Method for reforming recycled NH3 at high pressure and low temperature

Abstract

The present invention relates to a method for reforming NH3, the method comprising the following steps: (i) providing a feed stream comprising NH3 to a reactor unit, the reactor unit having a reactor unit inlet and a reactor unit outlet, the reactor unit containing a catalyst material; (ii) contacting the feed stream with a catalyst material in a reactor unit to obtain a product stream comprising H, N, NH, and optionally HO, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 750°C; (iii) optionally separating the HO in the product stream obtained in (ii) to obtain a dehydrated product stream comprising H, N, and NH; (iv) separating NH3 from the product stream obtained in (ii) or the dehydrated product stream obtained in (iii) to obtain a purified product stream comprising N2 and H2; (v) Reusing the separated NH3 obtained in (iv) to (i). Includes.

Description

[Technical Field]

[0001] The present invention relates to a method for reforming NH3 at high pressure and low temperature with a recycling concept, in particular, separating unreacted NH3 from the reactor outlet and recycling it to the reactor inlet, and hydrogen contained in the product stream is extracted under high pressure reaction conditions. [Background technology]

[0002] NH3 is considered the energy vector of the future, and significant amounts of H2 can be stored chemically. The reforming of NH3 according to equation (I) is the final step to return hydrogen to chemical processes or other uses. The NH3 reforming process itself is an endothermic reaction (45.6 kJ / mol), so additional energy input is required. Also, the evaporation of liquid to gaseous NH3 must be considered as an energy-intensive process (23 kJ / mol).

[0003]

number

[0004] Due to the endothermic nature of the reforming process, high temperatures are advantageous for achieving high NH conversion. However, thermodynamic limitations must be considered in this regard. This is particularly true for pressure, since high pressures are typically undesirable given the thermodynamic limitations. However, from the perspective of hydrogen as the target product, high pressures are advantageous. The process of the present invention generally follows the concept of NH reforming, with NH being subsequently separated from the reactor outlet stream and fed back to the reactor inlet, allowing for a process design that avoids certain limitations. In particular, depending on the downstream application, a combination of temperature and pressure settings can be applied in the process design of the present invention. For example, a combination of low temperature and high pressure conditions can be applied.

[0005] US8961923B2 relates to autothermal ammonia decomposition. Disclosed is a method for autothermal decomposition of ammonia using air or oxygen, in which an ammonia and oxygen-containing gas mixture is combusted, preferably at a specific combination of temperature and pressure, such as a temperature above 1200°C and a pressure of 10 bar, or a temperature of 1300°C and a pressure of 1 bar.

[0006] US8691182B2 relates to a method for decomposing ammonia, which comprises burning a mixture of ammonia and an oxygen-containing gas, the combustion being preferably carried out at a temperature above 1100°C and preferably at a pressure of about 1 atmosphere.

[0007] US8464515B2 relates to an ammonia-burning internal combustion engine, which includes, inter alia, a reformer for reforming the ammonia arranged upstream of the combustion chamber.

[0008] US 2,578,193 discloses an ammonia dissociator, in which the dissociation of ammonia can be carried out at a temperature of about 650°C (1200°F).

[0009] WO2019 / 038251A1 relates to an autothermal ammonia decomposition process. In particular, it discloses a process for producing a product gas containing nitrogen and hydrogen from ammonia, which process comprises a step of non-catalytic partial oxidation of ammonia with an oxygen-containing gas.

[0010] Banares-Alcántara et al., in Applied Energy 2021, 282, 116009, present a forecast on the role of ammonia as an energy carrier, particularly in combined-cycle gas turbines for power generation. In particular, they present a modeled NH3 reformer assuming 99% conversion at 850°C.

[0011] As mentioned above, the process of reforming NH is an endothermic, volume-increasing equilibrium reaction. This means that low pressure and high temperature are required to obtain high conversion. However, the use of hydrogen obtained from NH reforming typically requires providing a hydrogen stream having a relatively high pressure and a relatively low temperature. Therefore, there was a need to provide a new method in which a product stream from NH reforming can be obtained at a relatively high pressure and a relatively low temperature. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] US8961923B2 [Patent Document 2] US8691182B2 [Patent Document 3] US8464515B2 [Patent Document 4] US2578193 [Patent Document 5] WO2019 / 038251A1 [Non-patent literature]

[0013] [Non-Patent Document 1] Banares-Alcantara et al., Applied Energy 2021,282,116009 Summary of the Invention [Problem to be solved by the invention]

[0014] It has thus surprisingly been found that a method according to the invention can be provided for producing a hydrogen-containing stream having a relatively high pressure, or a relatively high pressure and a relatively low temperature. In particular, the invention allows a method design in which the tubes are particularly small, whereby the hydrogen is produced at a particularly high pressure and therefore at a particularly low temperature, and which allows for a considerably smaller space requirement for the plant.

[0015] The advantage of this recycling process concept is that it avoids thermodynamic limitations and develops a dedicated, compact process design for any downstream application. In particular, the process of the present invention is advantageous in terms of resource and energy efficiency, especially its operating costs, given the low reaction temperatures combined with the high pressure H2 production.

[0016] In particular, the method for reforming NH3 according to the present invention features a recycle format, allowing for a process design that overcomes thermodynamic limitations on temperature and pressure, thereby enabling a dedicated process design for any downstream application and providing a low OPEX and CAPEX solution for the process for reforming NH3. [Means for solving the problem]

[0017] Accordingly, the present invention relates to a method for reforming NH3, the method comprising the following steps: (i) providing a feed stream comprising NH3 to a reactor unit, the reactor unit having a reactor unit inlet and a reactor unit outlet, the reactor unit containing a catalyst material; (ii) contacting the feed stream with a catalyst material in a reactor unit to obtain a product stream comprising H, N, NH, and optionally HO, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 750°C; (iii) optionally separating the HO in the product stream obtained in (ii) to obtain a dehydrated product stream comprising H, N, and NH; (iv) separating NH3 from the product stream obtained in (ii) or the dehydrated product stream obtained in (iii) to obtain a purified product stream comprising N2 and H2; (v) Reusing the separated NH3 obtained in (iv) to (i). Includes. [Brief explanation of the drawings]

[0018] [Figure 1]FIG. 1 shows a parity plot of simulated and experimental values ​​for the Ru-containing low-temperature NH3 reforming catalyst material according to the reference example. DETAILED DESCRIPTION OF THE INVENTION

[0019] Preferably, 90 to 100% by volume of the feed stream according to (i) consists of NH3, more preferably 93 to 100% by volume, more preferably 95 to 100% by volume.

[0020] The supply of the feed stream to the reactor unit according to (i) is 400 to 40,000 h -1 range, more preferably 2,000 to 12,000 h -1 It is preferable that the gas hourly space velocity is in the range of 100-200 rpm.

[0021] The feeding of the feed stream to the reactor unit according to (i) is preferably carried out at a molar flow rate in the range of 10 to 1000 kmol / h, more preferably in the range of 100 to 700 kmol / h, more preferably in the range of 140 to 660 kmol / h.

[0022] The feeding of the feed stream to the reactor unit according to (i) is preferably carried out at a mass flow rate in the range of 100 to 25000 kg / h, more preferably in the range of 1500 to 13000 kg / h, more preferably in the range of 2400 to 11500 kg / h.

[0023] The feed stream to the reactor unit according to (i) is 250 to 55,000 m 3 / h range, more preferably 5000 to 45000 m 3 / h range, more preferably 9250 to 41250 m 3 It is preferably carried out at a volume flow rate in the range of / h.

[0024] The feed stream to the reactor unit according to (i) is 50 to 2500 m 3 / h range, more preferably 250 to 1000m 3 / h, preferably 400 to 725 m 3It is preferably carried out at a volume flow rate in the range of / h.

[0025] It is preferred that the feed stream further comprises H2O, and the feed stream more preferably comprises 0 to 1 vol. % H2O, more preferably 0 to 0.5 vol. %, more preferably 0 to 0.21 vol. % H2O.

[0026] It is preferred that the feed stream further contains H2, more preferably 0 to 1% by volume, more preferably 0 to 0.1% by volume, more preferably 0 to 0.01% by volume of H2.

[0027] It is preferred that the feed stream further comprises N2, more preferably the feed stream comprises 0 to 5% by volume, preferably 0 to 1% by volume, more preferably 0 to 0.5% by volume of N2.

[0028] The contact in (ii) is preferably carried out at a pressure in the range of 5 to 55 bar (abs), more preferably in the range of 10 to 50 bar (abs), more preferably in the range of 15 to 45 bar (abs), more preferably in the range of 20 to 40, more preferably in the range of 25 to 35, more preferably in the range of 27 to 33, more preferably in the range of 29 to 31 bar (abs).

[0029] The contacting in (ii) is preferably carried out at a temperature in the range of 100 to 750°C, more preferably in the range of 160 to 650°C, more preferably in the range of 170 to 580°C, more preferably in the range of 180 to 570°C, more preferably in the range of 190 to 560°C, more preferably in the range of 200 to 550°C, more preferably in the range of 210 to 540°C, more preferably in the range of 220 to 530°C, more preferably in the range of 230 to 520°C, more preferably in the range of 240 to 510°C, more preferably in the range of 250 to 500°C.

[0030] Preferably, the contacting according to (ii) comprises increasing the temperature from the reactor unit inlet to the reactor unit outlet.

[0031] When the contacting according to (ii) comprises increasing the temperature from the reactor unit inlet to the reactor unit outlet, it is preferred that the temperature be increased from 175°C, more preferably 200°C, more preferably 225°C at the reactor unit inlet to 350°C, preferably 375°C, more preferably 400°C at the reactor unit outlet. Alternatively, it is even more preferred that the temperature be increased from 375°C, more preferably 400°C, more preferably 425°C at the reactor unit inlet to 550°C, preferably 575°C, more preferably 600°C at the reactor unit outlet.

[0032] In accordance with the present invention, the contacting according to (ii) preferably involves transferring heat from the reaction of the chemical conversion process, the heat transfer being carried out using a heat exchanger or a heat pump.

[0033] When the contacting according to (ii) involves transferring heat from a reaction in a chemical conversion process, and the heat transfer is accomplished using a heat exchanger or heat pump, it is preferred that the heat transferred is obtained from an exothermic reaction, or that the heat transferred is surplus heat from that used to carry out an autothermal or endothermic reaction.

[0034] When the heat transferred is obtained from an exothermic reaction, it is preferred that the exothermic reaction comprises one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and the selective oxidation of one or more of alkanes, alkenes, and alkynes, more preferably the selective oxidation of one or more of alkanes, alkenes, and alkynes to acrolein or acrylic acid.

[0035] When the heat transferred is excess heat to that used to carry out an endothermic reaction, the endothermic reaction preferably comprises one or more of steam cracking, ethane dehydrogenation, propane dehydrogenation, butane dehydrogenation, steam reforming, dry reforming, styrene production, methanol reforming, dimethyl ether reforming, reverse water-gas shift, alcohol dehydration, and NH3 reforming.

[0036] When the heat transferred is excess heat from the heat used to carry out the autothermal reaction, the autothermal reaction is preferably selected from the group consisting of autothermal reforming of natural gas and hydrocarbons, and partial oxidation (POx) processes of hydrocarbons, and the hydrocarbons are selected from the group consisting of (C1 to C 10 )alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0037] According to the invention, the reactor unit preferably comprises one or more reactors, the catalytic material being contained in one or more reactors.

[0038] When the reactor unit comprises one or more reactors and the catalytic material is contained in one or more reactors, it is preferred that each of the one or more reactors, independently of one another, be selected from the group consisting of a polytropic reactor, a two-stage reactor, an adiabatic reactor, and a combination of a polytropic reactor and an adiabatic reactor.

[0039] Furthermore, it is preferred that each of the one or more reactors independently of one another is tubular, and the tubular reactor preferably comprises, or more preferably consists of, 1 to 15,000, more preferably 100 to 12,000, and more preferably 500 to 5,000 tubes, each of the tubes independently of one another preferably having a diameter in the range of 1 to 50 cm, more preferably in the range of 5 to 25 cm, more preferably in the range of 8 to 22 cm.

[0040] Furthermore, it is preferred that each of the one or more reactors independently of one another has a length in the range of 1 to 15 m, more preferably in the range of 2 to 12 m, more preferably in the range of 3 to 9 m.

[0041] Furthermore, it is preferred that each of the one or more reactors independently of one another has a diameter in the range of 0.5 to 12 m, more preferably in the range of 0.5 to 4 m, more preferably in the range of 1.0 to 3.0 m, more preferably in the range of 1.5 to 2.5 m.

[0042] Further, each of the one or more reactors may be independently operated at a temperature of 0.5 to 150 m3 range, more preferably 1 to 80 m 3 range, more preferably 2 to 50 m 3 range, more preferably 3 to 30 m 3 range, more preferably 4 to 20 m 3 range, more preferably 5.0 to 16.5 m 3 It is preferred that the volume be in the range of

[0043] Furthermore, independently thereof, it is preferred that the reactor unit comprises, preferably consists of, one reactor, the reactor unit inlet is the reactor inlet, and the reactor unit outlet is the reactor outlet.

[0044] It is further preferred that the reactor unit comprises, more preferably consists of, two or more reactors, preferably two adiabatic reactors, the two reactors being a first reactor and a second reactor, the first reactor being disposed upstream of the second reactor, the first reactor having a first reactor inlet and a first reactor outlet, the reactor unit inlet being the first reactor inlet and the reactor unit outlet being the second reactor outlet; The providing according to (i) and the contacting according to (ii) are carried out by the following steps: (i.1) feeding a feed stream comprising NH3 into a first reactor to obtain an intermediate stream; (ii.1) contacting the feed stream with a catalyst material in a first reactor, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 750°C; (i.2) feeding the intermediate stream obtained in (i.1) into a second reactor; (ii.2) contacting the intermediate stream with a catalytic material in a second reactor, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 700°C; obtaining a product stream comprising H2, N2, NH3, and optionally H2O. Includes.

[0045] When the reactor unit comprises two or more reactors, the catalytic material is preferably contained in one or both of the two reactors, more preferably in the first reactor and the second reactor.

[0046] Furthermore, independently thereof, it is preferred that feeding the intermediate stream to the second reactor according to (i.2) is carried out at a pressure in the range of 1 to 100 bar (abs), more preferably in the range of 5 to 50 bar (abs).

[0047] Furthermore, independently thereof, feeding the intermediate stream to the second reactor according to (i.2) is preferably carried out at a temperature in the range of 250 to 650°C, more preferably in the range of 400 to 600°C. Furthermore, independently thereof, it is preferred that the feeding of the intermediate stream to the second reactor via (i.2) is carried out at the same pressure and at the same temperature as the feeding of the feed stream to the first reactor via (i.1).

[0048] Furthermore, independently, it is preferred that the contacting with one or both of (ii.1) and (ii.2) is carried out at a pressure in the range of 5 to 80 bar (abs), more preferably in the range of 10 to 60 bar (abs), more preferably in the range of 15 to 45 bar (abs), more preferably in the range of 20 to 40, more preferably in the range of 25 to 35, more preferably in the range of 27 to 33, more preferably in the range of 29 to 31 bar (abs).

[0049] Furthermore, independently, the contacting by one or both of (ii.1) and (ii.2) is preferably carried out in the range of 100 to 750°C, more preferably in the range of 160 to 650°C, more preferably in the range of 170 to 580°C, more preferably in the range of 180 to 570°C, more preferably in the range of 190 to 560°C, more preferably in the range of 200 to 550°C, more preferably in the range of 210 to 540°C, more preferably in the range of 220 to 530°C, more preferably in the range of 230 to 520°C, more preferably in the range of 240 to 510°C, more preferably in the range of 250 to 500°C.

[0050] Additionally, independently, contacting with one or both of (ii.1) and (ii.2) preferably comprises increasing the temperature from the reactor inlet to the reactor outlet.

[0051] When the contacting with one or both of (ii.1) and (ii.2) involves increasing the temperature from the reactor inlet to the reactor outlet, it is preferred that the temperature be increased from 175° C., more preferably 200° C., more preferably 225° C. at the reactor inlet to 350° C., preferably 375° C., more preferably 400° C. at the reactor outlet. Alternatively, it is also preferred that the temperature be increased from 375° C., more preferably 400° C., more preferably 425° C. at the reactor inlet to 550° C., preferably 575° C., more preferably 600° C. at the reactor outlet.

[0052] Additionally, independently, it is preferred that the contacting with one or both of (ii.1) and (ii.2) includes transferring heat from the reaction of the chemical conversion process, the heat transfer being accomplished using a heat exchanger or a heat pump.

[0053] When the contacting by one or both of (ii.1) and (ii.2) involves transferring heat from a reaction in a chemical conversion process, and the heat transfer is accomplished using a heat exchanger or heat pump, it is preferred that the heat transferred is obtained from an exothermic reaction, or that the heat transferred is excess heat from that used to carry out an autothermal or endothermic reaction.

[0054] When the heat transferred is obtained from an exothermic reaction, it is preferred that the exothermic reaction comprises one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and the selective oxidation of one or more of alkanes, alkenes, and alkynes, more preferably the selective oxidation of one or more of alkanes, alkenes, and alkynes to acrolein or acrylic acid.

[0055] When the heat transferred is excess heat to that used to carry out an endothermic reaction, the endothermic reaction preferably comprises one or more of steam cracking, ethane dehydrogenation, propane dehydrogenation, butane dehydrogenation, steam reforming, dry reforming, styrene production, methanol reforming, dimethyl ether reforming, reverse water-gas shift, alcohol dehydration, and NH3 reforming.

[0056] When the heat transferred is excess heat from that used to carry out an autothermal reaction, the autothermal reaction is preferably selected from the group consisting of autothermal reforming of natural gas and hydrocarbons, including partial oxidation of hydrocarbons (POx) processes, and the hydrocarbons are selected from the group consisting of (C1 to C 10 )alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0057] Furthermore, independently thereof, the reactor unit comprises two or more reactors, and the reactor unit further comprises one or more heaters, preferably positioned between the two reactors.

[0058] When the reactor unit includes two or more reactors, it is preferred that the reactor unit includes two reactors, and the reactor unit further includes one heater, which is disposed downstream of the first reactor and upstream of the second reactor for heating the intermediate stream.

[0059] According to the present invention, the reactor unit preferably comprises one or more reactors, the catalytic material being contained in one or more of the one or more reactors.

[0060] Preferably, the catalytic material comprises a metal M1, where M1 is Ni, Co, or Ni and Co.

[0061] When the catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co, it is preferred that the catalytic material further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably K, Na, Cs, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably K, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, and more preferably M2 comprises Fe, Ru, or Fe and Ru, more preferably M2 comprises Ru, more preferably M2 is Ru.

[0062] Furthermore, independently thereof, it is preferred that the catalytic material further comprises one or more support materials on which the metal M1 or the metals M1 and M2 are supported, the one or more support materials being more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably Al2O3, SiO2, and mixtures thereof, and more preferably the support material comprises Al2O3.

[0063] Furthermore, independently thereof, it is preferred that the catalyst material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, more preferably 0.5:99.5 to 75:25, more preferably 1:99 to 70:30, more preferably 5:95 to 65:35, more preferably 15:85 to 60:40, more preferably 30:70 to 55:45, and more preferably 40:60 to 50:50.

[0064] Furthermore, independently thereof, it is preferred that M2 comprises Fe, more preferably is Fe, and the catalyst material exhibits an M2:M1 atomic ratio in the range of 1:99 to 80:20, more preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, and more preferably 40:60 to 50:50.

[0065] Furthermore, independently thereof, it is preferred that M2 comprises Ru, more preferably is Ru, and the catalyst material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 30:70, preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, and more preferably 5:95 to 6:94.

[0066] Furthermore, independently, it is preferred that the catalyst material further comprises Al and O.

[0067] When the catalytic material further comprises Al and O, it is preferred that the catalytic material comprises Ni as the metal M1, and more preferably the metal M1 is Ni.

[0068] When the catalyst material contains Ni as the metal M1, it is preferable that the catalyst material further contains Mg, and the molar ratio of Ni:Mg:Al is more preferably in the range of 1:(0.1-12):(0.5-20), more preferably 1:(0.5-8):(1-12), more preferably 1:(1-5):(3-8), more preferably 1:(1.5-3):(3.5-5), and more preferably 1:(2.0-2.4):(4.0-4.4).

[0069] Furthermore, independently of this, it is preferable that 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of the catalyst material consist of Ni, Mg, Al, and O.

[0070] Furthermore, independently of this, it is preferable that 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of the catalyst material consists of M2, Ni, Mg, Al, and O.

[0071] When the catalytic material further comprises Al and O, it is preferred that the catalytic material comprises Co as the metal M1, and more preferably the metal M1 is Co.

[0072] When the catalyst material contains Co as the metal M1, it is preferable that the catalyst material further contains La, and the molar ratio of Co:La:Al is more preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), and more preferably 1:(1.3-1.7):(10-12).

[0073] Furthermore, independently of this, it is preferable that 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of the catalyst material consist of Co, La, Al, and O.

[0074] Furthermore, independently of this, it is preferable that 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of the catalyst material consists of M2, Co, La, Al, and O.

[0075] According to the present invention, the catalytic material preferably comprises Ru and one or more support materials, wherein Ru is supported on one or more support materials, and the one or more support materials are 20 m 2 / g or more, the BET specific surface area being preferably measured in accordance with ISO 9277:2010, and the catalyst material contains 1 mass % or less of Ni and Co, each calculated as an element relative to 100 mass % of the catalyst material.

[0076] When the catalytic material comprises Ru and one or more support materials, it is preferred that the catalytic material contain no more than 0.5%, more preferably no more than 0.1%, more preferably no more than 0.05%, more preferably no more than 0.01%, more preferably no more than 0.005%, and more preferably no more than 0.001%, by weight of Ni and Co, each calculated as the element relative to 100% by weight of the catalytic material.

[0077] When the catalytic material comprises Ru and one or more support materials, it is also preferred that the reactor unit contains no more than 1% by weight, more preferably no more than 0.5% by weight, more preferably no more than 0.1% by weight, more preferably no more than 0.05% by weight, more preferably no more than 0.01% by weight, more preferably no more than 0.005% by weight, and more preferably no more than 0.001% by weight of Ni and Co, each calculated as the element relative to 100% by weight of the total contents of the reactor. Additionally, independently, one or more support materials may have a BET surface area of ​​30 to 800 m 2 / g, more preferably 40 to 500m 2 / g, more preferably 50 to 300m 2 / g, more preferably 60 to 200m 2 / g, more preferably 70 to 100m 2 / g, and more preferably 75 to 80 m 2 It is preferable that the range is / g.

[0078] Additionally, independently, one or more support materials may have a BET surface area greater 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, and more preferably 25 to 35 m 2 It is preferable that the range is / g.

[0079] Furthermore, independently, it is preferred that the one or more support materials exhibit a pore volume in the range of 0.2 to 3 ml / g, more preferably 0.4 to 1.5 ml / g, more preferably 0.6 to 1 ml / g, and more preferably 0.8 to 0.85 ml / g, the pore volume preferably being measured in accordance with ISO 15901-2:2022.

[0080] Furthermore, independently, the catalyst material has a BET surface area of ​​20 to 800 m 2 / g, more preferably 30 to 500m 2 / g, more preferably 40 to 300m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, and more preferably 70 to 75 m 2 / g, the BET surface area being preferably measured according to ISO 9277:2010.

[0081] Furthermore, independently thereof, it is preferred that the catalyst material exhibits a pore volume in the range of 0.1 to 2 ml / g, more preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, and more preferably 0.3 to 0.35 ml / g, the pore volume preferably being measured in accordance with ISO 15901-2:2022.

[0082] Furthermore, independently of this, it is preferable that 90 to 100 mass%, more preferably 95 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of Ru, calculated as elemental Ru relative to 100 mass% of Ru contained in the catalyst material, be supported on one or more support materials contained in the catalyst material.

[0083] Furthermore, independently, it is preferred that Ru is supported on one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, the one or more ruthenium salts more preferably comprising Ru(NO)(NO3)3, and more preferably Ru(NO)(NO3)3 is used as the one or more ruthenium salts.

[0084] Furthermore, independently, it is preferred that 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, and rare earth metals, and combinations of two or more thereof, more preferably Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, and Nd, and combinations of two or more thereof, more preferably Al, Ti, Zr, Mg, Ca, and La, and combinations of two or more thereof, more preferably Al, Z and 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, and spinel, and combinations of two or more thereof, preferably ZrO2 and spinel, and combinations of two or more thereof; more preferably, the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably comprise ZrO2; more preferably, the one or more support materials consist of ZrO2 and / or MgAl2O4, preferably consist of ZrO2.

[0085] 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, and the one or more crystalline phases of ZrO2 are selected from the group consisting of monoclinic, tetragonal, and cubic phases of ZrO2, and mixtures of two or three thereof.

[0086] Furthermore, independently, it is preferred that the one or more support materials are substantially free of CaO and / or MgO, more preferably substantially free of CaO and MgO, more preferably substantially free of alkaline earth metal oxides, more preferably substantially free of Ca and / or Mg, more preferably substantially free of Ca and Mg, and more preferably substantially free of alkaline earth metals.

[0087] Furthermore, independently, 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, and more preferably substantially free of Al and Si.

[0088] Additionally, independently, it is preferred that the one or more support materials be substantially free of carbon nanotubes, more preferably substantially free of elemental carbon, and even more preferably substantially free of carbon.

[0089] Furthermore, independently, it is preferred that the catalytic material 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 %, and more preferably 4.5 to 5.5 wt %, relative to 100 wt % of the total amount of the one or more support materials.

[0090] Furthermore, independently, it is preferred that 95 to 100% by mass of the catalyst material consists of Ru and one or more support materials, 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, and more preferably 99.9 to 100% by mass.

[0091] Furthermore, independently thereof, it is preferred that the catalytic material further comprises one or more alkali metal and / or alkaline earth metal hydroxides, which are supported on one or more support materials that support Ru, and the alkali metal and / or alkaline earth metal hydroxides are more preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH, and KOH, and mixtures of two or more thereof, more preferably Mg(OH)2, Ca(OH)2, LiOH, NaOH, and KOH, and mixtures of two or more thereof, more preferably LiOH, NaOH, and KOH, and mixtures of two or more thereof, and more preferably the catalytic material further comprises KOH and / or LiOH, preferably KOH.

[0092] When the catalytic material further comprises one or more alkali metal and / or alkaline earth metal hydroxides, it is preferred that the catalytic material comprises the one or more alkali metal hydroxides in an amount in the range of 0.5 to 15 mass %, more preferably 1 to 10 mass %, more preferably 2 to 8 mass %, more preferably 3 to 6.5 mass %, more preferably 4 to 6 mass %, and more preferably 4.5 to 5.5 mass %, relative to 100 mass % of the total amount of the one or more support materials.

[0093] Furthermore, independently thereof, it is preferred that 95 to 100 mass %, more preferably 97 to 100 mass %, more preferably 98 to 100 mass %, more preferably 99 to 100 mass %, more preferably 99.5 to 100 mass %, and more preferably 99.9 to 100 mass % of the catalyst material consists of Ru, one or more alkali metal hydroxides, and one or more support materials.

[0094] Furthermore, independently, it is preferred that the catalyst material is in the form of extrusions and / or powder, more preferably in the form of extrudates, and more preferably in the form of extrudates.

[0095] When the catalyst material is in the form of extrudates, it is preferred that the extrudates have a diameter in the range of from 0.5 to 10 mm, more preferably from 1 to 7 mm, more preferably from 1.5 to 5 mm, more preferably from 2 to 4 mm, and more preferably from 2.5 to 3.5 mm.

[0096] According to the present invention, it is even more preferred that the catalytic material comprises Ni, Ru, and a promoter metal M1', wherein the catalytic material 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, and Ba, and mixtures of two or more thereof, and the catalytic material further comprises one or more support materials on which Ni, Ru, and the promoter metal M1' are respectively supported.

[0097] When the catalyst material comprises Ni, Ru, and a promoter metal M1′, it is preferred that the catalyst material 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, and more preferably 0.025:1 to 0.035:1.

[0098] Furthermore, independently thereof, it is preferred that the promoter metal M1' is selected from the group consisting of Li, K, Na, Cs, Mg, and Ca, and mixtures of two or more thereof, more preferably the group consisting of Li, K, Na, and Cs, and mixtures of two or more thereof, more preferably the group consisting of Li, K, and 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.

[0099] Furthermore, independently thereof, it is preferred that the catalyst material 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, and more preferably 2.9:1 to 3:1.

[0100] Furthermore, independently, it is preferred that 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, and rare earth metals and combinations of two or more thereof, more preferably Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, and Nd and combinations of two or more thereof, more preferably Al, Ti, Zr, Mg, Ca, and La and combinations of two or more thereof, and more preferably Al, Zr, and 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, and spinel and mixtures of two or more thereof, preferably ZrO2, and spinel and mixtures of two or more thereof, more preferably ZrO2, NiMgO2, and 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 consist of NiMgO2 and MgAl2O4, preferably NiMgO2 and MgAl2O4.

[0101] Furthermore, independently of this, it is preferred that 90 to 100 mass%, more preferably 95 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of Ni and Ru, calculated as elements, relative to 100 mass% of Ni and Ru contained in the catalyst material, are supported on one or more support materials contained in the catalyst material.

[0102] Furthermore, independently of this, it is preferable that 90 to 100 mass%, more preferably 95 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of Ni, Ru, and promoter metal M1', calculated as elements, relative to 100 mass% of Ni, Ru, and promoter metal M1' contained in the catalyst material, are supported on one or more support materials contained in the catalyst material.

[0103] Furthermore, independently thereof, it is preferred that the catalyst material comprises 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 %, and more preferably 14 to 16 mass %, calculated as the element relative to 100 mass % of the catalyst material.

[0104] Furthermore, independently thereof, it is preferred that the catalyst material comprises 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 %, and more preferably 0.4 to 0.6 mass %, calculated as the element relative to 100 mass % of the catalyst material.

[0105] Furthermore, independently thereof, it is preferred that the catalyst material comprises the promoter metal M1' in an amount in the range of 0.05 to 25 mass %, more preferably 0.1 to 15 mass %, more preferably 0.5 to 10 mass %, more preferably 1 to 8 mass %, more preferably 2 to 5 mass %, and more preferably 3 to 4 mass %, calculated as the element relative to 100 mass % of the catalyst material.

[0106] Furthermore, independently, it is preferred that 95 to 100% by weight, more preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the catalyst material consists of Ni, Ru, the promoter metal M1', and one or more support materials, with Ni, Ru, and the promoter metal M1' each present as an element, an oxide, and / or a salt.

[0107] Furthermore, independently thereof, it is preferred that the catalytic material comprises 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 catalytic material as its hydroxide salt.

[0108] Furthermore, independently, it is preferred that Ru is supported on one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, the one or more ruthenium salts more preferably comprising Ru(NO)(NO3)3, and more preferably Ru(NO)(NO3)3 is used as the one or more ruthenium salts.

[0109] Furthermore, independently, it is preferred that the catalyst material is in the form of a molding, an extrudate, and / or a powder, more preferably in the form of a molding or an extrudate, and more preferably in the form of a molding.

[0110] When the catalyst material is in the form of extrudates, it is preferred that the extrudates have a diameter in the range of from 0.5 to 10 mm, more preferably from 1 to 7 mm, more preferably from 1.5 to 5 mm, more preferably from 2 to 4 mm, more preferably from 2.5 to 3.5 mm.

[0111] When the catalyst material is in the form of a molding, it is preferred that the molding has a diameter in the range of 1 to 20 mm, more preferably in the range of 1 to 15 mm.

[0112] Furthermore, independently, it is preferred that the molding be four-lobed.

[0113] According to the invention, the separation according to (iii) is preferably carried out in a first separator, which is arranged downstream of the reactor unit.

[0114] Preferably, the separation according to (iii) comprises cooling the product stream to a temperature in the range of from 0 to 100°C, more preferably in the range of from 30 to 70°C, more preferably in the range of from 45 to 55°C.

[0115] Preferably, the separation according to (iii) comprises compressing the product stream to a pressure in the range of from 5 to 100 bar (abs), more preferably in the range of from 20 to 50 bar (abs), more preferably in the range of from 25 to 35 bar (abs).

[0116] Preferably, the separation according to (iv) is carried out in a second separator, which is located downstream of the reactor unit or downstream of the first separator.

[0117] Preferably, the separation according to (iv) comprises heating the product stream or dehydrated product stream to a temperature in the range of from -180 to 0°C, more preferably in the range of from -100 to -50°C, more preferably in the range of from -85 to -75°C.

[0118] Preferably, the separation according to (iv) comprises compressing the product stream or dehydrated product stream to a pressure in the range of from 10 to 100 bar (abs), more preferably in the range of from 35 to 65 bar (abs), more preferably in the range of from 45 to 55 bar (abs).

[0119] Preferably, the method of the present invention further comprises, after (iv) and before (v), heating the NH3 obtained in (iv) to a temperature in the range of 50 to 750°C, more preferably in the range of 175 to 575°C, more preferably in the range of 300 to 550°C.

[0120] Preferably, the process of the present invention further comprises, after (iv) and before (v), expanding the NH obtained in (iv) to a pressure in the range of 1 to 50 bar (abs), more preferably in the range of 1 to 35 bar (abs), more preferably in the range of 1 to 30 bar (abs).

[0121] The unit bar (abs) means absolute pressure, and 1 bar is 10 5 Equivalent to Pa.

[0122] The present invention is further illustrated by the following set 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, for example in the context of a term such as "the method of any one of embodiments 1 to 4," all embodiments within this range are meant to be expressly disclosed for those skilled in the art, i.e., this expression means that those skilled in the art will understand that it is synonymous with "the method of any one of embodiments 1, 2, 3, and 4." Furthermore, it is expressly noted that the following set of embodiments represents a suitably structured part of the description directed to the general and preferred aspects of the present invention, rather than a set of claims determining the scope of protection.

[0123] 1. A method for reforming NH3, comprising the steps of: (i) providing a feed stream comprising NH3 to a reactor unit, the reactor unit having a reactor unit inlet and a reactor unit outlet, the reactor unit containing a catalyst material; (ii) contacting the feed stream with a catalyst material in a reactor unit to obtain a product stream comprising H, N, NH, and optionally HO, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 750°C; (iii) optionally separating the HO in the product stream obtained in (ii) to obtain a dehydrated product stream comprising H, N, and NH; (iv) separating NH3 from the product stream obtained in (ii) or the dehydrated product stream obtained in (iii) to obtain a purified product stream comprising N2 and H2; (v) Reusing the separated NH3 obtained in (iv) to (i). A method comprising:

[0124] 2. The process of embodiment 1, wherein 90-100% by volume, preferably 93-100% by volume, more preferably 95-100% by volume of the feed stream from (i) consists of NH3.

[0125] 3. The supply of the feed stream to the reactor unit according to (i) is 400 to 40,000 h -1 range, preferably 2,000 to 12,000 h -1 3. The method of embodiment 1 or 2, wherein the gas hourly space velocity is in the range of

[0126] 4. The process of any one of embodiments 1 to 3, wherein the supply of the feed stream to the reactor unit according to (i) is carried out at a molar flow rate in the range of 10 to 1000 kmol / h, preferably in the range of 100 to 700 kmol / h, more preferably in the range of 140 to 660 kmol / h.

[0127] 5. The process of any one of embodiments 1 to 4, wherein the supply of the feed stream to the reactor unit according to (i) is carried out at a mass flow rate in the range of 100 to 25000 kg / h, preferably in the range of 1500 to 13000 kg / h, more preferably in the range of 2400 to 11500 kg / h.

[0128] 6. The supply of the feed stream to the reactor unit according to (i) is 250 to 55,000 m 3 / h range, preferably 5000 to 45000 m 3 / h range, more preferably 9250 to 41250 m 3 6. The method of any one of embodiments 1 to 5, wherein the process is carried out at a volumetric flow rate in the range of / h.

[0129] 7. The supply of the feed stream to the reactor unit according to (i) is 50 to 2500 m 3 / h range, preferably 250 to 1000m 3 / h, preferably 400 to 725 m 3 7. The method of any one of embodiments 1 to 6, wherein the process is carried out at a volumetric flow rate in the range of / h.

[0130] 8. The method of any one of embodiments 1 to 7, wherein the feed stream further comprises HO, preferably the feed stream comprises 0-1 vol%, more preferably 0-0.5 vol%, more preferably 0-0.21 vol% HO.

[0131] 9. The method of any one of embodiments 1 to 8, wherein the feed stream further comprises H2, and wherein the feed stream preferably comprises 0-1 vol%, more preferably 0-0.1 vol%, more preferably 0-0.01 vol% H2.

[0132] 10. The method of any one of embodiments 1 to 9, wherein the feed stream further comprises N2, and the feed stream preferably comprises 0-5 vol.%, more preferably 0-1 vol.%, more preferably 0-0.5 vol.% N2.

[0133] 11. The process of any one of embodiments 1 to 10, wherein the contacting according to (ii) is carried out at a pressure in the range of 5 to 55 bar (abs), preferably in the range of 10 to 50 bar (abs), more preferably in the range of 15 to 45 bar (abs), more preferably in the range of 20 to 40, more preferably in the range of 25 to 35, more preferably in the range of 27 to 33, more preferably in the range of 29 to 31 bar (abs).

[0134] 12. The process of any one of embodiments 1 to 11, wherein the contacting according to (ii) is carried out at a temperature in the range of 100 to 750°C, more preferably in the range of 160 to 650°C, more preferably in the range of 170 to 580°C, more preferably in the range of 180 to 570°C, more preferably in the range of 190 to 560°C, more preferably in the range of 200 to 550°C, more preferably in the range of 210 to 540°C, more preferably in the range of 220 to 530°C, more preferably in the range of 230 to 520°C, more preferably in the range of 240 to 510°C, more preferably in the range of 250 to 500°C.

[0135] 13. The process of any one of embodiments 1 to 12, wherein the contacting according to (ii) comprises increasing the temperature from the reactor unit inlet to the reactor unit outlet.

[0136] 14. The process of embodiment 13, wherein the temperature is increased from 175°C, preferably 200°C, more preferably 225°C at the reactor unit inlet to 350°C, preferably 375°C, more preferably 400°C at the reactor unit outlet.

[0137] 15. The process of embodiment 13, wherein the temperature is increased from 375°C, preferably 400°C, more preferably 425°C at the reactor unit inlet to 550°C, preferably 575°C, more preferably 600°C at the reactor unit outlet.

[0138] 16. The method of any one of embodiments 1 to 15, wherein the contacting according to (ii) comprises transferring heat from a reaction of a chemical conversion process, and the heat transfer is performed using a heat exchanger or a heat pump.

[0139] 17. The method of embodiment 16, wherein the heat transferred is obtained from an exothermic reaction, or the heat transferred is excess heat from heat used to carry out an autothermal or endothermic reaction.

[0140] 18. The method of embodiment 17, wherein the exothermic reaction comprises one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and selective oxidation of one or more of alkanes, alkenes, and alkynes, preferably selective oxidation of one or more of alkanes, alkenes, and alkynes to acrolein or acrylic acid.

[0141] 19. The method of embodiment 17, wherein the endothermic reaction comprises one or more of steam cracking, ethane dehydrogenation, propane dehydrogenation, butane dehydrogenation, steam reforming, dry reforming, styrene production, methanol reforming, dimethyl ether reforming, reverse water-gas shift, alcohol dehydration, and NH3 reforming.

[0142] 20. The autothermal reaction is selected from the group consisting of autothermal reforming of natural gas and hydrocarbons, and partial oxidation of hydrocarbons (POx) processes, and the hydrocarbons are selected from the group consisting of (C1 to C 10 18. The method of embodiment 17, wherein the alkyl group is selected from the group consisting of (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0143] 21. The method of any one of embodiments 1 to 20, wherein the reactor unit comprises one or more reactors, and the catalytic material is comprised in one or more reactors.

[0144] 22. The method of embodiment 21, wherein each of the one or more reactors is independently selected from the group consisting of a polytropic reactor, a two-stage reactor, an adiabatic reactor, and a combination of a polytropic reactor and an adiabatic reactor.

[0145] 23. The process of embodiment 21 or 22, wherein each of the one or more reactors, independently of one another, is tubular, and the tubular reactor preferably comprises, more preferably consists of, 1 to 15,000, more preferably 100 to 12,000, and more preferably 500 to 5,000 tubes, each of the tubes, independently of one another, more preferably has a diameter in the range of 1 to 50 cm, more preferably in the range of 5 to 25 cm, more preferably in the range of 8 to 22 cm.

[0146] 24. The process of any one of embodiments 21 to 23, wherein each of the one or more reactors independently of one another has a length in the range of 1 to 15 m, more preferably in the range of 2 to 12 m, more preferably in the range of 3 to 9 m.

[0147] 25. The process of any one of embodiments 21 to 24, wherein each of the one or more reactors independently of one another has a diameter in the range of 0.5 to 12 m, preferably in the range of 0.5 to 4 m, more preferably in the range of 1.0 to 3.0 m, more preferably in the range of 1.5 to 2.5 m.

[0148] 26. One or more reactors, each of which is independently 0.5 to 150 m 3 range, preferably 1 to 80 m 3 range, more preferably 2 to 50 m 3 range, more preferably 3 to 30 m 3 range, more preferably 4 to 20 m 3 range, more preferably 5.0 to 16.5 m 3 26. The method of any one of embodiments 21 to 25, wherein the volume is in the range of

[0149] 27. The process of any one of embodiments 21 to 26, wherein the reactor unit comprises, and preferably consists of, one reactor, the reactor unit inlet is the reactor inlet, and the reactor unit outlet is the reactor outlet.

[0150] 28. The reactor unit comprises, preferably consists of, two or more reactors, preferably two adiabatic reactors, the two reactors being a first reactor and a second reactor, the first reactor being disposed upstream of the second reactor, the first reactor having a first reactor inlet and a first reactor outlet, the reactor unit inlet being the first reactor inlet and the reactor unit outlet being the second reactor outlet; providing according to (i) and contacting according to (ii) comprising the steps of: (i.1) feeding a feed stream comprising NH3 into a first reactor to obtain an intermediate stream; (ii.1) contacting the feed stream with a catalyst material in a first reactor, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 750°C; (i.2) feeding the intermediate stream obtained in (i.1) into a second reactor; (ii.2) contacting the intermediate stream with a catalytic material in a second reactor, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 700°C; obtaining a product stream comprising H2, N2, NH3, and optionally H2O. 27. The method of any one of embodiments 21 to 26, comprising:

[0151] 29. The method of embodiment 28, wherein the catalytic material is contained in one or both of the two reactors, the catalytic material being preferably contained in the first reactor and the second reactor.

[0152] 30. The process of embodiment 28 or 29, wherein feeding the intermediate stream to the second reactor according to (i.2) is carried out at a pressure in the range of 1 to 100 bar (abs), preferably in the range of 5 to 50 bar (abs).

[0153] 31. The process of any one of embodiments 28 to 30, wherein feeding the intermediate stream to the second reactor according to (i.2) is carried out at a temperature in the range of 250 to 650°C, preferably in the range of 400 to 600°C.

[0154] 32. The process of any one of embodiments 28 to 31, wherein feeding the intermediate stream to the second reactor via (i.2) is conducted at the same pressure and at the same temperature as feeding the feed stream to the first reactor via (i.1).

[0155] 33. The method of any one of embodiments 28 to 32, wherein the contacting with one or both of (ii.1) and (ii.2) is carried out at a pressure in the range of 5 to 80 bar (abs), preferably in the range of 10 to 60 bar (abs), more preferably in the range of 15 to 45 bar (abs), more preferably in the range of 20 to 40, more preferably in the range of 25 to 35, more preferably in the range of 27 to 33, more preferably in the range of 29 to 31 bar (abs).

[0156] 34. The method of any one of embodiments 28 to 33, wherein the contacting by one or both of (ii.1) and (ii.2) is carried out at a temperature in the range of 100 to 750°C, more preferably in the range of 160 to 650°C, more preferably in the range of 170 to 580°C, more preferably in the range of 180 to 570°C, more preferably in the range of 190 to 560°C, more preferably in the range of 200 to 550°C, more preferably in the range of 210 to 540°C, more preferably in the range of 220 to 530°C, more preferably in the range of 230 to 520°C, more preferably in the range of 240 to 510°C, or more preferably in the range of 250 to 500°C.

[0157] 35. The process of any one of embodiments 28 to 34, wherein the contacting with one or both of (ii.1) and (ii.2) comprises increasing the temperature from the reactor inlet to the reactor outlet.

[0158] 36. The process of embodiment 35, wherein the temperature is increased from 175°C, preferably 200°C, more preferably 225°C at the reactor inlet to 350°C, preferably 375°C, more preferably 400°C at the reactor outlet.

[0159] 37. The method of embodiment 35, wherein the temperature is increased from 375°C, preferably 400°C, more preferably 425°C at the reactor inlet to 550°C, preferably 575°C, more preferably 600°C at the reactor outlet.

[0160] 38. The method of any one of embodiments 28 to 37, wherein the contacting with one or both of (ii.1) and (ii.2) comprises transferring heat from a reaction of a chemical conversion process, and the heat transfer is performed using a heat exchanger or a heat pump.

[0161] 39. The method of embodiment 38, wherein the heat transferred is obtained from an exothermic reaction, or the heat transferred is excess heat from heat used to carry out an autothermal or endothermic reaction.

[0162] 40. The method of embodiment 39, wherein the exothermic reaction comprises one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and selective oxidation of one or more of alkanes, alkenes, and alkynes, preferably selective oxidation of one or more of alkanes, alkenes, and alkynes to acrolein or acrylic acid.

[0163] 41. The method of embodiment 39, wherein the endothermic reaction comprises one or more of steam cracking, ethane dehydrogenation, propane dehydrogenation, butane dehydrogenation, steam reforming, dry reforming, styrene production, methanol reforming, dimethyl ether reforming, reverse water-gas shift, alcohol dehydration, and NH3 reforming.

[0164] 42. The autothermal reaction is selected from the group consisting of autothermal reforming of natural gas and hydrocarbons, and partial oxidation of hydrocarbons (POx) processes, and the hydrocarbons are selected from the group consisting of (C1 to C 10 40. The method of embodiment 39, wherein the alkyl group is selected from the group consisting of: (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0165] 43. The method of any one of embodiments 28 to 42, preferably embodiment 42, wherein the reactor unit comprises two or more reactors, the reactor unit further comprises one or more heaters, and the heaters are disposed between the two reactors.

[0166] 44. The process of embodiment 43, wherein the reactor unit comprises two reactors, and the reactor unit further comprises a heater, the heater being disposed downstream of the first reactor and upstream of the second reactor for heating the intermediate stream.

[0167] 45. The method of any one of embodiments 1 to 44, wherein the reactor unit comprises one or more reactors, and the catalytic material is comprised in one or more of the one or more reactors.

[0168] 46. ​​The method of any one of embodiments 1 to 45, wherein the catalytic material comprises a metal M1, and M1 is Ni, Co, or Ni and Co.

[0169] 47. The method of embodiment 46, wherein the catalytic material further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and mixtures of two or more thereof, preferably Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably K, Na, Cs, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably K, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, wherein M2 more preferably comprises Fe, Ru, or Fe and Ru, more preferably M2 comprises Ru, and more preferably M2 is Ru.

[0170] 48. The method of embodiment 46 or 47, wherein the catalytic material further comprises one or more support materials on which the metal M1 or the metals M1 and M2 are supported, the one or more support materials preferably being selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably Al2O3, SiO2, and mixtures thereof, and more preferably the support material comprises Al2O3.

[0171] 49. The method of any one of embodiments 47 or 48, wherein the catalyst material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, preferably 0.5:99.5 to 75:25, more preferably 1:99 to 70:30, more preferably 5:95 to 65:35, more preferably 15:85 to 60:40, more preferably 30:70 to 55:45, and more preferably 40:60 to 50:50.

[0172] 50. The method of any of embodiments 47 to 49, wherein M2 comprises Fe, preferably is Fe, and the catalytic material exhibits an M2:M1 atomic ratio in the range of 1:99 to 80:20, preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, and more preferably 40:60 to 50:50.

[0173] 51. The method of any of embodiments 47 to 50, wherein M2 comprises Ru, preferably is Ru, and the catalytic material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 30:70, preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, and more preferably 5:95 to 6:94.

[0174] 52. The method of any one of embodiments 46 to 51, wherein the catalytic material further comprises Al and O.

[0175] 53. The method of embodiment 52, wherein the catalytic material comprises Ni as the metal M1, and preferably the metal M1 is Ni.

[0176] 54. The method of embodiment 53, wherein the catalytic material further comprises Mg, and the molar ratio of Ni:Mg:Al is preferably in the range of 1:(0.1-12):(0.5-20), more preferably 1:(0.5-8):(1-12), more preferably 1:(1-5):(3-8), more preferably 1:(1.5-3):(3.5-5), and more preferably 1:(2.0-2.4):(4.0-4.4).

[0177] 55. The method of embodiment 53 or 54, 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, and more preferably 99.9 to 100% by weight of the catalyst material consists of Ni, Mg, Al, and O.

[0178] 56. The method of embodiment 53 or 54, 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, and more preferably 99.9 to 100% by weight of the catalyst material consists of M2, Ni, Mg, Al, and O.

[0179] 57. The method of embodiment 52, wherein the catalytic material comprises Co as the metal M1, and preferably the metal M1 is Co.

[0180] 58. The method of embodiment 57, wherein the catalytic material further comprises La, and the molar ratio of Co:La:Al is preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), and more preferably 1:(1.3-1.7):(10-12).

[0181] 59. The method of embodiment 57 or 58, 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, and more preferably 99.9 to 100% by weight of the catalyst material consists of Co, La, Al, O.

[0182] 60. The method of embodiment 58 or 59, 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, and more preferably 99.9 to 100% by weight of the catalyst material consists of M2, Co, La, Al, and O.

[0183] 61. The catalytic material comprises Ru and one or more support materials, wherein Ru is supported on one or more support materials, and the one or more support materials are 20 m 2 46. ​​The process of any one of the preceding embodiments, wherein the catalyst material exhibits a BET specific surface area of ​​1 / g or more, the BET specific surface area being preferably measured according to ISO 9277:2010, and wherein the catalyst material contains 1% by weight or less of Ni and Co, each calculated as the element relative to 100% by weight of the catalyst material.

[0184] 62. The method of embodiment 61, wherein the catalytic material contains 0.5% by weight or less, 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, and more preferably 0.001% by weight or less of Ni and Co, each calculated as the element relative to 100% by weight of the catalytic material.

[0185] 63. The method of embodiment 61, wherein the reactor unit contains 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, and more preferably 0.001% by weight or less of Ni and Co, each calculated as the element relative to 100% by weight of the total contents of the reactor.

[0186] 64. One or more support materials have a BET surface area between 30 and 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, and more preferably 75 to 80 m 2 64. The method of any one of embodiments 61 to 63, wherein the range of 1 / g is

[0187] 65. One or more support materials have a BET surface area greater 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, and more preferably 25 to 35 m 2 65. The method of any one of embodiments 61 to 64, wherein the range of 1 / g is shown.

[0188] 66. The method of any one of embodiments 61 to 65, wherein the one or more support materials exhibit a pore volume in the range of 0.2 to 3 ml / g, preferably 0.4 to 1.5 ml / g, more preferably 0.6 to 1 ml / g, and more preferably 0.8 to 0.85 ml / g, the pore volume preferably being measured according to ISO15901-2:2022.

[0189] 67. The catalyst material has a BET surface area of ​​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, and more preferably 70 to 75 m 2 67. The method of any one of embodiments 61 to 66, wherein the BET surface area is preferably in the range of / g, and is measured according to ISO 9277:2010.

[0190] 68. The method of any one of embodiments 61 to 67, wherein the catalytic material exhibits a pore volume in the range of 0.1 to 2 ml / g, preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, and more preferably 0.3 to 0.35 ml / g, the pore volume preferably being measured according to ISO 15901-2:2022.

[0191] 69. The method of any one of embodiments 61 to 68, wherein 90 to 100 mass %, preferably 95 to 100 mass %, more preferably 99 to 100 mass %, more preferably 99.5 to 100 mass %, and more preferably 99.9 to 100 mass % of Ru, calculated as element, relative to 100 mass % of Ru contained in the catalytic material, is supported on one or more support materials contained in the catalytic material.

[0192] 70. The method of any one of embodiments 61 to 69, wherein Ru is supported on one or more support materials by an 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.

[0193] 71. 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, and rare earth metals, and combinations of two or more thereof, more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, and Nd, and combinations of two or more thereof, more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca, and La, and combinations of two or more thereof, more preferably selected from the group consisting of Al, Zr, and Mg, and combinations of two or more thereof. 71. The method of any one of embodiments 61 to 70, wherein the one or more support materials comprise one or more metal oxides selected from the group consisting of Al2O3, ZrO2, and spinel, and combinations of two or more thereof, preferably ZrO2 and spinel, and combinations of two or more thereof; more preferably the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably comprise ZrO2; more preferably the one or more support materials consist of ZrO2 and / or MgAl2O4, preferably consist of ZrO2.

[0194] 72. The method of embodiment 71, wherein the ZrO2 comprises one or more crystalline phases and / or is amorphous, and the one or more crystalline phases of ZrO2 are selected from the group consisting of the monoclinic, tetragonal, and cubic phases of ZrO2, and mixtures of two or three thereof.

[0195] 73. The method of any one of embodiments 61 to 72, wherein the one or more support materials are substantially free of CaO and / or MgO, preferably substantially free of CaO and MgO, more preferably substantially free of alkaline earth metal oxides, more preferably substantially free of Ca and / or Mg, more preferably substantially free of Ca and Mg, and more preferably substantially free of alkaline earth metals.

[0196] 74. The method of any one of embodiments 61 to 73, wherein the one or more support materials are substantially free of Al2O3 and / or SiO2, preferably substantially free of Al2O3 and SiO2, more preferably substantially free of Al and / or Si, and more preferably substantially free of Al and Si.

[0197] 75. The method of any one of embodiments 61 to 74, wherein the one or more support materials are substantially free of carbon nanotubes, preferably substantially free of elemental carbon, and more preferably substantially free of carbon.

[0198] 76. The method of any one of embodiments 61 to 75, wherein the catalytic material comprises Ru in an amount ranging from 0.5 to 15 wt%, preferably 1 to 10 wt%, more preferably 2 to 8 wt%, more preferably 3 to 6.5 wt%, more preferably 4 to 6 wt%, and more preferably 4.5 to 5.5 wt%, relative to 100 wt% of the total amount of the one or more support materials.

[0199] 77. The method of any one of embodiments 61 to 76, 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, and more preferably 99.9 to 100% by weight of the catalyst material consists of Ru and one or more support materials.

[0200] 78. The method of any one of embodiments 61 to 77, wherein the catalytic material 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 that support Ru, and 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, and mixtures of two or more thereof, more preferably from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH, and KOH, and mixtures of two or more thereof, more preferably from the group consisting of LiOH, NaOH, and KOH, and mixtures of two or more thereof, and more preferably wherein the catalytic material further comprises KOH and / or LiOH, preferably KOH.

[0201] 79. The method of embodiment 78, wherein the catalytic material comprises one or more alkali metal hydroxides in an amount ranging from 0.5 to 15% by weight, preferably from 1 to 10% by weight, more preferably from 2 to 8% by weight, more preferably from 3 to 6.5% by weight, more preferably from 4 to 6% by weight, and more preferably from 4.5 to 5.5% by weight, relative to 100% by weight of the total amount of the one or more support materials.

[0202] 80. The method of any one of embodiments 61 to 79, 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, and more preferably 99.9 to 100% by weight of the catalyst material consists of Ru, one or more alkali metal hydroxides, and one or more support materials.

[0203] 81. The method of any one of embodiments 61 to 80, wherein the catalyst material is in the form of a molding and / or a powder, preferably in the form of a molding, and more preferably in the form of an extrudate.

[0204] 82. The method of embodiment 81, wherein the extrudate has a diameter in the range of 0.5 to 10 mm, preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and more preferably 2.5 to 3.5 mm.

[0205] 83. The method of any one of embodiments 1 to 45, wherein the catalytic material comprises Ni, Ru, and a promoter metal M1′, wherein the catalytic material 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, and Ba, and mixtures of two or more thereof, and the catalytic material further comprises one or more support materials on which Ni, Ru, and the promoter metal M1′ are respectively supported.

[0206] 84. The method of embodiment 83, wherein the catalytic material 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, and more preferably 0.025:1 to 0.035:1.

[0207] 85. The method of embodiment 83 or 84, wherein the promoter metal M1′ is selected from the group consisting of Li, K, Na, Cs, Mg, and Ca, and mixtures of two or more thereof, preferably the group consisting of Li, K, Na, and Cs, and mixtures of two or more thereof, more preferably the group consisting of Li, K, and 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.

[0208] 86. The method of any one of embodiments 83 to 85, wherein the catalytic material 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, and more preferably 2.9:1 to 3:1.

[0209] 87. 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, and rare earth metals and combinations of two or more thereof, more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, and Nd and combinations of two or more thereof, more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca, and La and combinations of two or more thereof, and more preferably selected from the group consisting of Al, Zr, and Mg and combinations of two or more thereof, and more preferably selected from the group consisting of A 87. The method of any one of embodiments 83 to 86, wherein the one or more support materials comprise one or more metal oxides selected from the group consisting of I2O3, ZrO2, and spinel and mixtures of two or more thereof, preferably the group consisting of ZrO2, and spinel and mixtures of two or more thereof, more preferably the group consisting of ZrO2, NiMgO2, and MgAl2O4 and mixtures of two or more thereof; more preferably the one or more support materials comprise MgAl2O4, preferably comprise NiMgO2 and MgAl2O4, more preferably the one or more support materials consist of MgAl2O4 or consist of NiMgO2 and MgAl2O4, preferably consist of NiMgO2 and MgAl2O4.

[0210] 88. The method of any one of embodiments 83 to 87, wherein 90 to 100 mass %, preferably 95 to 100 mass %, more preferably 99 to 100 mass %, more preferably 99.5 to 100 mass %, and more preferably 99.9 to 100 mass % of the Ni and Ru, calculated as elements, respectively, relative to 100 mass % of the Ni and Ru contained in the catalytic material, is supported on one or more support materials contained in the catalytic material.

[0211] 89. The method of any one of embodiments 83 to 88, wherein 90 to 100 mass %, preferably 95 to 100 mass %, more preferably 99 to 100 mass %, more preferably 99.5 to 100 mass %, and more preferably 99.9 to 100 mass % of Ni, Ru, and promoter metal M1′, calculated as elements, respectively, relative to 100 mass % of Ni, Ru, and promoter metal M1′ contained in the catalytic material, are supported on one or more support materials contained in the catalytic material.

[0212] 90. The method of any one of embodiments 83 to 89, wherein the catalytic material comprises 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, and more preferably from 14 to 16% by weight, calculated as the element relative to 100% by weight of the catalytic material.

[0213] 91. The method of any one of embodiments 83 to 90, wherein the catalytic material comprises Ru in an amount ranging from 0.01 to 5%, preferably 0.05 to 2.5%, more preferably 0.1 to 1.5%, more preferably 0.2 to 1%, more preferably 0.3 to 0.8%, and more preferably 0.4 to 0.6%, by weight, calculated as the element relative to 100% by weight of the catalytic material.

[0214] 92. The method of any one of embodiments 83 to 91, wherein the catalytic material comprises 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, and more preferably from 3 to 4% by weight, calculated as the element relative to 100% by weight of the catalytic material.

[0215] 93. The method of any one of embodiments 83 to 92, 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 material consists of Ni, Ru, promoter metal M1′, and one or more support materials, wherein Ni, Ru, and promoter metal M1′ are each present as elements, as oxides, and / or as salts.

[0216] 94. The method of any one of embodiments 83 to 93, wherein the catalytic material comprises 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 catalytic material as their hydroxide salts.

[0217] 95. The method of any one of embodiments 83 to 94, wherein Ru is supported on one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, and the one or more ruthenium salts preferably comprise Ru(NO)(NO3)3, more preferably Ru(NO)(NO3)3 is used as the one or more ruthenium salts.

[0218] 96. The method of any one of embodiments 83 to 95, wherein the catalyst material is in the form of a molding, an extrudate, and / or a powder, preferably in the form of a molding or an extrudate, and more preferably in the form of a molding.

[0219] 97. The method of embodiment 96, wherein the extrudate has a diameter in the range of 0.5 to 10 mm, preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

[0220] 98. The method of embodiment 96, wherein the molding has a diameter in the range of 1 to 20 mm, preferably in the range of 1 to 15 mm.

[0221] 99. The method of any one of embodiments 96 or 98, wherein the molding is four-lobed.

[0222] 100. The process of any one of embodiments 1 to 99, wherein the separation according to (iii) is carried out in a first separator, and the first separator is located downstream of the reactor unit.

[0223] 101. The process of any one of embodiments 1 to 100, wherein the separating according to (iii) comprises cooling the product stream to a temperature in the range of 0 to 100°C, preferably in the range of 30 to 70°C, more preferably in the range of 45 to 55°C.

[0224] 102. The process of any one of the preceding embodiments, wherein the separation according to (iii) comprises compressing the product stream to a pressure in the range of 5 to 100 bar (abs), preferably in the range of 20 to 50 bar (abs), more preferably in the range of 25 to 35 bar (abs).

[0225] 103. The process of any one of embodiments 1 to 102, wherein the separation according to (iv) is carried out in a second separator, the second separator being located downstream of the reactor unit or downstream of the first separator defined in embodiment 101.

[0226] 104. The process of any one of embodiments 1 to 103, wherein the separating according to (iv) comprises heating the product stream or the dehydrated product stream to a temperature in the range of −180 to 0°C, preferably in the range of −100 to −50°C, more preferably in the range of −85 to −75°C.

[0227] 105. The process of any one of embodiments 1 to 104, wherein the separating according to (iv) comprises compressing the product stream or the dehydrated product stream to a pressure in the range of 10 to 100 bar (abs), preferably in the range of 35 to 65 bar (abs), more preferably in the range of 45 to 55 bar (abs).

[0228] 106. The process of any one of the preceding embodiments, further comprising, after (iv) and before (v), heating the NH3 obtained in (iv) to a temperature in the range of 50 to 750°C, preferably in the range of 175 to 575°C, more preferably in the range of 300 to 550°C.

[0229] 107. The process of any one of the preceding embodiments, further comprising, after (iv) and before (v), expanding the NH3 obtained in (iv) to a pressure in the range of 1 to 50 bar (abs), preferably in the range of 1 to 35 bar (abs), more preferably in the range of 1 to 30 bar (abs).

[0230] The present invention will be further explained by the following Reference Examples, Examples and Comparative Examples. [Example]

[0231] The following example was simulated using Aspen Plus software version 12.

[0232] Reference example 1: Ru-containing catalyst material A low-temperature active NH3 reforming catalyst material was provided.

[0233] A catalyst containing Ru (5% by weight) and KOH (5% by weight) supported on ZrO was used. The catalyst was prepared as follows: 5 g samples of 5% by weight Ru on ZrO extrudates obtained from Example 1 were impregnated with a KOH solution. For this purpose, 5 g of the extrudates obtained from Example 1 were divided to form a fraction in the range of 315-500 microns, which was then impregnated via wet 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 at 500°C for 2 hours under an inert atmosphere.

[0234] Additionally, a kinetic model was developed for the provided Ru-containing catalyst material to allow for proper simulation of conversion rates taking into account the boundaries and concepts described herein (see Figure...).

[0235] Reference Example 2: Providing a feed stream containing NH3 In the simulation of the NH3 reforming process with recycle, a reference scenario was defined using approximately 10 t / h of NH3 as the feed stream. Furthermore, the pressure and temperature of the feed stream were set as shown in each example. The NH3-containing feed stream consisted of 99-99.9 vol.% NH3 and 0.1-1 vol.% HO.

[0236] Example 1: Method for reforming NH3 in a polytropic reactor with recycle of unconverted NH3 A reactor unit was set up containing a single polytropic heated reactor containing the Ru-containing catalyst material according to Example 1. The reactor dimensions were fixed at 5 m in length and 2 m in diameter. A feed stream was provided according to Example 2. NH3 reforming was simulated in the polytropic reactor at a pressure of 1 bar (abs) and an initial temperature of 250°C (this temperature was increased along the reactor bed length to reach 350°C at the outlet). The resulting conversion profile is shown in Figure 2, and the properties of the individual process streams are shown in Tables 1a and 1b below, respectively.

[0237] [Table 1]

[0238] From the results shown in Tables 1a and 1b, under steady-state recycle conditions, a conversion of 60% could be measured at the reactor outlet. Residual NH in the H-containing product stream was reduced to 1000 ppm in the separation step.

[0239] Example 2: Method for reforming NH3 in a polytropic reactor with recycle of unconverted NH3 A reactor unit was set up containing a single polytropic heated reactor containing the Ru-containing catalyst material according to Example 1. The reactor dimensions were fixed at 5 m in length and 2 m in diameter. A feed stream according to Example 2 was provided. NH reforming was simulated in the polytropic reactor at a pressure of 1 bar (abs) and an initial temperature of 450°C (this temperature was increased along the reactor bed length to reach 550°C at the outlet). The resulting conversion profile is shown in Figure 3, and the properties of the individual process streams are shown in Tables 2a and 2b below, respectively.

[0240] [Table 2]

[0241] The results shown in Tables 2a and 2b show that under steady-state recycle conditions, a conversion of 92% was measured at the reactor outlet. This indicates that the increased temperature profile was beneficial to the overall conversion. As a result, relatively less NH3 was available for recycle than in the process of Example 1. Residual NH3 in the H2-containing product stream was reduced to 1000 ppm in the separation step.

[0242] Example 3: Method for reforming NH3 in a polytropic reactor with recycle of unconverted NH3 A reactor unit was set up containing a single polytropic heated reactor containing the Ru-containing catalyst material according to Example 1. The reactor dimensions were fixed at 5 m in length and 2 m in diameter. A feed stream according to Example 2 was provided. NH reforming was simulated in the polytropic reactor at a high pressure of 30 bar (abs) and an initial temperature of 250°C (this temperature was increased along the reactor bed length to reach 350°C at the outlet). The resulting conversion profile is shown in Figure 4, and the properties of the individual process streams are shown in Tables 3a and 3b below, respectively.

[0243] [Table 3]

[0244] The results shown in Table 3 show that under steady state recycle conditions, a conversion of 15% could be measured at the reactor outlet.

[0245] Example 4: Method for reforming NH3 in an adiabatic reactor with recycle of unconverted NH3 A reactor unit was set up containing a single adiabatic reactor containing the Ru-containing catalyst material according to Example 1. The reactor dimensions were fixed at 5 m in length and 2 m in diameter. A feed stream was provided according to Example 2. NH reforming was simulated for the polytropic reactor at a pressure of 1 bar (abs) and an initial temperature of 500°C. The resulting conversion profile is shown in Figure 5, and the properties of the individual process streams are shown in Tables 4a and 4b below, respectively.

[0246] [Table 4]

[0247] From the results shown in Tables 4a and 4b, under steady-state recycle conditions, a conversion of 35% could be measured at the reactor outlet. Residual NH in the H-containing product stream was reduced to 1000 ppm in the separation step.

[0248] Example 5: Method for reforming NH3 in a reactor cascade containing two adiabatic reactors with recycle of unconverted NH3 A reactor unit was set up containing two adiabatic reactors arranged in series, with a heater positioned between the reactors to heat the outlet stream of the upstream reactor. Both reactors contained Ru-containing catalyst material according to Example 1. Each reactor had a length of 5 m and a diameter of 2 m. A feed stream according to Example 2 was provided. NH reforming was simulated for the reactor cascade at a pressure of 1 bar (abs) and an initial temperature of 500°C for each reactor. The resulting conversion profile is shown in Figure 6, and the characteristics of the individual process streams are shown in Tables 5a and 5b below, respectively.

[0249] [Table 5]

[0250] The results shown in Tables 5a and 5b show that under steady-state recycle conditions, a conversion of 54% could be obtained at the reactor unit outlet. In particular, the conversion after the first reactor was 35%, which was comparable to the conversion obtained in Example 4. Residual NH in the H-containing product stream was reduced to 1000 ppm in the separation step.

[0251] BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a parity plot of simulated and experimental values ​​for a Ru-containing low-temperature NH3 reforming catalyst material according to a reference example.

[0252] References -US8961923B2 -US8691182B2 -US8464515B2 -WO2019 / 038251A1 -Banares-Alcantara et al., Applied Energy 2021,282,116009

Claims

1. NH ３ A method for modifying a material comprising the steps of: (i) NH ３ to a reactor unit, said reactor unit having a reactor unit inlet and a reactor unit outlet, said reactor unit containing a catalyst material; (ii) contacting the feed stream with the catalytic material in the reactor unit to produce H ２ , N ２ , N.H. ３ , and optionally H ２ obtaining a product stream comprising O, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 750°C; (iii) optionally, H in the product stream obtained in (ii); ２ Separate O and H ２ , N ２ , and N.H. ３ obtaining a dehydrated product stream comprising: (iv) extracting NH from the product stream obtained in (ii) or the dehydrated product stream obtained in (iii). ３ Separate and N ２ and H ２ obtaining a purified product stream comprising: (v) The separated NH obtained in (iv) ３ (i) A method comprising:

2. 90-100% by volume of said feed stream from (i) is NH ３ The method of claim 1, comprising:

3. (i) providing the feed stream to the reactor unit for 400 to 40,000 h －１ 3. The method according to claim 1, wherein the gas hourly space velocity is in the range of

4. 3. The method of claim 1 or 2, wherein the contacting according to (ii) comprises transferring heat from a reaction of the chemical conversion process, and the heat transfer is accomplished using a heat exchanger or a heat pump.

5. 5. The method of claim 4, wherein the heat transferred is obtained from an exothermic reaction or the heat transferred is excess heat from heat used to carry out an autothermal or endothermic reaction.

6. 3. The method of claim 1 or 2, wherein the reactor unit comprises one or more reactors, and the catalytic material is contained in the one or more reactors.

7. 7. The method of claim 6, wherein each of the one or more reactors, independently of one another, is selected from the group consisting of a polytropic reactor, a two-stage reactor, an adiabatic reactor, and a combination of a polytropic reactor and an adiabatic reactor.

8. 7. The method of claim 6, wherein each of the one or more reactors is independently tubular.

9. 7. The method of claim 6, wherein the reactor unit comprises, the reactor unit inlet is a reactor inlet, and the reactor unit outlet is a reactor outlet.

10. the reactor unit includes two or more reactors, the two reactors being a first reactor and a second reactor, the first reactor being disposed upstream of the second reactor, the first reactor having a first reactor inlet and a first reactor outlet, the reactor unit inlet being the first reactor inlet, and the reactor unit outlet being the second reactor outlet; The providing according to (i) and the contacting according to (ii) comprises the steps of: (i.1) NH ３ to the first reactor to obtain an intermediate stream; (ii.1) contacting the feed stream with the catalytic material in the first reactor, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 750°C; (i.2) feeding the intermediate stream obtained in (i.1) into the second reactor; (ii.2) contacting the intermediate stream with the catalytic material in the second reactor, wherein the contacting is carried out at a pressure in the range of 1 to 100 bar (abs) and a temperature in the range of 50 to 700°C; H ２ , N ２ , N.H. ３ , and optionally H ２ obtaining said product stream comprising O. The method of claim 6, comprising:

11. 3. The method of claim 1 or 2, wherein the reactor unit comprises one or more reactors, and the catalytic material is contained in one or more of the one or more reactors.

12. 3. The method of claim 1 or 2, wherein the catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

13. The catalytic material comprises Ru and one or more support materials, the Ru being supported on the one or more support materials, and the one or more support materials are 20 m ２ 3. The method according to claim 1, wherein the catalytic material exhibits a BET specific surface area of ​​1 / g or more, and the catalytic material contains 1% by mass or less of Ni and Co, each calculated as an element relative to 100% by mass of the catalytic material.

14. 3. The method of claim 1, wherein the catalytic material comprises Ni, Ru, and a promoter metal M1′, the catalytic material 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, and Ba, and mixtures of two or more thereof, and the catalytic material further comprises one or more support materials on which the Ni, Ru, and promoter metal M1′ are respectively supported.

15. After (iv) and before (v), NH obtained in (iv) ３ The method of claim 1 or 2, further comprising expanding the

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