Low-temperature NH3 reforming under high pressure

Abstract

The present invention relates to a method for reforming ammonia, the method comprising the steps of: (i) providing a reactor containing a catalyst comprising Ru supported on one or more support materials, the one or more support materials being at least 20 μm in diameter; 2 / g or more BET surface area, the catalyst containing 1 wt. % or less Ni and Co; (ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in (ii) into a reactor and contacting the feed gas stream with a catalyst at a pressure greater than 10 bara and a temperature in the range of 200 to 750°C; (iv) withdrawing an effluent gas stream comprising H2 and N2 from the reactor. Includes.

Description

[Technical field]

[0001] The present invention relates to a method for reforming ammonia, and more particularly to a method for reforming ammonia using a Ru-containing catalyst at low temperature and high pressure. [Background technology]

[0002] NH3 is considered as the energy vector of the future, capable of storing large amounts of H2 chemically. Therefore, sustainable NH3 production from renewable energy sources is possible on a large scale. Reforming of NH3 (see equation 1 below) on-site where H2 is needed could be the final step to close the H2 value chain based on renewable electricity. (1) 2NH3⇔N2+3H2

[0003] The use of supported Ru catalysts has been described to promote the decomposition of ammonia into nitrogen and hydrogen. Thus, for example, K. Lamb et al., Int. J. of Hydrogen Energy 2019, 44, 3726-3736, study the kinetics of ammonia decomposition on Ru / Al2O3 promoted with LiOH, while A. Di Carlo et al., Int. J. of Hydrogen Energy 2014, 39, 808-814, study ammonia decomposition on commercial Ru / Al2O3 catalysts at different operating pressures and temperatures, where it should be noted that higher dissociation rates are achieved at lower pressures.

[0004] TALe et al., Korean J.Chem.Eng.2021,38(6),1087-1103, reported that CO x The development of ruthenium and nickel catalysts for free H2 production is described. However, the literature indicates that alkaline earth metal oxide supports, in particular basic supports such as MgO or neutral supports such as carbon nanotubes, may give better results than amphoteric supports such as Cr2O3 and TiO2 or acidic supports such as Al2O3, ZrO2, or SiO2.

[0005] M. Miyamoto et al., Int. J. of Hydrogen Energy 2018, 43, 730-738, relates to the addition of ZrO2 supports to increase their basicity with La and their use in reactions for the production of hydrogen. Similarly, B. Lorenzut et al., ChemCatChem 2010, 2, 1096-1106, disclose the use of lanthanum-stabilized zirconia and show that basic oxides may be more efficient as supports for Ru catalysts compared to acidic oxides. Z. Wang et al., Int. J. of Hydrogen Energy 2019, 44, 7300-7307, in part, relates to Ba-modified ZrO2 supports for Ru and their use for ammonia decomposition.

[0006] Ru supported on ZrO2 has also been used as a catalyst for other reasons, where WO 2015 / 086639 A2 relates to a Ru / ZrO2 catalyst applied in the hydrogenation of aromatic compounds, while WO 2018 / 046393 A1 relates to a Ru / ZrO2 catalyst applied in the hydrogenation of nitriles.

[0007] On the other hand, S.-F. Yin et al., Applied Catalysis B Environmental 2004, 48, 237-241, concern the use of carbon nanotubes (CNTs) as a support for Ru nanoparticles in the production of hydrogen by ammonia decomposition, where it is shown that the order of activity for the various supports is ranked as follows: Ru / CNTs>Ru / MgO>Ru / activated carbon>Ru / ZrO2≒Ru / Al2O3.

[0008] However, to obtain H2 directly at high pressures (10-50 bara), the NH3 reforming itself must also be carried out at these pressures. Therefore, there is still a need for improved, cost-efficient NH3 reforming processes that allow to directly supply H2 at the conditions required for further reactions.

[0009] In this regard, S.Sayas et al., Catal.Sci.Technol.2020,10,5027-5035, study high pressure ammonia decomposition on Ru-K / CaO catalysts at pressures up to 40 bar. In TALe et al., Korean J.Chem.Eng.2021,38(6),1087-1103, S.Sayas et al. teach that the nature of the support has been shown to have a strong influence on the catalytic performance of Ru-based catalysts, where the use of basic supports such as MgO and La2O3, neutral supports such as carbon nanotubes, and acidic supports such as Al2O3, among others, generally results in better catalytic properties. Summary of the Invention [Problem to be solved by the invention]

[0010] However, there remains a need for a highly effective method for the decomposition of ammonia at high pressure.Furthermore, there remains a need for a method for the decomposition of ammonia that is highly active at low temperatures, especially when used in applications requiring high pressure.In addition, there remains a need for a method using an ammonia decomposition catalyst that exhibits high hydrothermal resistance, especially when used under high pressure conditions, taking into account the water that may be present during the reaction, especially the small amount present in technical grade ammonia for stabilization. [Brief description of the drawings]

[0011] [Figure 1]Results are shown for NH3 reforming at GHSV of 2000 h-1, p(NH3)=30 bara and simultaneous feeding of 10,000 ppm by volume of H2O. The catalysts were tested at 350-650°C. Results are shown for 5 wt% ZrO2 supported Ru without (catalyst from example 1) and with 5 wt% KOH promoter (catalyst from example 2), as well as the results obtained with a Mg-Al-spinel support loaded with 2.5 wt% Ru and promoted with 4.5 wt% LiOH according to example 3. [Diagram 2] The results of NH3 reforming and simultaneous feeding of 5,000 ppm by volume of H2O for the catalyst according to Example 2 at a GHSV of 8000 h-1, p(NH3)=10 bara are shown. The catalyst was tested at 300-600 °C. [Diagram 3] 1 shows the XRD pattern of the catalyst of Example 3, in which the Mg, Al-spinel structure is clearly identified as the constituent support material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] It has now been unexpectedly discovered that a highly efficient method for the high pressure (>10 bar) decomposition of ammonia using low temperatures (200-750°C, preferably 200-650°C, more preferably 200-600°C) can further be used in the presence of small amounts of water, such as that present in technical grade ammonia.

[0013] The present invention therefore provides a method for reforming ammonia, comprising the steps of: (i) providing a reactor containing a catalyst comprising Ru and one or more support materials, wherein the Ru is supported on the one or more support materials, the one or more support materials being at least 20 μm in thickness; 2 / g or more, the BET surface area being preferably determined according to ISO 9277:2010, the catalyst containing no more than 1 wt. % Ni and Co, calculated as the respective elements, based on 100 wt. % of the catalyst; (ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in (ii) into the reactor provided in (i) and contacting the feed gas stream with a catalyst, the contacting being at a pressure greater than 10 bara and at a temperature in the range of 200 to 750° C.; (iv) withdrawing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2. The present invention relates to a method comprising the steps of:

[0014] Within the meaning of the present invention, the BET surface area of ​​one or more support materials refers to the BET surface area of ​​the one or more support materials that are not loaded with any elements and / or compounds. Furthermore, within the meaning of the present invention, when the catalyst comprises two or more support materials, the BET surface area refers to the respective BET surface area of ​​the one or more support materials, such that each of the two or more support materials exhibits a BET surface area within the range of surface areas defined in the present invention.

[0015] According to the present invention, the catalyst in (i) preferably contains substantially no Ni and Co.

[0016] Here, in (i), it is preferred that the catalyst contains 0.5 wt.% or less, 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, more preferably 0.001 wt.% or less of Ni and Co, calculated as the respective elements and based on 100 wt.% of the catalyst.

[0017] In particular, in (i), it is preferred that the reactor contains at most 1 wt.-% Ni and Co, calculated as the respective element and based on 100 wt.-% of the total content of the reactor, more preferably at most 0.5 wt.-% Ni and Co, more preferably at most 0.1 wt.-% Ni and Co, more preferably at most 0.05 wt.-% Ni and Co, more preferably at most 0.01 wt.-% Ni and Co, more preferably at most 0.005 wt.-% Ni and Co, more preferably at most 0.001 wt.-% Ni and Co, calculated as the respective element and based on 100 wt.-% of the total content of the reactor.

[0018] The following two preferred alternatives apply with respect to the BET surface area of ​​the support material(s).

[0019] According to a first alternative, in (i), the one or more support materials are 2 / g, more preferably 40 to 500m 2 / g, more preferably 50 to 300m 2 / g, more preferably 60 to 200m 2 / g, more preferably 70 to 100m 2 / g, more preferably 75 to 80m 2 It is preferred that the material exhibit a BET surface area in the range of 1 / g.

[0020] According to a second alternative, in (i), the one or more support materials have a thickness of more than 20 to 150 m 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, more preferably 25 to 35m 2 It is preferred that the material exhibit a BET surface area in the range of 1 / g.

[0021] In (i), it is preferred that the one or more support materials exhibit a pore volume in the range of 0.2-3 ml / g, more preferably 0.4-1.5 ml / g, more preferably 0.6-1 ml / g, more preferably 0.8-0.85 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0022] Within the meaning of the present invention, the pore volume of one or more support materials refers to the pore volume of the one or more support materials that is not loaded with any element and / or compound. Furthermore, within the meaning of the present invention, when the catalyst comprises two or more support materials, the pore volume refers to the pore volume of each of the one or more support materials, such that each of the two or more support materials exhibits a pore volume within the range of the pore volume defined in the present invention.

[0023] In (i), the catalyst is 20 to 800 m 2 / g, preferably 30 to 500m 2 / g, more preferably 40 to 300m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, more preferably 70 to 75m 2 / g, the BET surface area being preferably determined in accordance with ISO 9277:2010.

[0024] In (i), it is preferred that the catalyst exhibits a pore volume in the range of 0.1-2 ml / g, more preferably 0.15-1.2 ml / g, more preferably 0.2-0.8 ml / g, more preferably 0.25-0.5 ml / g, more preferably 0.3-0.35 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0025] In (i), it is preferred that 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 contained in the catalyst, calculated as element, is supported on one or more types of support materials contained in the catalyst.

[0026] In (i), it is preferred that Ru is supported on one or more support materials by impregnation techniques using an aqueous solution of one or more ruthenium salts, the one or more ruthenium salts preferably comprising Ru(NO)(NO3)3, more preferably Ru(NO)(NO3)3 is used as the one or more ruthenium salts.

[0027] In (i), 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 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 from the group consisting of Al, Ti, Zr, Mg, Ca, and La (including combinations of two or more thereof), more preferably Al, Zr and Mg (including combinations of two or more thereof); more preferably the one or more support materials comprise one or more metal oxides selected from the group consisting of Al2O3, ZrO2, and spinel (including mixtures of two or more thereof), preferably from the group consisting of ZrO2 and spinel (including mixtures of two or more thereof); more preferably the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2; more preferably the one or more support materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0028] In (i), when the one or more support materials comprise ZrO2, it is preferred that the ZrO2 comprises one or more crystalline phases and / or is amorphous, wherein the one or more crystalline phases of ZrO2 are selected from the group consisting of a monoclinic phase, a tetragonal phase, and a cubic phase of ZrO2 (including mixtures of two or three thereof).

[0029] In (i), 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, more preferably substantially free of alkaline earth metals.

[0030] In (i), it is preferred that the one or more support 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, more preferably substantially free of Al and Si.

[0031] In (i), it is preferred that the one or more support materials are substantially free of carbon nanotubes, more preferably substantially free of elemental carbon, more preferably substantially free of carbon.

[0032] Within the meaning of the present invention, the term "substantially free" as used in this patent application indicates that the corresponding element or compound is contained in the corresponding component in an amount of 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, based on 100% by weight of the corresponding component.

[0033] In (i), it is preferred that the catalyst comprises Ru in an amount in the range of 0.5 to 15 wt %, more preferably 1 to 10 wt %, more preferably 2 to 8 wt %, more preferably 3 to 6.5 wt %, more preferably 4 to 6 wt %, more preferably 4.5 to 5.5 wt %, based on 100 wt % of the total amount of the one or more support materials.

[0034] In (i), it is preferable that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst consists of Ru and one or more types of support materials.

[0035] In (i), it is preferred that the catalyst 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 support materials supporting Ru, wherein the alkali metal and / or alkaline earth metal hydroxides are preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH, and KOH (including mixtures of two or more thereof), more preferably from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH, and KOH (including mixtures of two or more thereof), more preferably from the group consisting of LiOH, NaOH, and KOH (including mixtures of two or more thereof), and more preferably the catalyst further comprises KOH and / or LiOH, preferably KOH.

[0036] When the catalyst further comprises one or more alkali metal hydroxides, it is preferred that the catalyst comprises the one or more alkali metal hydroxides in an amount in the range of 0.5 to 15 wt %, more preferably 1 to 10 wt %, more preferably 2 to 8 wt %, more preferably 3 to 6.5 wt %, more preferably 4 to 6 wt %, more preferably 4.5 to 5.5 wt %, based on 100 wt % of the total amount of the one or more support materials.

[0037] Furthermore, when the catalyst further contains one or more alkali metal hydroxides, it is preferable that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst consists of Ru, one or more alkali metal hydroxides, and one or more support materials.

[0038] In (i), it is preferred that the catalyst is in the form of mouldings and / or in powder form, more preferably in the form of mouldings, more preferably in the form of extrudates or tablets.

[0039] In (i), when the catalyst 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, more preferably 2.5 to 3.5 mm.

[0040] Furthermore, in (i), when the catalyst is in the form of an extrudate, it is preferred that the extrudate is a divided body and that the catalyst is in the form of an extrudate of a divided sieve fraction in the range of 50 μm to 2.5 mm, more preferably 100 μm to 1.5 mm, more preferably 200 μm to 1 mm, more preferably 250 to 700 μm, more preferably 300 to 500 μm.

[0041] In (i), when the catalyst is in the form of a tablet, it is preferred that the tablet has a four-hole cross section, more preferably a four-hole cross section and four grooves.

[0042] The contact is preferably carried out at a pressure in the range of 11-50 bara, more preferably 15-45 bara, more preferably 15-40 bara, more preferably 18-35 bara, more preferably 19-31 bara, more preferably 20-28 bara, more preferably 20-25 bara.

[0043] The contact is preferably carried out at a temperature in the range of 200 to 650°C, more preferably 250 to 600°C, more preferably 300 to 550°C, more preferably 350 to 520°C, more preferably 400 to 500°C, more preferably 430 to 470°C.

[0044] The feed gas stream prepared in (ii) preferably comprises 1-100 vol.% NH3, more preferably 3-99.99 vol.%, more preferably 5-99.95 vol.%, more preferably 10-99.9 vol.%, more preferably 15-99.9 vol.%, more preferably 20-99.8 vol.%, more preferably 30-99.7 vol.%, more preferably 40-99.6 vol.%, more preferably 50-99.5 vol.%.

[0045] It is preferred that the feed gas stream prepared in (ii) 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.%.

[0046] The feed gas stream prepared in (ii) preferably comprises 0-75 vol.% H, more preferably 0-60 vol.%, more preferably 0-50 vol.%, more preferably 0-40 vol.%, more preferably 0-35 vol.%, more preferably 0-30 vol.% H.

[0047] It is preferred that the feed gas stream prepared in (ii) comprises 100-50,000 ppmv, more preferably 200-30,000 ppmv, more preferably 500-25,000 ppmv, more preferably 500-20,000 ppmv, more preferably 500-15,000 ppmv, more preferably 750-15,000 ppmv, more preferably 1,000-11,000 ppmv, more preferably 1,000-10,000 ppmv, more preferably 2,000-8,000 ppmv, more preferably 3,000-7,500 ppmv, more preferably 4,500-7,000 ppmv, more preferably 5,000-6,500 ppmv of HO.

[0048] The total amount of NH3, N2, and H2 contained in the feed gas stream prepared in (ii) is preferably in the range of 90 to 100 wt%, more preferably 95 to 99.95 vol%, more preferably 98 to 99.9 vol%, more preferably 99 to 99.85 vol%, more preferably 99.7 to 99.8 vol%.

[0049] After (i) and before (iii), it is preferred that the catalyst contained in the reactor provided in (i) is reduced in an atmosphere comprising hydrogen.

[0050] If after (i) and before (iii), the catalyst contained in the reactor provided in (i) is reduced in an atmosphere comprising hydrogen, it is preferred that the reduction is carried out at a temperature in the range of 20-100°C, more preferably 24-50°C, more preferably 26-35°C, more preferably 28-32°C.

[0051] Furthermore, after (i) and before (iii), if the catalyst contained in the reactor provided in (i) is reduced in an atmosphere comprising hydrogen, it is preferred that the reduction is carried out in an atmosphere comprising 1-50 vol.%, more preferably 2-20 vol.%, more preferably 3-10 vol.%, more preferably 4-6 vol.% H2.

[0052] Furthermore, after (i) and before (iii), when the catalyst contained in the reactor provided in (i) is reduced in an atmosphere containing hydrogen, it is preferred that the atmosphere contains 50-99% by volume, more preferably 80-98% by volume, more preferably 90-97% by volume, more preferably 94-96% by volume of an inert gas. Furthermore, it is preferred that the inert gas contains one or more gases selected from the group consisting of rare gases, CO2, and nitrogen, more preferably He, Ar, Ne, and N2, CO2, more preferably the inert gas contains CO2, N2, or CO2 and N2, more preferably the inert gas contains N2, more preferably the inert gas is N2.

[0053] Preferably, the process is for the reforming of ammonia and hydrocarbons, and the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and the effluent gas stream withdrawn in (iv) further comprises CO.

[0054] The following three preferred alternatives apply with respect to the composition of the gas stream prepared in (ii) when the process is for the reforming of ammonia and hydrocarbons, where the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and the effluent gas stream withdrawn in (iv) further comprises CO.

[0055] According to a first alternative, it is preferred that the feed gas stream prepared in (ii) further comprises CO2 and one or more hydrocarbons, and that the feed gas stream comprises more preferably 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.

[0056] According to a second alternative, it is preferred that the feed gas stream prepared in (ii) further comprises HO and one or more hydrocarbons, and that the feed gas stream preferably comprises not more than 5% CO by volume, more preferably not more than 3% by volume, more preferably not more than 1% by volume, more preferably not more than 0.5% by volume, more preferably not more than 0.1% by volume, more preferably not more than 0.05% by volume, more preferably not more than 0.01% by volume of CO.

[0057] According to a third alternative, it is preferred that the feed gas stream prepared in (ii) further comprises CO2, H2O and one or more hydrocarbons.

[0058] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof, preferably C1-C10 alkanes and mixtures thereof, more preferably C3-C9 alkanes and mixtures thereof, more preferably C4-C8 alkanes and mixtures thereof, more preferably C5-C7 alkanes and mixtures thereof, more preferably C6 alkanes and mixtures thereof.

[0059] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the contacting is carried out at a pressure in the range of from greater than 10 to 50 bara, more preferably from 12 to 45 bara, more preferably from 15 to 40 bara, more preferably from 18 to 35 bara, more preferably from 20 to 30 bara.

[0060] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, the effluent gas stream withdrawn in (iv) further comprises CO, and the feed gas stream prepared in (ii) comprises 0.1-75% by volume of NH3, more preferably 0.3-60% by volume, more preferably 0.5-50% by volume, more preferably 0.8-40% by volume, more preferably 1-30% by volume.

[0061] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the feed gas stream prepared in (ii) comprises 10-70% by volume of one or more hydrocarbons, more preferably 12-60% by volume, more preferably 15-50% by volume.

[0062] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream extracted in (iv) further comprises CO, and that the feed gas stream prepared in (ii) comprises 0-75% by volume HO, more preferably 0.5-70% by volume, more preferably 1-68% by volume, more preferably 3-66% by volume, more preferably 5-64% by volume, more preferably 8-62% by volume, more preferably 10-60% by volume.

[0063] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream extracted in (iv) further comprises CO, and that the feed gas stream prepared in (ii) comprises 0-60% by volume CO2, more preferably 1-58% by volume, more preferably 3-56% by volume, more preferably 5-54% by volume, more preferably 8-52% by volume, more preferably 10-50% by volume.

[0064] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the feed stream exhibits a HO:C molar ratio of HO to carbon contained in the one or more hydrocarbons in the range 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.

[0065] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, the feed stream exhibiting a CO2:C molar ratio of CO2 to carbon contained in the one or more hydrocarbons in the range from 0 to 4, more preferably from 0.1 to 3, more preferably from 0.2 to 2, more preferably from 0.3 to 1.5.

[0066] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the feed stream exhibits an NH3:C molar ratio, NH3 to carbon contained in the one or more hydrocarbons, in the range from 0 to 5, more preferably from 0 to 4, more preferably from 0.001 to 3, more preferably from 0.005 to 2, more preferably from 0.01 to 1.

[0067] Supply flow is 500~20,000h -1 , more preferably 500 to 16,000 hours -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 , more preferably 3,000 to 5,000 hours -1 It is preferred that the gas be fed to the reactor at a gas hourly space velocity in the range of

[0068] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream extracted in (iv) further comprises CO, and that the effluent gas stream extracted in (iv) further comprises CO2.

[0069] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the effluent gas stream withdrawn in (iv) exhibits a H2:CO molar ratio greater than 2.

[0070] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the effluent gas stream withdrawn in (iv) exhibits a stoichiometric coefficient R in the range of 0.1 to 3, where R is represented by the formula (I):

number

[0071] The following three alternatives apply with respect to the stoichiometric coefficient R of the effluent gas stream withdrawn in (iv):

[0072] According to a first alternative, it is preferred that the effluent gas stream extracted in (iv) exhibits a stoichiometric coefficient R in the range from 0.1 to 3, where R is defined according to formula (I) and it is preferred that the stoichiometric coefficient R is in the range from 1 to 2.5, more preferably from 1.3 to 2.2.

[0073] According to a second alternative, it is preferred that the effluent gas stream withdrawn in (iv) exhibits a stoichiometric coefficient R>2. Furthermore, according to a second alternative, it is preferred that the effluent gas stream withdrawn in (iv) exhibits a H2:CO molar ratio greater than 2.

[0074] According to a third alternative, it is preferred that the stoichiometric coefficient R is in the range of 0.5 to 3, preferably 1 to 2.2, more preferably 1.3 to 1.7.

[0075] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the effluent gas stream withdrawn in (iv) comprises 10-90% by volume H2, more preferably 20-80% by volume, more preferably 30-70% by volume, more preferably 40-65% by volume, more preferably 45-60% by volume.

[0076] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the effluent gas stream withdrawn in (iv) comprises 1 to 70% by volume CO, more 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.

[0077] Furthermore, when the process is for the reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and that the effluent gas stream withdrawn in (iv) further comprises CO, and that the effluent gas stream withdrawn in (iv) 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.

[0078] The effluent gas stream withdrawn in (iv) is preferably used in a process for the production of methanol, a process for the production of dimethyl ether, or a process for the production of methanol and dimethyl ether.

[0079] The effluent gas stream withdrawn in (iv) is preferably used in a hydrocarbon production process, more preferably according to a Fischer-Tropsch process.

[0080] The effluent gas stream withdrawn in (iv) is preferably used 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.

[0081] In the initial stages of the process, it is preferred that the feed gas stream prepared in (ii) and fed to the reactor in (iii) further comprises H2 for reducing the catalyst.

[0082] In the initial stages of the process, when the feed gas stream prepared in (ii) and fed to the reactor in (iii) further comprises H2 for reducing the catalyst, it is preferred that the feed gas stream prepared in (ii) and fed to the reactor in (iii) further comprises 0.5 to 80 vol. % H2, more preferably 1 to 70 vol. %, more preferably 2 to 60 vol. %, more preferably 5 to 50 vol. %, more preferably 15 to 40 vol. % H2.

[0083] The present invention is further illustrated by the following set of embodiments and combinations of embodiments, which are derived from the indicated dependencies and back references. In particular, it should be noted that in each instance where a range of embodiments is mentioned in conjunction with terms such as "the method according to any one of embodiments 1 to 4", it means that all embodiments within this range are expressly disclosed to those skilled in the art, i.e., the usage of this term should be understood by those skilled in the art to be equivalent to "the method according to any one of embodiments 1, 2, 3 and 4". Furthermore, it should be expressly noted that the following set of embodiments represents a preferred construction of the present specification, which is directed to the general and preferred aspects of the present invention, rather than a set of claims defining the scope of protection.

[0084] 1. A method for reforming ammonia, comprising: (i) providing a reactor containing a catalyst comprising Ru and one or more support materials, wherein the Ru is supported on the one or more support materials, the one or more support materials being at least 20 μm in thickness; 2 / g or more, the BET surface area being preferably determined according to ISO 9277:2010, the catalyst containing no more than 1 wt. % Ni and Co, calculated as the respective elements, based on 100 wt. % of the catalyst; (ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in (ii) into the reactor provided in (i) and contacting the feed gas stream with a catalyst, the contacting being at a pressure greater than 10 bara and at a temperature in the range of 200 to 750° C.; (iv) withdrawing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2. The method includes:

[0085] 2. The method of embodiment 1, wherein in (i), the catalyst contains no more than 0.5 wt.%, preferably no more than 0.1 wt.%, more preferably no more than 0.05 wt.%, more preferably no more than 0.01 wt.%, more preferably no more than 0.005 wt.%, more preferably no more than 0.001 wt.%, Ni and Co, calculated as the respective elements, based on 100 wt.% of the catalyst.

[0086] 3. The method of embodiment 1, wherein in (i) the reactor contains at most 1 wt.-% Ni and at most 0.5 wt.-% more preferably at most 0.1 wt.-% more preferably at most 0.05 wt.-% more preferably at most 0.01 wt.-% more preferably at most 0.005 wt.-% more preferably at most 0.001 wt.-% Ni and at most 0.001 wt.-% based on 100 wt.-% of the total content of the reactor, calculated as the respective elements.

[0087] In 4.(i), one or more carrier materials are 30 to 800 m 2 / g, preferably 40 to 500m 2 / g, more preferably 50 to 300m 2 / g, more preferably 60 to 200m 2 / g, more preferably 70 to 100m 2 / g, more preferably 75 to 80m 2 4. The method of any one of the preceding claims, wherein the cation exchange layer exhibits a BET surface area in the range of 1 / g.

[0088] 5. In (i), one or more carrier materials are more than 20 to 150 m 2 / g, 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, more preferably 25 to 35m 2 4. The method of any one of the preceding claims, wherein the cation exchange layer exhibits a BET surface area in the range of 1 / g.

[0089] 6. The method according to any of the preceding embodiments, wherein in (i) the one or more support materials exhibit a pore volume in the range of 0.2 to 3 ml / g, preferably 0.4 to 1.5 ml / g, more preferably 0.6 to 1 ml / g, more preferably 0.8 to 0.85 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0090] 7. In (i), the catalyst is 20 to 800 m 2 / g, preferably 30 to 500m 2 / g, more preferably 40 to 300m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, more preferably 70 to 75m 2 7. The method according to any one of the preceding claims, wherein the BET surface area is preferably determined according to ISO 9277:2010.

[0091] 8. The method according to any of the preceding embodiments, wherein in (i), the catalyst exhibits a pore volume in the range of 0.1-2 ml / g, preferably 0.15-1.2 ml / g, more preferably 0.2-0.8 ml / g, more preferably 0.25-0.5 ml / g, more preferably 0.3-0.35 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0092] 9. The method of any of embodiments 1 to 8, wherein in (i), 90 to 100 wt.%, preferably 95 to 100 wt.%, more preferably 99 to 100 wt.%, more preferably 99.5 to 100 wt.%, more preferably 99.9 to 100 wt.%, of Ru in the catalyst is supported on one or more support materials, based on 100 wt.% of Ru in the catalyst, calculated as element.

[0093] 10. The method according to any of the preceding embodiments 1 to 9, wherein in (i) Ru is supported on one or more support materials by impregnation technique using an aqueous solution of one or more ruthenium salts, the one or more ruthenium salts preferably comprising Ru(NO)(NO3)3, more preferably Ru(NO)(NO3)3 is used as the one or more ruthenium salts.

[0094] 11. In (i), 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, Mg, Ca, and La (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Zr, and Mg. 11. The method of any of the preceding embodiments, wherein the one or more support materials comprise one or more metal oxides selected from the group consisting of Al2O3, ZrO2, and spinel (including mixtures of two or more thereof), preferably from the group consisting of ZrO2 and spinel (including mixtures of two or more thereof), more preferably the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2, more preferably the one or more support materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0095] 12. The method of embodiment 11, wherein the ZrO2 comprises one or more crystalline phases and / or is amorphous, and wherein the one or more crystalline phases of ZrO2 are selected from the group consisting of a monoclinic phase, a tetragonal phase, and a cubic phase of ZrO2 (including mixtures of two or three thereof).

[0096] 13. The method of any of embodiments 1 to 12, wherein in (i) the one or more support materials are substantially free of CaO and / or MgO, preferably substantially free of CaO and MgO, more preferably substantially free of alkaline earth metal oxides, more preferably substantially free of Ca and / or Mg, more preferably substantially free of Ca and Mg, more preferably substantially free of alkaline earth metals.

[0097] 14. The method of any of embodiments 1 to 13, wherein in (i) the one or more support materials are substantially free of Al2O3 and / or SiO2, preferably substantially free of Al2O3 and SiO2, more preferably substantially free of Al and / or Si, more preferably substantially free of Al and Si.

[0098] 15. The method according to any one of the preceding embodiments, wherein in (i) the one or more support materials are substantially free of carbon nanotubes, preferably substantially free of elemental carbon, more preferably substantially free of carbon.

[0099] 16. The method of any of embodiments 1 to 15, wherein in (i), the catalyst comprises Ru in an amount in the range of 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.%, more preferably 4.5 to 5.5 wt.%, based on 100 wt.% of the total amount of the one or more support materials.

[0100] 17. The method according to any of the preceding embodiments, wherein in (i), 95-100% by weight, preferably 97-100% by weight, more preferably 98-100% by weight, more preferably 99-100% by weight, more preferably 99.5-100% by weight, more preferably 99.9-100% by weight of the catalyst consists of Ru and one or more support materials.

[0101] 18. The method of any of the preceding embodiments, wherein in (i), the catalyst 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 support materials supporting Ru, wherein the alkali metal and / or alkaline earth metal hydroxides are preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH, and KOH (including mixtures of two or more thereof), more preferably from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH, and KOH (including mixtures of two or more thereof), more preferably from the group consisting of LiOH, NaOH, and KOH (including mixtures of two or more thereof), more preferably the catalyst further comprises KOH and / or LiOH, preferably KOH.

[0102] 19. The method of embodiment 18, wherein the catalyst comprises one or more alkali metal hydroxides in an amount in the range of 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.%, more preferably 4.5 to 5.5 wt.%, based on 100 wt.% of the total amount of the one or more support materials.

[0103] 20. The method of embodiment 18 or 19, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the catalyst consists of Ru, one or more alkali metal hydroxides, and one or more support materials.

[0104] 21. The method according to any of the preceding embodiments, wherein in (i) the catalyst is in the form of a molding and / or in the form of a powder, preferably in the form of a molding, more preferably in the form of an extrudate or tablet.

[0105] 22. The method according to embodiment 21, 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, more preferably 2.5 to 3.5 mm.

[0106] 23. The method according to embodiment 21 or 22, wherein the extrudates are split bodies and the catalyst is in the form of split sieve fraction extrudates 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 to 700 μm, more preferably 300 to 500 μm.

[0107] 24. The method according to embodiment 21, wherein the tablet has a four-hole cross section, preferably a four-hole cross section and four grooves.

[0108] 25. The method of any of the preceding embodiments, wherein the contacting is carried out at a pressure in the range of 11 to 50 bara, preferably 15 to 45 bara, more preferably 15 to 40 bara, more preferably 18 to 35 bara, more preferably 19 to 31 bara, more preferably 20 to 28 bara, more preferably 20 to 25 bara.

[0109] 26. The method according to any of the preceding embodiments 1 to 25, wherein the contacting is carried out at a temperature in the range of 200 to 650°C, preferably 250 to 600°C, more preferably 300 to 550°C, more preferably 350 to 520°C, more preferably 400 to 500°C, more preferably 430 to 470°C.

[0110] 27. The method of any of the preceding embodiments 1-26, wherein the feed gas stream prepared in (ii) comprises 1-100% by volume NH3, more preferably 3-99.99% by volume, more preferably 5-99.95% by volume, more preferably 10-99.9% by volume, more preferably 15-99.9% by volume, more preferably 20-99.8% by volume, more preferably 30-99.7% by volume, more preferably 40-99.6% by volume, more preferably 50-99.5% by volume.

[0111] 28. The method according to any of the preceding embodiments, wherein the feed gas stream prepared in (ii) comprises 0-50 vol.%, preferably 0.01-30 vol.%, more preferably 0.03-15 vol.%, more preferably 0.05-5 vol.%, more preferably 0.1-1 vol.%, more preferably 0.12-0.5 vol.%, more preferably 0.14-0.16 vol.% N2.

[0112] 29. The method of any of the preceding embodiments, wherein the feed gas stream prepared in (ii) comprises 0-75% by volume H2, preferably 0-60% by volume, more preferably 0-50% by volume, more preferably 0-40% by volume, more preferably 0-35% by volume, more preferably 0-30% by volume.

[0113] 30. The method of any of the preceding embodiments, wherein the feed gas stream prepared in (ii) comprises 100-50,000 ppmv, preferably 200-30,000 ppmv, more preferably 500-25,000 ppmv, more preferably 500-20,000 ppmv, more preferably 500-15,000 ppmv, more preferably 750-15,000 ppmv, more preferably 1,000-11,000 ppmv, more preferably 1,000-10,000 ppmv, more preferably 2,000-8,000 ppmv, more preferably 3,000-7,500 ppmv, more preferably 4,500-7,000 ppmv, more preferably 5,000-6,500 ppmv of HO.

[0114] 31. The method according to any of the preceding embodiments, wherein the combined amount of NH3, N2, and H2 in the feed gas stream prepared in (ii) is in the range of 90-100% by weight, preferably 95-99.95% by volume, more preferably 98-99.9% by volume, more preferably 99-99.85% by volume, more preferably 99.7-99.8% by volume.

[0115] 32. The method of any of the preceding embodiments, wherein after (i) and before (iii), the catalyst contained in the reactor provided in (i) is reduced in an atmosphere comprising hydrogen.

[0116] 33. The method according to embodiment 32, wherein the reduction is carried out at a temperature in the range of 20 to 100°C, preferably 24 to 50°C, more preferably 26 to 35°C, more preferably 28 to 32°C.

[0117] 34. The method according to embodiment 32 or 33, wherein the reduction is carried out in an atmosphere containing 1 to 50% by volume of H2, preferably 2 to 20% by volume, more preferably 3 to 10% by volume, more preferably 4 to 6% by volume.

[0118] 35. The method according to any of embodiments 32 to 34, wherein the atmosphere comprises 50 to 99% by volume, preferably 80 to 98% by volume, more preferably 90 to 97% by volume, more preferably 94 to 96% by volume of inert gas.

[0119] 36. The method of any of the preceding embodiments, which is a process for the reforming of ammonia and hydrocarbons, wherein the feed gas stream prepared in (ii) further comprises one or more hydrocarbons and one or more of CO2 and HO, and the effluent gas stream withdrawn in (iv) further comprises CO.

[0120] 37. The method of embodiment 36, wherein the feed gas stream prepared in (ii) further comprises CO2 and one or more hydrocarbons, and wherein the feed gas stream preferably comprises 5 vol.% or less of H2O, more preferably 3 vol.% or less, more preferably 1 vol.% or less, more preferably 0.5 vol.% or less, more preferably 0.1 vol.% or less, more preferably 0.05 vol.% or less, more preferably 0.01 vol.% or less of H2O.

[0121] 38. The method of embodiment 36, wherein the feed gas stream prepared in (ii) further comprises H2O and one or more hydrocarbons, and wherein the feed gas stream comprises 5 vol.% or less of CO2, more preferably 3 vol.% or less, more preferably 1 vol.% or less, more preferably 0.5 vol.% or less, more preferably 0.1 vol.% or less, more preferably 0.05 vol.% or less, more preferably 0.01 vol.% or less of CO2.

[0122] 39. The method of embodiment 36, wherein the feed gas stream prepared in (ii) further comprises CO2, H2O, and one or more hydrocarbons.

[0123] 40. The method of any of embodiments 36-39, wherein the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof, preferably C1-C10 alkanes and mixtures thereof, more preferably C3-C9 alkanes and mixtures thereof, more preferably C4-C8 alkanes and mixtures thereof, more preferably C5-C7 alkanes and mixtures thereof, more preferably C6 alkanes and mixtures thereof.

[0124] 41. The method according to any of embodiments 36 to 40, wherein the contacting is carried out at a pressure in the range of more than 10 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.

[0125] 42. The method of any of embodiments 36-41, wherein the feed gas stream prepared in (ii) comprises 0.1-75 vol.%, preferably 0.3-60 vol.%, more preferably 0.5-50 vol.%, more preferably 0.8-40 vol.%, more preferably 1-30 vol.% NH3.

[0126] 43. The method of any of embodiments 36-42, wherein the feed gas stream prepared in (ii) comprises 10-70% by volume, preferably 12-60% by volume, more preferably 15-50% by volume of one or more hydrocarbons.

[0127] 44. The method of any of embodiments 36-43, wherein the feed gas stream prepared in (ii) comprises 0-75% by volume HO, preferably 0.5-70% by volume, more preferably 1-68% by volume, more preferably 3-66% by volume, more preferably 5-64% by volume, more preferably 8-62% by volume, more preferably 10-60% by volume.

[0128] 45. The method of any of embodiments 36-44, wherein the feed gas stream prepared in (ii) comprises 0-60% by volume CO2, preferably 1-58% by volume, more preferably 3-56% by volume, more preferably 5-54% by volume, more preferably 8-52% by volume, more preferably 10-50% by volume.

[0129] 46. ​​The method of any of embodiments 36-45, wherein the feed stream exhibits a H2O:C molar ratio, H2O to carbon contained in the one or more hydrocarbons, in the range of 0 to 4, more preferably 0.1 to 3, more preferably 0.3 to 2.5, more preferably 0.4 to 2, more preferably 0.5 to 1.6.

[0130] 47. The method of any of embodiments 36-46, wherein the feed stream exhibits a CO2:C molar ratio, 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.

[0131] 48. The method of any of embodiments 36-47, wherein the feed stream exhibits an NH3:C molar ratio, 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.

[0132] 49. Supply flow is 500-20,000h -1 , preferably 500 to 16,000h -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 , more preferably 3,000 to 5,000 hours -1 49. The method of any one of the preceding embodiments, wherein the gas is fed to the reactor at a gas hourly space velocity in the range of

[0133] 50. The method of any of embodiments 36-49, wherein the effluent gas stream withdrawn in (iv) further comprises CO2.

[0134] 51. The effluent gas stream withdrawn in (iv) exhibits a stoichiometric coefficient R in the range of 0.1 to 3, where R satisfies the formula (I):

number

[0135] 52. The method according to embodiment 51, wherein the stoichiometric coefficient R is in the range of 1 to 2.5, preferably 1.3 to 2.2.

[0136] 53. The method of embodiment 51, wherein R>2.

[0137] 54. The method of any one of embodiments 36 to 50 and 53, wherein the effluent gas stream withdrawn in (iv) exhibits a H2:CO molar ratio of greater than 2.

[0138] 55. The method according to embodiment 51, wherein the stoichiometric coefficient R is in the range of 0.5 to 3, preferably 1 to 2.2, more preferably 1.3 to 1.7.

[0139] 56. The method of any of embodiments 36-55, wherein the effluent gas stream withdrawn in (iv) comprises 10-90% by volume H2, preferably 20-80% by volume, more preferably 30-70% by volume, more preferably 40-65% by volume, more preferably 45-60% by volume H2.

[0140] 57. The method of any of embodiments 36-56, wherein the effluent gas stream withdrawn in (iv) comprises 1-70% by volume CO, preferably 3-50% by volume, more preferably 5-40% by volume, more preferably 10-35% by volume, more preferably 15-30% by volume.

[0141] 58. The method of any of embodiments 36-57, wherein the effluent gas stream withdrawn in (iv) comprises 1-50% by volume CO2, preferably 3-45% by volume, more preferably 5-40% by volume, more preferably 8-35% by volume, more preferably 10-30% by volume, more preferably 12-25% by volume.

[0142] 59. The process of any of the preceding embodiments, wherein the effluent gas stream withdrawn in (iv) is used in a process for the production of methanol, a process for the production of dimethyl ether, or a process for the production of methanol and dimethyl ether.

[0143] 60. The method of any one of the preceding embodiments, wherein the effluent gas stream withdrawn in (iv) is used in a process for the production of hydrocarbons, preferably according to a Fischer-Tropsch process.

[0144] 61. The method of any of the preceding embodiments, wherein the effluent gas stream withdrawn in (iv) is used 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.

[0145] 62. The method of any of the preceding embodiments, wherein in an initial stage, the feed gas stream prepared in (ii) and fed to the reactor in (iii) further comprises H2 for reducing the catalyst.

[0146] 63. The method of embodiment 62, wherein the feed gas stream prepared in (ii) and fed to the reactor in (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.

[0147] 64. The method of embodiment 35, 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, and N2, 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. EXAMPLES

[0148] The present invention is further illustrated by the following examples.

[0149] Example 1: Preparation of Ru (5 wt%) supported on ZrO2 Zirconium oxide powder (D9-89, BASF, BET surface area: 78 m) was used to obtain Ru supported on ZrO2 at a loading of 5 wt.%. 2 The catalyst was prepared according to Example 8 of WO 2015 / 086639 by impregnation of a ruthenium salt solution into a ruthenium oxide nanoparticle (0.1 ml / g, pore volume: 0.84 ml / g) of ruthenium oxide nanoparticles. The catalyst was then extruded to form extrudates with a diameter of 3 mm.

[0150] Example 2: Preparation of Ru (5 wt%) and KOH (5 wt%) supported on ZrO A 5 g sample of 5 wt. % Ru supported on ZrO2 extrudates obtained from Example 1 was impregnated with a KOH solution. To this effect, 5 g of extrudates obtained from Example 1 were divided to form a fraction in the range of 315-500 microns, which was then impregnated by incipient wetness impregnation with 0.25 g of KOH dissolved in 1.65 ml of water. The sample was then dried at 120° C. and subsequently calcined under an inert atmosphere at 500° C. for 2 hours.

[0151] Example 3: Preparation of Ru (2.5 wt%) and LiOH (4.5 wt%) supported on MgAlO spinel Hydrotalcite precursor (Pural MG30 from Sasol) was calcined at 950°C for 1 hour and used as support. 10 g of support as 315-500 micron fraction was impregnated with 1.41 g of Ru(NO)(NO3)3 solution (19.7 wt% Ru in solution), where the solution was further mixed with 9.5 g water and 1.38 g Li(NO3) prior to impregnation. The solution was then impregnated into the support, dried at 120°C for 2 hours, and calcined at 500°C for 2 hours under synthetic air consisting of 21 vol% O2 and 79 vol% N2.

[0152] Example 4: Catalyst testing in NH3 reforming under high pressure Prior to the tests, the catalyst was activated under a decreasing atmosphere of 5% H2 in Ar at a temperature of 30°C (residence time 1 h, heating rate 2°C / min). After the catalyst was activated, the feed was applied (see table below, NH3 + H2O + 5% by volume of Ar). In each test, the pressure p(NH3) was set at 1, 10, 30, and 50 bara. The gas hourly space velocity (GHSV) with respect to the NH3 content was set at 2,000, 4,000, 8,000, or 16,000 h -1 The temperature was changed from 300 to 650°C.

[0153] A residence time of 36 hours at 650°C was used as an aging step to monitor the stability of the catalyst. The baseline conversion at 450°C was then measured after the aging step. As can be seen from the results shown in Table 1, the deactivation was less than 10% of the initial activity.

[0154] [Table 1]

[0155] Table 2 shows the results for the catalysts from each of Examples 1 to 3 at p(NH3) = 30 bara for 2,000 h. -1Figure 1 shows the results from an experiment at a gas hourly space velocity (GHSV) of 10,000 ppm. The H2O content in the feed was set at 10,000 ppmvol. The temperature was increased in steps of 50°C. The NH3-conversion is shown in %. As can be derived from the results from the test shown in Figure 1, at 550°C the catalyst approaches equilibrium conversion, where the most active catalyst from Example 2 already approaches equilibrium conversion at 450°C.

[0156] [Table 2]

[0157] Table 3 shows the results of the 2,000h test at two reference temperatures, p(NH3) = 30 and 50 bara. -1 The water content in the feed was set at 10,000 ppmv.

[0158] [Table 3]

[0159] Table 4 shows the NH3 conversion of the most active 5 wt% ZrO2 supported Ru promoted with 5 wt% KOH. The experiments were carried out at 1, 10 and 30 bara ammonia p(NH3). The temperature was 8000 h. -1 The GHSV was varied from 300 to 600°C. The water content in the feed was set at 5,000 ppmv. As can be seen from the results from the test shown in Figure 2, equilibrium conversion was reached with the catalyst according to Example 2 at 450°C, where almost 80% NH3 conversion was already reached at 400°C.

[0160] [Table 4]

[0161] Here, as can be seen from the results obtained from the testing of the respective catalysts, a process is provided by the present invention that unexpectedly results in a highly effective decomposition of ammonia at high pressure.Furthermore, and quite unexpectedly, the process results in a highly effective decomposition at low temperatures, despite the high pressures required.In addition, it has also been found quite unexpectedly that the process of the present invention also results in a highly effective process when using technical grade ammonia containing small amounts of water for stabilization, despite the harsh hydrothermal conditions at high pressure due to the water present during the ammonia decomposition reaction.

[0162] Example 5: Preparation of MgAlO spinel supported Ru (5 wt%) and KOH (5 wt%; corresponding to 3.5 wt% K) A hydrotalcite precursor (Pural MG30 from Sasol) was calcined at temperatures ranging from 850 to 980°C and for periods ranging from 1 to 3 hours and then used as a support. 93 g of the support as a mould was impregnated with 27 g of Ru(NO)(NO3)3 solution (19.7 wt% Ru in solution). After drying at 180°C for 4 hours, the Ru containing mould was impregnated with 5.105 g of K(OH). The resulting material was then dried at 120°C for 2 hours and calcined at 500°C for 2 hours under synthetic air consisting of 21 vol% O2 and 79 vol% N2.

[0163] Example 6: Catalyst testing in NH3 reforming under high pressure Prior to the tests, the catalyst according to Example 4 was activated in a decreasing atmosphere of 5% H2 in Ar at a temperature of 30°C (residence time 1 h, heating rate 2°C / min). After activation of the catalyst, the feed was applied (see table below, NH3 + H2O + 5% by volume of Ar). In each test, the pressure p(NH3) was set at 30 bara. The gas hourly space velocity (GHSV) with respect to the NH3 content was calculated as 4,000 h -1 The temperature was changed from 300 to 650°C.

[0164] Table 5 shows the results from the experiment. The H2O content in the feed was set at 5,000 ppm by volume (ppmvol). The temperature was increased in 50°C increments. The NH3-conversion is given in %. As can be seen from the results from the test shown in Table 5, at 500°C the catalyst approached equilibrium conversion.

[0165] [Table 5]

[0166] With respect to the testing of the catalysts of Examples 1-3, it can be seen from the results obtained from the testing of the catalyst of Example 5 that the present invention provides a process that unexpectedly results in highly effective decomposition of ammonia at high pressure.Furthermore, and quite unexpectedly, the process results in highly effective decomposition at low temperatures, despite the high pressure required.In addition, it has been found quite unexpectedly that the process of the present invention also results in a highly effective process when using technical grade ammonia containing a small amount of water for stabilization, despite the harsh hydrothermal conditions at high pressure due to the water present in the ammonia decomposition reaction.

[0167] Cited Prior Art -K.Lamb et.al.in Int.J.of Hydrogen Energy 2019,44,3726-3736 -A.Di Carlo et al.in Int.J.of Hydrogen Energy 2014,39,808-814 -TALe et al.in Korean J.Chem.Eng.2021,38(6),1087-1103 -M.Miyamoto et al.in Int.J.of Hydrogen Energy 2018,43,730-738 -B.Lorenzut et al.in ChemCatChem 2010,2,1096-1106 -Z.Wang et al.in Int.J.of Hydrogen Energy 2019,44,7300-7307 -International Publication No. 2015 / 086639 A2 Brochure -International Publication No. 2018 / 046393 A1 Brochure -S.-F.Yin et al.in Applied Catalysis B Environmental 2004,48,237-241 -S.Sayas et al.in Catal.Sci.Technol.2020,10,5027-5035

Claims

1. 1. A method for reforming ammonia, comprising: (i) providing a reactor containing a catalyst comprising Ru and one or more support materials, wherein Ru is supported on the one or more support materials, and the one or more support materials are 20 m ２ / g or greater BET surface area, said catalyst containing 1 wt. % or less of Ni and Co, calculated as the respective elements, based on 100 wt. % of said catalyst; (ii) NH ３ preparing a feed gas stream comprising: (iii) feeding the feed gas stream prepared in (ii) into the reactor provided in (i) and contacting the feed gas stream with the catalyst, wherein the contacting is conducted at a pressure greater than 10 bara and at a temperature in the range of 200 to 750°C; (iv) withdrawing an effluent gas stream from the reactor, wherein the effluent gas stream is H ２ and N ２ and steps including A method comprising:

2. 2. The method of claim 1, wherein in (i), the one or more support materials exhibit a pore volume in the range of 0.2 to 3 ml / g.

3. 2. The method of claim 1, wherein in (i), the one or more support materials are selected from the group consisting of metal oxides.

4. 2. The method of claim 1, wherein in (i), the one or more support materials are substantially free of CaO and / or MgO.

5. 2. The method of claim 1, wherein in (i), the catalyst comprises Ru in an amount ranging from 0.5 to 15 wt. %, based on 100 wt. % of the total amount of the one or more support materials.

6. 2. The method of claim 1, wherein in (i), the catalyst further comprises one or more alkali metal and / or alkaline earth metal hydroxides, wherein the one or more alkali metal and / or alkaline earth metal hydroxides are supported on the one or more support materials that support Ru.

7. 7. The method of claim 6, wherein the catalyst comprises the one or more alkali metal hydroxides in an amount ranging from 0.5 to 15 wt. %, based on 100 wt. % of the total amount of the one or more support materials.

8. The method according to claim 1, wherein in (i), the catalyst is in the form of a molded article and / or a powder.

9. (ii) the feed gas stream prepared in step (ii) is 100 to 50,000 ppmv H ２ The method of claim 1 , comprising:

10. (ii) the NH contained in the feed gas stream prepared in ３ , N ２ , and H ２ 2. The method of claim 1, wherein the total amount of is in the range of 90 to 100% by weight, 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.

11. 1. A process for the reforming of ammonia and hydrocarbons, wherein the feed gas stream prepared in (ii) comprises one or more hydrocarbons and CO ２ and H ２ and one or more of O, and the effluent gas stream withdrawn in (iv) further comprises CO.

12. (ii) the feed gas stream prepared in ２ and one or more hydrocarbons.

13. (ii) the feed gas stream prepared in ２ 12. The method of claim 11 further comprising O and one or more hydrocarbons.

14. (ii) the feed gas stream prepared in ２ , H ２ 12. The method of claim 11 , further comprising: O; and one or more hydrocarbons.

15. 12. The method of claim 11, wherein the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof.

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