from 0.4 to 2, more preferably from 0.5 to 1.6.

[0066] Additionally, independently, the feed stream preferably exhibits a CO2:C molar ratio of CO2 to carbon contained in the one or more hydrocarbons in the range of 0 to 4, more preferably 0.1 to 3, more preferably 0.2 to 2, more preferably 0.3 to 1.5.

[0067] Furthermore, independently thereof, the feed stream preferably exhibits an NH3:C molar ratio of NH3 to carbon contained in the one or more hydrocarbons in the range of 0 to 5, more preferably 0 to 4, more preferably 0.001 to 3, more preferably 0.005 to 2, more preferably 0.01 to 1.

[0068] Furthermore, independently, the feed stream is preferably between 500 and 16,000 h -1, more preferably 700 to 14,000 h -1 , more preferably 800 to 12,000 h -1 , more preferably 900 to 10,000 hours -1 , more preferably 1,000 to 8,000 hours -1 The gas is fed to the reactor at a gas hourly space velocity in the range of 0.1 to 1.0.

[0069] Furthermore, independently thereof, it is preferred that the effluent gas stream removed in step (iv) further comprises CO2.

[0070] Furthermore, independently thereof, it is preferred that the effluent gas stream removed in step (iv) exhibits a stoichiometric number R in the range of 0.1 to 3, where R is defined according to formula (I): [ka] (where c(H2), c(CO2), and c(CO) represent the molar concentrations of H2, CO2, and CO, respectively, in the effluent gas stream.) The stoichiometric number R is preferably in the range of 1 to 2.5, more preferably 1.3 to 2.2. Alternatively, preferably, R>2.

[0071] Furthermore, independently, it is preferred that the effluent gas stream removed in step (iv) exhibits a H2:CO molar ratio >2.

[0072] When the effluent gas stream removed in step (iv) exhibits a H2:CO molar ratio >2, the stoichiometric number R is preferably in the range of 0.5 to 3, more preferably 1 to 2.2, more preferably 1.3 to 1.7.

[0073] When the process of the present invention is for the reforming of ammonia and hydrocarbons, the effluent gas stream removed in step (iv) preferably comprises 10 to 90% by volume H, more preferably 20 to 80% by volume, more preferably 30 to 70% by volume, more preferably 40 to 65% by volume, more preferably 45 to 60% by volume H.

[0074] Furthermore, independently thereto, the effluent gas stream removed in step (iv) preferably comprises 1 to 70% by volume CO, more preferably 3 to 50% by volume CO, more preferably 5 to 40% by volume CO, more preferably 10 to 35% by volume CO, more preferably 15 to 30% by volume CO.

[0075] Furthermore, independently thereto, the effluent gas stream removed in step (iv) preferably comprises 1 to 50% by volume CO2, more preferably 3 to 45% by volume, more preferably 5 to 40% by volume, more preferably 8 to 35% by volume, more preferably 10 to 30% by volume, more preferably 12 to 25% by volume CO2.

[0076] According to the process for reforming ammonia of the present invention, the effluent gas stream removed in step (iv) is preferably employed in a process for producing methanol, a process for producing dimethyl ether, or a process for producing methanol and dimethyl ether.

[0077] Further, preferably, the effluent gas stream removed in step (iv) is employed in a process for the production of hydrocarbons by a Fischer-Tropsch process.

[0078] Furthermore, the effluent gas stream removed in step (iv) is preferably employed in a process for the production of an alcohol, more preferably an alkanol, more preferably a C1-C10 alkanol, more preferably a C2-C8 alkanol, more preferably a C2-C6 alkanol, more preferably a C2-C4 alkanol, more preferably a C2 alkanol, more preferably ethanol.

[0079] Furthermore, preferably, in the initial stage of the process, the feed gas stream prepared in step (ii) and fed to the reactor in step (iii) further comprises H2 to reduce the catalyst. Preferably, the feed gas stream prepared in step (ii) and fed to the reactor in step (iii) further comprises 0.5 to 80 vol.%, preferably 1 to 70 vol.%, more preferably 2 to 60 vol.%, more preferably 5 to 50 vol.%, more preferably 15 to 40 vol.% H2.

[0080] Finally, the present invention also relates to the use of a catalyst comprising Ni, Ru and a promoter metal M1 according to any one of the particular preferred embodiments of the present invention in the reforming of NH3 to N2 and H2.

[0081] The present invention is further described by the following series of embodiments and combinations of embodiments resulting from the indicated dependencies and backward references. In particular, it should be noted that in each instance where a range of embodiments is mentioned, such as in the context of terms such as "the composite oxide according to any one of embodiments 1 to 4," all embodiments within this range are expressly disclosed to those skilled in the art, i.e., this expression is understood by those skilled in the art to be synonymous with "the composite oxide according to any one of embodiments 1, 2, 3, and 4." Furthermore, it is expressly intended that the following series of embodiments represent a conveniently organized part of the description directed to general and preferred aspects of the present invention, rather than a series of claims determining the scope of protection.

[0082] 1. A catalyst comprising Ni, Ru, and a promoter metal M1, the catalyst exhibiting a Ru:Ni mass ratio in the range of 0.0001:1 to 0.5:1, the promoter metal M1 being selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, and mixtures of two or more thereof, and further comprising one or more support materials on which the Ni, Ru, and promoter metal M1 are respectively supported.

[0083] 2. The catalyst according to embodiment 1, wherein the catalyst exhibits a Ru:Ni mass ratio in the range of 0.001:1 to 0.9:1, preferably 0.005:1 to 0.5:1, more preferably 0.01:1 to 0.1:1, more preferably 0.02:1 to 0.05:1, more preferably 0.025:1 to 0.035:1.

[0084] 3. The catalyst of embodiment 1 or 2, wherein the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, and mixtures of two or more thereof, preferably from the group consisting of Li, K, Na, Cs, and mixtures of two or more thereof, more preferably from the group consisting of Li, K, Na, and mixtures of two or more thereof; more preferably, the promoter metal M1 is Li, K, or Li and K; more preferably, the promoter metal M1 is K; more preferably, the promoter metal M1 consists of Li, K, or Li and K; more preferably, the promoter metal M1 consists of K.

[0085] 4. The catalyst according to any one of embodiments 1 to 3, wherein the catalyst exhibits a Ni:M1 atomic ratio in the range of 0.1:1 to 30:1, preferably 0.5:1 to 20:1, more preferably 1:1 to 15:1, more preferably 1.5:1 to 10:1, more preferably 2:1 to 6:1, more preferably 2.5:1 to 4:1, more preferably 2.7:1 to 3.5:1, more preferably 2.9:1 to 3:1.

[0086] 5. The one or more support materials are selected from the group consisting of metal oxides, and the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, rare earth metals, and combinations of two or more thereof, more preferably from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, Nd, and combinations of two or more thereof, more preferably from the group consisting of Al, Ti, Zr, Mg, Ca, La, and combinations of two or more thereof, more preferably from the group consisting of Al, Zr, Mg, and combinations of two or more thereof, and more preferably from the group consisting of 5. The catalyst of any one of the preceding claims, comprising one or more metal oxides selected from the group consisting of Al2O3, ZrO2, spinel, and mixtures of two or more thereof, preferably from the group consisting of ZrO2, spinel, and mixtures of two or more thereof, more preferably from the group consisting of ZrO2, NiMgO2, MgAl2O4, and mixtures of two or more thereof; more preferably the one or more support materials comprise MgAl2O4, preferably NiMgO2 and MgAl2O4; more preferably the one or more support materials consist of MgAl2O4, or NiMgO2 and MgAl2O4, preferably NiMgO2 and MgAl2O4.

[0087] 6. The catalyst according to any one of embodiments 1 to 5, wherein 90% by mass to 100% by mass, more preferably 95% by mass to 100% by mass, more preferably 99% by mass to 100% by mass, more preferably 99.5% by mass to 100% by mass, and more preferably 99.9% by mass to 100% by mass of Ni and Ru, calculated as each element, based on 100% by mass of Ni and Ru contained in the catalyst, is supported on the one or more support materials contained in the catalyst.

[0088] 7. The catalyst according to any one of embodiments 1 to 6, wherein 90% to 100% by weight, preferably 95% to 100% by weight, more preferably 99% to 100% by weight, more preferably 99.5% to 100% by weight, more preferably 99.9% to 100% by weight, of Ni, Ru, and promoter metal M1, calculated as each element, based on 100% by weight of Ni, Ru, and promoter metal M1 contained in the catalyst, is supported on the one or more support materials contained in the catalyst.

[0089] 8. The catalyst of any one of embodiments 1 to 7, comprising Ni in an amount ranging from 1 to 75% by weight, preferably from 3 to 60% by weight, more preferably from 5 to 40% by weight, more preferably from 10 to 25% by weight, more preferably from 12 to 18% by weight, more preferably from 14 to 16% by weight, calculated as the element, based on 100% by weight of the catalyst.

[0090] 9. The catalyst of any one of embodiments 1 to 8, comprising Ru in an amount ranging from 0.01 to 5% by weight, preferably from 0.05 to 2.5% by weight, more preferably from 0.1 to 1.5% by weight, more preferably from 0.2 to 1% by weight, more preferably from 0.3 to 0.8% by weight, more preferably from 0.4 to 0.6% by weight, calculated as the element, based on 100% by weight of the catalyst.

[0091] 10. The catalyst according to any one of the preceding embodiments, comprising the promoter metal M1 in an amount ranging from 0.05 to 25% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, more preferably from 1 to 8% by weight, more preferably from 2 to 5% by weight, more preferably from 3 to 4% by weight, calculated as the element, based on 100% by weight of the catalyst.

[0092] 11. The catalyst according to any one of the preceding embodiments, wherein 95 to 100% by weight of the catalyst consists of Ni, Ru, the promoter metal M1, and one or more support materials, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight, and wherein Ni, Ru, and the promoter metal M1 can each be present as an element, an oxide, and / or a salt.

[0093] 12. The catalyst according to any one of the preceding embodiments, wherein the catalyst comprises the one or more promoter metals M1 as hydroxides, bicarbonates and / or carbonates, preferably as hydroxides and / or bicarbonates, more preferably as hydroxides, and more preferably the promoter metals M1 are contained in the catalyst as their hydroxide salts.

[0094] 13. The catalyst according to any one of the preceding embodiments, wherein Ru is supported on the one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, preferably the one or more ruthenium salts comprise Ru(NO)(NO3)3, more preferably Ru(NO)(NO3)3 is employed as the one or more ruthenium salts.

[0095] 14. The catalyst according to any one of the preceding embodiments, in the form of extrusions, extrudates, and / or powders, preferably in the form of extrusions or extrudates, more preferably in the form of extrusions.

[0096] 15. The catalyst of embodiment 14, wherein the extrudates have a diameter in the range of 0.5 to 10 mm, preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and even more preferably 2.5 to 3.5 mm.

[0097] 16. The catalyst of embodiment 14, wherein the moldings have a diameter in the range of 1 to 20 mm, preferably in the range of 1 to 15 mm.

[0098] 17. The catalyst of embodiment 14 or 16, wherein the molding is quadrilateral in shape.

[0099] 18. A method for preparing a catalyst comprising Ni, Ru, and a promoter metal M1, preferably a catalyst comprising Ni, Ru, and a promoter metal M1 according to any one of embodiments 1 to 17, comprising the following steps: (1) preparing a mixture comprising one or more Ni sources, one or more support materials and / or one or more precursors thereof, and water; (2) molding the mixture obtained in step (1); (3) firing the molded body obtained in step (2); (4) impregnating the calcined compact obtained in step (3) with an aqueous solution of one or more Ru salts; (5) firing the impregnated compact obtained in step (4); (6) impregnating the fired compact obtained in step (5) with an aqueous solution of one or more salts of a promoter metal M1, wherein the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, and mixtures of two or more thereof; (7) firing the impregnated molded body obtained in step (6); A method comprising:

[0100] 19. In step (1), the one or more Ni sources comprise one or more Ni salts, and the anions of the one or more Ni salts are preferably selected from the group consisting of halides, carbonates, hydrogen carbonates, sulfates, hydrogen sulfates, hydroxides, nitrates, phosphates, hydrogen phosphates, dihydrogen phosphates, acetates, and combinations of two or more thereof, more preferably from the group consisting of chlorides, bromides, fluorides, hydrogen carbonates, hydrogen sulfates, nitrates, dihydrogen phosphates, acetates, and combinations of two or more thereof, more preferably from the group consisting of chlorides, fluorides, nitrates, acetates, and combinations of two or more thereof; 19. The method of embodiment 18, wherein the anion of the one or more Ni salts is chloride and / or nitrate, preferably nitrate; more preferably, the one or more Ni sources comprise nickel(II) nitrate; more preferably, the one or more Ni sources are nickel(II) nitrate.

[0101] 20. The method of embodiment 19, wherein the one or more Ni sources are provided as an aqueous solution of one or more nickel salts.

[0102] 21. In step (1), the one or more support materials are selected from the group consisting of metal oxides, and the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, rare earth metals, and combinations of two or more thereof, more preferably from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, Nd, and combinations of two or more thereof, more preferably from the group consisting of Al, Ti, Zr, Mg, Ca, La, and combinations of two or more thereof, more preferably from the group consisting of Al, Zr, Mg, and combinations of two or more thereof, and more preferably from the group consisting of Al, Zr, Mg, and combinations of two or more thereof, and the one or more support materials are more preferably 21. The method of any one of embodiments 18 to 20, wherein the material comprises one or more metal oxides selected from the group consisting of Al2O3, ZrO2, spinel, and mixtures of two or more thereof, preferably from the group consisting of ZrO2, spinel, and mixtures of two or more thereof, more preferably from the group consisting of ZrO2, NiMgO2, MgAl2O4, and mixtures of two or more thereof; more preferably the one or more support materials comprise MgAl2O4, preferably NiMgO2 and MgAl2O4; more preferably the one or more support materials consist of MgAl2O4, or NiMgO2 and MgAl2O4, preferably NiMgO2 and MgAl2O4.

[0103] 22. The method of any one of embodiments 18 to 21, wherein in step (1), the one or more precursors of the one or more support materials comprise hydrotalcite, preferably the one or more precursors of the one or more support materials are hydrotalcite.

[0104] 23. The method of any one of embodiments 18 to 22, wherein step (1) comprises preparing a mixture comprising one or more Ni sources, one or more precursors of one or more support materials, and water, preferably wherein step (1) consists of preparing a mixture comprising one or more Ni sources, one or more precursors of one or more support materials, and water.

[0105] 24. The method of any one of embodiments 18 to 23, wherein in step (2), shaping is achieved by molding or extruding the mixture obtained in step (1), preferably by extrusion.

[0106] 25. The method of any one of embodiments 18 to 24, wherein the calcination in step (3) is carried out at a temperature in the range of 500 to 1,150°C, preferably 700 to 1,100°C, more preferably 850 to 1,050°C, more preferably 950 to 1,050°C.

[0107] 26. The method of any one of embodiments 18 to 25, wherein the calcination in step (3) is carried out for a duration in the range of 0.5 to 9 hours, preferably 1.5 to 6 hours, more preferably 2 to 3 hours.

[0108] 27. In step (4), the anion of the one or more Ru salts is selected from the group consisting of halide, carbonate, hydrogencarbonate, sulfate, hydrogensulfate, hydroxide, nitrate, phosphate, hydrogenphosphate, dihydrogenphosphate, acetate, and combinations of two or more thereof, preferably chloride, bromide, fluoride, hydrogencarbonate, hydrogensulfate, nitrate, dihydrogenphosphate, acetate, and combinations of two or more thereof, more preferably chloride, fluoride, nitrate, acetate, and combinations of two or more thereof, more preferably the anion of the one or more Ru salts is chloride and / or nitrate, preferably nitrate; 27. The method of any one of embodiments 18 to 26, wherein the one or more Ru salts comprise Ru(NO)(NO3)3, and more preferably, the one or more Ru salts are Ru(NO)(NO3)3.

[0109] 28. The method of any one of embodiments 18 to 27, wherein the impregnation in steps (4) and (6), independently of each other, is achieved by incipient wetness.

[0110] 29. The method of any one of embodiments 18 to 28, wherein the calcinations in steps (5) and (7) are carried out independently of each other at temperatures in the range of 100 to 800°C, preferably 350 to 700°C, more preferably 400 to 600°C, more preferably 450 to 550°C.

[0111] 30. The method of any one of embodiments 18 to 29, wherein the calcinations in steps (5) and (7) are carried out, independently of each other, for a duration ranging from 1 to 9 hours, preferably from 1.5 to 6 hours, more preferably from 2 to 3 hours.

[0112] 31. The method of any one of embodiments 18 to 30, wherein in step (6), the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, and combinations of two or more thereof, preferably from the group consisting of Li, K, Na, Cs, and combinations of two or more thereof, more preferably from the group consisting of Li, K, Na, and combinations of two or more thereof, more preferably the promoter metal M1 is Li, K, or Li and K, more preferably the promoter metal M1 is K, more preferably the promoter metal M1 consists of Li, K, or Li and K, more preferably the promoter metal M1 consists of K.

[0113] 32. The method of any one of embodiments 18 to 31, wherein in step (6), the one or more salts of the promoter metal M1 are selected from the group consisting of hydroxides, carboxylates, carbonates, and combinations of two or more thereof, preferably the one or more salts of the promoter metal M1 are hydroxides and / or carboxylates, preferably hydroxides, more preferably the one or more salts of the promoter metal M1 in step (6) are hydroxides.

[0114] 33. A catalyst comprising Ni, Ru, and a promoter metal M1, preferably as described in any one of embodiments 1 to 17, obtained or obtainable according to the method of any one of embodiments 18 to 32.

[0115] 34. The following steps: (i) providing a reactor containing the catalyst of any one of embodiments 1 to 17 and 33; (ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in step (ii) into the reactor provided in step (i) and contacting the feed gas stream with the catalyst; (iv) removing an effluent gas stream comprising H2 and N2 from the reactor; 1. A method for reforming ammonia, comprising:

[0116] 35. The method of embodiment 34, wherein the contacting in step (iii) is carried out at a pressure in the range of 1 to 100 bara, preferably 10 to 75 bara, more preferably 15 to 40 bara, more preferably 18 to 35 bara, more preferably 20 to 28 bara, more preferably 20 to 25 bara.

[0117] 36. The method of embodiment 34 or 35, wherein the contacting in step (iii) is carried out at a temperature in the range of 300 to 1,100°C, preferably 450 to 1,000°C, preferably 500 to 900°C, more preferably 500 to 800°C, more preferably 500 to 600°C.

[0118] 37. The method of any one of embodiments 34 to 36, wherein the feed gas stream prepared in step (ii) comprises 1 to 100% by volume of NH3, preferably 3 to 99.99% by volume, more preferably 5 to 99.95% by volume, more preferably 10 to 99.9% by volume, more preferably 20 to 99.8% by volume, more preferably 30 to 99.7% by volume, more preferably 40 to 99.6% by volume, more preferably 50 to 99.5% by volume.

[0119] 38. The method of any one of embodiments 34 to 37, wherein the feed gas stream prepared in step (ii) comprises 0 to 50 vol.%, preferably 0.01 to 30 vol.%, more preferably 0.03 to 15 vol.%, more preferably 0.05 to 5 vol.%, more preferably 0.1 to 1 vol.%, more preferably 0.12 to 0.5 vol.%, more preferably 0.14 to 0.16 vol.% N2.

[0120] 39. The method of any one of embodiments 34 to 38, wherein the feed gas stream prepared in step (ii) comprises 0 to 75 vol.%, preferably 0 to 60 vol.%, more preferably 0 to 50 vol.%, more preferably 0 to 40 vol.%, more preferably 0 to 35 vol.%, more preferably 0 to 30 vol.% H2.

[0121] 40. The method of any one of embodiments 34 to 39, wherein the feed gas stream prepared in step (ii) comprises 100 to 50,000 ppmv, preferably 200 to 30,000 ppmv, more preferably 500 to 25,000 ppmv, more preferably 1,000 to 20,000 ppmv, more preferably 3,000 to 15,000 ppmv, more preferably 5,000 to 10,000 ppmv of HO.

[0122] 41. The method of any one of embodiments 34 to 40, wherein the total amount of NH3, N2, and H2 contained in the feed gas stream prepared in step (ii) is in the range of 90 to 100% by mass, preferably 95 to 99.95% by volume, more preferably 98 to 99.9% by volume, more preferably 99 to 99.85% by volume, more preferably 99.7 to 99.8% by volume.

[0123] 42. The feed gas flow is 500 to 40,000 h -1 , preferably 700 to 20,000 h -1 , more preferably 800 to 16,000 h -1 , more preferably 900 to 10,000 hours -1 , more preferably 1,000 to 8,000 hours -1 42. The method of any one of embodiments 34 to 41, wherein the gas is fed to the reactor at a gas hourly space velocity in the range of

[0124] 43. The method of any one of embodiments 34 to 42, wherein after step (i) and before step (iii), the catalyst contained in the reactor provided in step (i) is reduced in an atmosphere comprising hydrogen and / or NH3, preferably hydrogen.

[0125] 44. The method of embodiment 43, wherein the reduction is carried out at a temperature in the range of 450 to 1050°C, preferably 500 to 950°C, more preferably 600 to 920°C, more preferably 600 to 890°C, more preferably 600 to 870°C, more preferably 600 to 700°C.

[0126] 45. The method of embodiment 43 or 44, wherein the reduction is carried out in an atmosphere containing 1 to 99% by volume of H2, preferably 3 to 90% by volume, more preferably 5 to 80% by volume, more preferably 6 to 50% by volume, more preferably 7 to 30% by volume, more preferably 8 to 20% by volume, more preferably 9 to 15% by volume.

[0127] 46. ​​The method of any one of embodiments 43 to 45, wherein the atmosphere comprises 1 to 99% by volume, preferably 5 to 95% by volume, more preferably 10 to 90% by volume, more preferably 30 to 70% by volume, more preferably 45 to 55% by volume of inert gas.

[0128] 47. The method of embodiment 46, wherein the inert gas comprises one or more gases selected from the group consisting of noble gases, CO2, and nitrogen gas, preferably from the group consisting of He, Ar, Ne, N2, and CO2; more preferably, the inert gas comprises CO2, N2, or CO2 and N2; more preferably, the inert gas comprises N2; more preferably, the inert gas is N2.

[0129] 48. The method of any one of embodiments 34 to 47, wherein the method is for the reforming of ammonia and hydrocarbons, and wherein the feed gas stream prepared in step (ii) further comprises one or more hydrocarbons, and one or more of CO2 and HO, and wherein the effluent gas stream removed in step (iv) further comprises CO.

[0130] 49. The method of embodiment 48, wherein the feed gas stream prepared in step (ii) further comprises CO2 and one or more hydrocarbons, preferably wherein the feed gas stream comprises 5% by volume or less of HO, more preferably 3% by volume or less, more preferably 1% by volume or less, more preferably 0.5% by volume or less, more preferably 0.1% by volume or less, more preferably 0.05% by volume or less, more preferably 0.01% by volume or less of HO.

[0131] 50. The method of embodiment 48, wherein the feed gas stream prepared in step (ii) further comprises H2O and one or more hydrocarbons, and wherein the feed gas stream preferably comprises 5% CO2 by volume or less, more preferably 3% by volume or less, even more preferably 1% by volume or less, more preferably 0.5% by volume or less, even more preferably 0.1% by volume or less, more preferably 0.05% by volume or less, even more preferably 0.01% by volume or less CO2.

[0132] 51. The method of embodiment 48, wherein the feed gas stream prepared in step (ii) further comprises CO2, H2O, and one or more hydrocarbons.

[0133] 52. The method of any one of embodiments 48 to 51, wherein the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof, preferably C1 to C10 alkanes and mixtures thereof, more preferably C3 to C9 alkanes and mixtures thereof, more preferably C4 to C8 alkanes and mixtures thereof, more preferably C5 to C7 alkanes and mixtures thereof, more preferably C6 alkanes and mixtures thereof.

[0134] 53. The method of any one of embodiments 48 to 52, wherein the contacting is carried out at a pressure in the range of more than 10 bara to 50 bara, preferably 12 to 45 bara, more preferably 15 to 40 bara, more preferably 18 to 35 bara, more preferably 20 to 30 bara.

[0135] 54. The method of any one of embodiments 48 to 53, wherein the feed gas stream prepared in step (ii) comprises 0.1 to 75 vol.%, preferably 0.3 to 60 vol.%, more preferably 0.5 to 50 vol.%, more preferably 0.8 to 40 vol.%, more preferably 1 to 30 vol.% NH3.

[0136] 55. The method of any one of embodiments 48 to 54, wherein the feed gas stream prepared in step (ii) comprises 10 to 70 vol.%, preferably 12 to 60 vol.%, more preferably 15 to 50 vol.% of one or more hydrocarbons.

[0137] 56. The method of any one of embodiments 48 to 55, wherein the feed gas stream prepared in step (ii) comprises 0 to 75% by volume, preferably 0.5 to 70% by volume, more preferably 1 to 68% by volume, more preferably 3 to 66% by volume, more preferably 5 to 64% by volume, more preferably 8 to 62% by volume, more preferably 10 to 60% by volume of HO.

[0138] 57. The method of any one of embodiments 48 to 56, wherein the feed gas stream prepared in step (ii) comprises 0 to 60% by volume CO2, preferably 1 to 58% by volume, more preferably 3 to 56% by volume, more preferably 5 to 54% by volume, more preferably 8 to 52% by volume, more preferably 10 to 50% by volume.

[0139] 58. The method of any one of embodiments 48 to 57, wherein the feed stream exhibits a HO:C molar ratio of HO to carbon contained in the one or more hydrocarbons in the range of 0 to 4, preferably 0.1 to 3, more preferably 0.3 to 2.5, more preferably 0.4 to 2, more preferably 0.5 to 1.6.

[0140] 59. The method of any one of embodiments 48 to 58, wherein the feed stream exhibits a CO2:C molar ratio of CO2 to carbon contained in the one or more hydrocarbons in the range of 0 to 4, preferably 0.1 to 3, more preferably 0.2 to 2, more preferably 0.3 to 1.5.

[0141] 60. The method of any one of embodiments 48 to 59, wherein the feed stream exhibits an NH3:C molar ratio of NH3 to carbon contained in the one or more hydrocarbons in the range of 0 to 5, preferably 0 to 4, more preferably 0.001 to 3, more preferably 0.005 to 2, more preferably 0.01 to 1.

[0142] 61. The supply stream is 500 to 16,000 h -1 , preferably 700 to 14,000 h -1 , more preferably 800 to 12,000 h -1 , more preferably 900 to 10,000 hours -1 , more preferably 1,000 to 8,000 hours -1 61. The method of any one of embodiments 48 to 60, wherein the gas is fed to the reactor at a gas hourly space velocity in the range of

[0143] 62. The method of any one of embodiments 48 to 61, wherein the effluent gas stream removed in step (iv) further comprises CO2.

[0144] 63. The effluent gas stream removed in step (iv) exhibits a stoichiometric number R in the range of 0.1 to 3, where R is defined according to formula (I): [ka] wherein c(H), c(CO), and c(CO) represent the molar concentrations of H, CO, and CO, respectively, in the effluent gas stream.

[0145] 64. The method according to embodiment 63, wherein the stoichiometric number R is in the range of 1 to 2.5, preferably 1.3 to 2.2.

[0146] 65. The method of embodiment 63, wherein R>2.

[0147] 66. The method of any one of embodiments 48 to 62 and 65, wherein the effluent gas stream removed in step (iv) exhibits a H2:CO molar ratio >2.

[0148] 67. The method of embodiment 63, wherein the stoichiometric number R is in the range of 0.5 to 3, preferably 1 to 2.2, more preferably 1.3 to 1.7.

[0149] 68. The method of any one of embodiments 48 to 67, wherein the effluent gas stream removed in step (iv) comprises 10 to 90% by volume H2, preferably 20 to 80% by volume, more preferably 30 to 70% by volume, more preferably 40 to 65% by volume, more preferably 45 to 60% by volume.

[0150] 69. The method of any one of embodiments 48 to 68, wherein the effluent gas stream removed in step (iv) comprises 1 to 70% by volume CO, preferably 3 to 50% by volume, more preferably 5 to 40% by volume, more preferably 10 to 35% by volume, more preferably 15 to 30% by volume.

[0151] 70. The method of any one of embodiments 48 to 69, wherein the effluent gas stream removed in step (iv) comprises 1 to 50% by volume CO2, preferably 3 to 45% by volume, more preferably 5 to 40% by volume, more preferably 8 to 35% by volume, more preferably 10 to 30% by volume, more preferably 12 to 25% by volume.

[0152] 71. The process of any one of embodiments 34 to 70, wherein the effluent gas stream removed in step (iv) is employed in a process for producing methanol, a process for producing dimethyl ether, or a process for producing methanol and dimethyl ether.

[0153] 72. The method of any one of embodiments 34 to 71, wherein the effluent gas stream removed in step (iv) is employed in a process for the production of hydrocarbons by a Fischer-Tropsch process.

[0154] 73. The method of any one of embodiments 34 to 72, wherein the effluent gas stream removed in step (iv) is employed in a process for the production of an alcohol, preferably an alkanol, more preferably a C1-C10 alkanol, more preferably a C2-C8 alkanol, more preferably a C2-C6 alkanol, more preferably a C2-C4 alkanol, more preferably a C2 alkanol, more preferably ethanol.

[0155] 74. The process of any one of embodiments 34 to 73, wherein, in an initial stage of the process, the feed gas stream prepared in step (ii) and fed to the reactor in step (iii) further comprises H2 to reduce the catalyst.

[0156] 75. The method of embodiment 74, wherein the feed gas stream prepared in step (ii) and fed to the reactor in step (iii) further comprises 0.5 to 80 vol.%, preferably 1 to 70 vol.%, more preferably 2 to 60 vol.%, more preferably 5 to 50 vol.%, more preferably 15 to 40 vol.% H2.

[0157] 76. Use of a catalyst comprising Ni, Ru and a promoter metal M1 according to any one of embodiments 1 to 17 or 33 in the reforming of NH3 to N2 and H2. [Example]

[0158] Experimental Section The present invention is further illustrated by the following examples.

[0159] Reference Example 1: Preparation of tableted Ni (15.5 wt%) catalyst supported on MgO / Al2O3 mixed oxide A Ni-containing catalyst was prepared according to the process described in Example E1 of WO 2013 / 068905 A1. In contrast to Example E1 of WO 2013 / 068905 A1, an aqueous nickel nitrate solution (Ni concentration 14% by weight) was used instead of ground nickel nitrate hexahydrate. The various components were mixed to form a paste, which was then extruded. After drying and low-temperature calcination, the extrudate was ground and sieved to a target fraction with a particle size of 200 to 900 μm.

[0160] The sieved powder was mixed with 2.8% by weight of graphite (Asbury Graphite 3160) and 5.5% by weight of cellulose (Arbocel BWW 40). The resulting mixture was compressed into a molded product with a four-hole cross section as shown in Figure 1 of WO 2020 / 157202 A. For sintering, the molded product was heated to a temperature of 1,030 to 1,050°C in an annealing furnace and held for 4 hours.

[0161] The sintered molded product had a nickel content of 15.5 mass %, a magnesium content of 14.0 mass %, and an aluminum content of 29.5 mass %.

[0162] Reference Example 2: Preparation of extruded Ni (15.0 wt%) catalyst supported on MgO / Al2O3 mixed oxide Regarding Reference Example 1, a Ni-containing catalyst was prepared based on the process described in Example E1 of WO 2013 / 068905 A1. The Ni-salt solution employed in Reference Example 1 was mixed with hydrotalcite and an appropriate amount of water to prepare an extrudable paste. This paste was then extruded in the next step. The resulting extrudates were subsequently heat-treated at a temperature between 850 and 1050°C.

[0163] The sintered extrudates had a nickel content of 15.0 wt %, a magnesium content of 14.0 wt %, and an aluminum content of 29.5 wt %.

[0164] Reference Example 3: Promotion of Ni catalysts of Examples 1 and 2 with Ru (0.1 and 0.5 wt%) The catalysts prepared in Examples 1 and 2 were impregnated with an aqueous solution of Ru(NO(NO3)3), respectively, based on the water absorption rate of the material. The Ru loadings were fixed at 0.1 and 0.5 mass%. The impregnated samples were then heat-treated to 500°C.

[0165] Example 4: Promotion of the Ni / Ru catalyst of Example 3 with K (3.5 wt%) The catalysts prepared in Example 3 were impregnated in KOH solution based on the water absorption rate of the materials. The KOH loading was fixed at 3.5 wt% (5 wt% KOH). The impregnated samples were then heat-treated up to 500°C.

[0166] Comparative Example 5: Promotion of the Ni catalyst of Example 1 with K (3.5 wt%) The catalyst prepared in Example 1 was impregnated in a KOH solution. The amount of KOH supported was fixed at 3.5% by mass (5% by mass KOH), and the impregnated sample was heated to 500°C.

[0167] Example 6: Catalytic testing of NH3 reforming under high pressure The catalysts of Examples 1 to 5 were activated at temperatures between 450 and 850°C under a reducing atmosphere of 5 to 50% by volume of H2 in an inert gas (Ar or N2). Catalytic NH3 reforming tests were carried out under conditions of ammonia partial pressure (p(NH3)) of 20 bar (see results in Table 1) and 30 bar (see results in Table 2). 5,000 vol.-ppm of H2O was added to the NH3 feed. Furthermore, the catalysts were heated for 4,000 h. -1 The GHSV was tested at 1000 kJ / s and the temperature was varied from 300 to 650°C. The conversion of NH3 as a function of temperature is shown in Figures 1 and 2 and Tables 1 and 2.

[0168] [Table 1]

[0169] Thus, as can be seen from the results obtained from testing each catalyst, shown in Table 1 and Figure 1, promoting the Ni-based catalyst of Example 2 with a relatively small amount of Ru already results in a significant improvement in ammonia conversion, and the catalyst of Example 3 can already achieve high conversion at lower temperatures. However, quite surprisingly, the additional addition of K as a promoter to the Ru-promoted Ni catalyst of Example 4 significantly improves ammonia conversion at low temperatures, achieving 50% ammonia conversion already at 490°C. Furthermore, the catalyst of the present invention according to Example 4 exhibits an ammonia conversion equivalent to equilibrium conversion at about 600°C, whereas the Ni catalyst of Example 2 exhibits only a conversion slightly above 60% at that temperature, and the conversion of the Ru-promoted Ni catalyst of Example 3 does not exceed 77%. Thus, it was quite unexpectedly discovered that the use of a relatively small amount of Ru in the K-promoted Ni-based catalyst results in unexpectedly high conversion at low temperatures when used for ammonia decomposition, where only a small amount of Ru is required to obtain a highly efficient catalyst.

[0170] [Table 2]

[0171] On the other hand, as can be seen from the results obtained from the testing of each catalyst shown in Table 2 and FIG. 2, comparable results were obtained for the tableted Ni catalyst of Reference Example 1 compared to the extruded Ni catalyst of Reference Example 2 shown in Table 1 and FIG. 1. The same applies to the tableted catalyst of Reference Example 3, which supported 0.5 wt. % Ru, and the tableted catalyst of the present invention of Example 4, which supported 0.5 wt. % Ru and 3.5 wt. % K. Table 2 and FIG. 2 also show the results obtained using the tableted Ni catalyst of Comparative Example 5, which supported only 3.5 wt. % K. As can be seen from these results, the Ni catalyst of the comparative example, which contained only K and no additional Ru, showed significantly inferior performance to the Ni catalyst of Reference Example 1. Therefore, it was completely unexpectedly discovered that adding a small amount of Ru to a catalyst containing Ni and K can produce a very strong synergistic effect, which is several tens of times greater than the improvement observed when the same small amount of Ru was added to a catalyst containing only Ni. Thus, it has been found quite surprisingly that the catalyst of the present invention exhibits a very strong synergistic effect between the Ni, Ru, and K components, which was by no means expected in view of the results obtained for catalysts containing only Ni, catalysts containing only Ni and Ru, and catalysts containing only Ni and K. This result is even more surprising in view of the fact that the performance of the catalyst containing only Ni and K is significantly worse than that of the catalyst containing only Ni.

[0172] References: - I. Lucentini et al., Eng. Chem. Res. 2021, 60, 18560-18611 - T.Le et al., Korean J.Chem.Eng.,2021,38(6),1087-1103 - Bell et al., Top Catal., 2016, 59, 1438-1457 - X.-K. Li et al., Journal of Catalysis, 2005, 236, 181-189

Claims

1. 1. A catalyst comprising Ni, Ru, and a promoter metal M1, the catalyst exhibiting a Ru:Ni mass ratio in the range of 0.0001:1 to 0.5:1, the promoter metal M1 being selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, and mixtures of two or more thereof, the catalyst further comprising one or more support materials on which the Ni, Ru, and promoter metal M1 are respectively supported.

2. Catalyst according to claim 1, exhibiting a Ni:M1 atomic ratio in the range of 0.1:1 to 30:

1.

3. 3. The catalyst according to claim 1, comprising Ni in an amount ranging from 1 to 75% by mass, calculated as the element, based on 100% by mass of the catalyst.

4. 4. The catalyst according to any one of claims 1 to 3, comprising Ru in an amount ranging from 0.01 to 5% by mass, calculated as the element, based on 100% by mass of the catalyst.

5. 5. A catalyst according to any one of claims 1 to 4, comprising the promoter metal M1 in an amount in the range of 0.05 to 25% by mass, calculated as the element, based on 100% by mass of the catalyst.

6. 6. The catalyst of claim 1, comprising the one or more promoter metals M1 as hydroxides, as bicarbonates and / or as carbonates.

7. 7. The catalyst according to any one of claims 1 to 6, in the form of moldings, extrudates and / or powders.

8. A method for preparing the catalyst according to any one of claims 1 to 7, comprising the following steps: (1) preparing a mixture comprising one or more Ni sources, one or more support materials and / or one or more precursors thereof, and water; (2) molding the mixture obtained in step (1); (3) firing the molded body obtained in step (2); (4) impregnating the fired compact obtained in step (3) with an aqueous solution of one or more Ru salts; (5) firing the impregnated compact obtained in step (4); (6) impregnating the fired compact obtained in step (5) with an aqueous solution of one or more salts of a promoter metal M1, wherein the promoter metal M1 is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, and mixtures of two or more thereof; (7) firing the impregnated molded body obtained in step (6); A method comprising:

9. The following process: (i) providing a reactor containing the catalyst of any one of claims 1 to 7; (ii) NH ３ preparing a feed gas stream comprising: (iii) feeding the feed gas stream prepared in step (ii) into the reactor provided in step (i) and contacting the feed gas stream with the catalyst; (iv) removing H from the reactor; ２ and N ２ removing an effluent gas stream comprising 1. A method for reforming ammonia, comprising:

10. 10. The method of claim 9, wherein the contacting in step (iii) is carried out at a temperature in the range of 300 to 1,100°C.

11. The feed gas stream prepared in step (ii) contains 100 to 50,000 ppmv H ２ 11. The method of claim 9 or 10, comprising:

12. NH contained in the feed gas stream prepared in step (ii) ３ , N ２ and H ２ The method according to any one of claims 9 to 11, wherein the total amount of is in the range of 90 to 100% by mass.

13. The feed gas flow is maintained for 500 to 40,000 h －１ 13. The method of any one of claims 9 to 12, wherein the gas is fed to the reactor at a gas hourly space velocity in the range of

14. After step (i) and before step (iii), the catalyst contained in the reactor provided in step (i) is ３ 14. The method according to claim 9, wherein the reduction is carried out in an atmosphere containing

15. NH ３ From N ２ and H ２ 8. Use of the catalyst according to any one of claims 1 to 7 in the reforming of

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