High pressure and low temperature recycle NH3 reforming process

Abstract

The present invention relates to a process for NH3 reforming, the process comprising (i) feeding a feed stream comprising NH3 to a reactor unit, where the reactor unit has a reactor unit inlet and a reactor unit outlet, where the reactor unit comprises a catalytic material; (ii) contacting the feed stream with the catalytic material in the reactor unit to obtain a product stream comprising H2, N2, NH3 and optionally H2O, where the contacting is carried out at a pressure in the range of from 1 to 100 bar (absolute) and at a temperature in the range of from 50 DEG C to 750 DEG C; (iii) optionally separating H2O in the product stream obtained in (ii) to obtain an dehydrated product stream comprising H2, N2 and NH3; (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) recycling the separated NH3 obtained in (iv) to (i).

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, unreacted NH3 from the reactor outlet will be separated and recycled to the reactor inlet. The hydrogen contained in the product stream is extracted under high pressure reaction conditions. Background Art

[0002] NH3 is considered as a future energy carrier, capable of storing chemically large amounts of H2. The reforming of NH3 according to formula (I) is the final step to reincorporate hydrogen into chemical processes or other applications. Since the NH3 reforming step itself is an endothermic reaction (45.6 kJ / mol), additional energy must be invested. Moreover, the evaporation of NH3 from liquid to gaseous state should be considered as a high energy consumption step (23 kJ / mol).

[0003]

[0004] The endothermic characteristics of the reforming step are conducive to high temperature to achieve high NH3 conversion. However, thermodynamic limitations must be considered in this regard. This is particularly applicable to pressure, because considering thermodynamic limitations, high pressure is typically undesirable. However, from the perspective of hydrogen as the target product, high pressure will be advantageous. The method of the present invention generally follows the NH3 reforming concept, wherein NH3 is subsequently separated from the reactor outlet stream and fed back to the reactor inlet, thereby allowing the method design to avoid certain restrictions. In particular, the combination of temperature and pressure settings (depending on downstream applications) can be applied to the method design of the present invention. For example, a combination of low temperature and high pressure conditions can be applied.

[0005] US 8961923 B2 relates to an autothermal ammonia cracker. A process for the autothermal cracking of ammonia with air or oxygen is disclosed, wherein a gas mixture containing ammonia and oxygen is preferably combusted at a specific combination of temperature and pressure, for example at a temperature above 1200° C. and a pressure of 10 bar or at a temperature of 1300° C. and a pressure of 1 bar.

[0006] US 8691182 B2 relates to a process for cracking ammonia, wherein a mixture of ammonia and an oxygen-containing gas is combusted. The combustion preferably takes place at a temperature above 1100° C. and preferably at a pressure of about 1 atmosphere.

[0007] US 8464515 B2 relates to an ammonia burning internal combustion engine, which comprises in particular a reformer for reforming ammonia, located upstream of a combustion chamber.

[0008] US2578193 discloses an ammonia dissociator in which the dissociation of ammonia can be carried out at a temperature of about 650°C (1200°F).

[0009] WO 2019 / 038251 A1 relates to an autothermal ammonia cracking process. In particular, a method for producing a product gas containing nitrogen and hydrogen from ammonia is disclosed, the method comprising a step of non-catalytically partially oxidizing ammonia with an oxygen-containing gas.

[0010] Banares-Alcantara et al. disclose predictions of ammonia as an energy carrier, particularly its role in combined cycle gas turbines for power generation, in Applied Energy 2021, 282, 116009. In particular, a modeled NH3 reformer is disclosed therein with an assumed conversion of 99% at 850°C.

[0011] As noted above, the NH3 reforming process is a balanced reaction of heat absorption and volume increase. This means that in order to achieve high conversion, low pressure and high temperature are required. However, for the use of the hydrogen obtained from the NH3 reforming, it is typically necessary to provide a hydrogen stream with a relatively high pressure and a relatively low temperature. Therefore, it is necessary to provide a novel method in which a product stream from the NH3 reforming can be obtained with a relatively high pressure and a relatively low temperature. DETAILED DESCRIPTION

[0012] Thus, it has been surprisingly found that the 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 in particular the pipework is compact and according to which hydrogen is produced in particular at high pressure, whereby the temperature in particular is relatively low and the space for the equipment can be quite small.

[0013] The advantage of this recycle process concept is that thermodynamic limitations are circumvented and a dedicated compact process design for any downstream application is developed. In particular, considering the low reaction temperature combined with the high pressure H2 product, the process of the present invention is advantageous in terms of resource and energy efficiency, especially in terms of its operating costs.

[0014] In particular, the NH3 reforming process characterized by the recycle mode according to the present invention allows a process design that overcomes thermodynamic limitations in terms of temperature and pressure. This allows a dedicated process design for any downstream application and provides a low OPEX and CAPEX solution for the NH3 reforming process.

[0015] Therefore, the present invention relates to a method for NH3 reforming, the method comprising

[0016] (i) feeding a feed stream comprising NH3 into a reactor unit, wherein the reactor unit has a reactor unit inlet and a reactor unit outlet, wherein the reactor unit comprises a catalytic material;

[0017] (ii) contacting the feed stream with the catalytic material in the reactor unit to obtain a product stream comprising H2, N2, NH3 and optionally H2O, wherein the contacting is carried out at a pressure in the range of 1 to 100 bara and at a temperature in the range of 50°C to 750°C;

[0018] (iii) optionally separating H2O in the product stream obtained in (ii) to obtain a dehydrated product stream comprising H2, N2 and NH3;

[0019] (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;

[0020] (v) recycling the separated NH3 obtained in (iv) to (i).

[0021] Preferably, 90 to 100 vol-%, more preferably 93 to 100 vol-%, more preferably 95 to 100 vol-% of the feed stream according to (i) consists of NH3.

[0022] Preferably, the feed stream fed to the reactor unit according to (i) is in the range of 400 to 40,000 h -1 In the range of 2,000 to 12,000 h -1 The reaction is carried out at a gas hourly space velocity within the range of .

[0023] Preferably, feeding the feed stream into the reactor unit according to (i) is 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.

[0024] Preferably, feeding the feed stream into the reactor unit according to (i) is 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.

[0025] Preferably, the feed stream to the reactor unit according to (i) is between 250 and 55000 m 3 In the range of 5000 to 45000 m / h, more preferably in the range of 5000 to 45000 m / h 3 In the range of 9250 to 41250 m / h, more preferably in the range of 9250 to 41250 m / h 3The flow rate is carried out in the range of 200 ℃ and 100 ℃.

[0026] Preferably, the feed stream to the reactor unit according to (i) is between 50 and 2500 m 3 In the range of 250 to 1000 m / h, more preferably in the range of 250 to 1000 m / h 3 In the range of 400 to 725 m / h, more preferably in the range of 400 to 725 m / h 3 The flow rate is carried out in the range of 200 ℃ and 100 ℃.

[0027] Preferably, the feed stream further comprises H2O, wherein the feed stream more preferably comprises 0 to 1 vol-%, more preferably 0 to 0.5 vol-%, more preferably 0 to 0.21 vol-% H2O.

[0028] Preferably, the feed stream further comprises H2, wherein the feed stream more preferably comprises 0 to 1 vol-%, more preferably 0 to 0.1 vol-%, more preferably 0 to 0.01 vol-% H2.

[0029] Preferably, the feed stream further comprises N2, wherein the feed stream more preferably comprises 0 to 5 vol-%, preferably 0 to 1 vol-%, more preferably 0 to 0.5 vol-% N2.

[0030] Preferably, the contacting according to (ii) is carried out at a pressure in the range of 5 to 55 bar (absolute pressure), more preferably in the range of 10 to 50 bar (absolute pressure), more preferably in the range of 15 to 45 bar (absolute pressure), 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 (absolute pressure).

[0031] Preferably, the contacting according to (ii) is carried out at a temperature in the range of 100°C to 750°C, more preferably in the range of 160°C to 650°C, more preferably in the range of 170°C to 580°C, more preferably in the range of 180°C to 570°C, more preferably in the range of 190°C to 560°C, more preferably in the range of 200°C to 550°C, more preferably in the range of 210°C to 540°C, more preferably in the range of 220°C to 530°C, more preferably in the range of 230°C to 520°C, more preferably in the range of 240°C to 510°C, more preferably in the range of 250°C to 500°C.

[0032] Preferably, the contacting according to (ii) comprises increasing the temperature from the reactor unit inlet to the reactor unit outlet.

[0033] In the case where 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 is 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 further preferred that the temperature is 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.

[0034] According to the present invention, it is preferred that the contacting according to (ii) comprises transferring heat from the reaction of the chemical conversion process, wherein the transferring heat is performed using a heat exchanger or a heat pump.

[0035] In the case where the contacting according to (ii) comprises transferring heat from a reaction of a chemical conversion process, wherein the transferring heat is carried out using a heat exchanger or a heat pump, preferably, the heat transferred is obtained from an exothermic reaction, or wherein the heat transferred is excess heat to the heat used to carry out an autothermal reaction or an endothermic reaction.

[0036] In the case where the heat transferred is obtained from an exothermic reaction, preferably, the exothermic reaction includes one or more of the following: methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and selective oxidation of one or more of alkanes, alkenes and alkynes (more preferably selective oxidation of one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid).

[0037] In the case where the heat transferred is excess heat to that used to carry out an endothermic reaction, preferably 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.

[0038] In the case where the heat transferred is excess heat to the heat used to carry out the autothermal reaction, preferably the autothermal reaction is selected from the group consisting of: autothermal reforming of natural gas and hydrocarbons, including partial oxidation (POx) of hydrocarbons, wherein the hydrocarbons are selected from (C1-C 10 )alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0039] According to the present invention, it is preferred that the reactor unit comprises one or more reactors, wherein the catalytic material is contained in the one or more reactors.

[0040] In the case where the reactor unit comprises one or more reactors (wherein the catalytic material is contained in the one or more reactors), it is preferred that 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.

[0041] Furthermore, it is preferred that each of the one or more reactors is independently tubular, wherein the tubular reactor preferably comprises, more preferably consists of, 1 to 15,000 tubes, more preferably 100 to 12,000 tubes, and more preferably 500 to 5,000 tubes, wherein each of these tubes independently of each other 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.

[0042] Furthermore, it is preferred that each of the one or more reactors independently of each other 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.

[0043] Furthermore, it is preferred that each of the one or more reactors independently of each other 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.

[0044] Furthermore, it is preferred that each of the one or more reactors independently has a temperature in the range of 0.5 to 150 m 3 In the range of 1 to 80 m 3 In the range of 2 to 50 m 3 In the range of 3 to 30 m 3 In the range of 4 to 20 m 3 In the range of 5.0 to 16.5 m 3 volume within the range of .

[0045] Additionally and independently thereof, it is preferred that the reactor unit comprises, preferably consists of, one reactor, wherein the reactor unit inlet is the reactor inlet and wherein the reactor unit outlet is the reactor outlet.

[0046] It is further preferred that the reactor unit comprises two or more reactors, preferably two adiabatic reactors, more preferably consists of two or more reactors, preferably two adiabatic reactors, the two reactors being a first reactor and a second reactor, wherein the first reactor is arranged upstream of the second reactor, wherein the first reactor has a first reactor inlet and a first reactor outlet, wherein the reactor unit inlet is the first reactor inlet, and wherein the reactor unit outlet is the second reactor outlet,

[0047] wherein the feeding according to (i) and the contacting according to (ii) comprise

[0048] (i.1) feeding the feed stream comprising NH3 into the first reactor to obtain an intermediate stream;

[0049] (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 (absolute) and at a temperature in the range of 50° C. to 750° C.;

[0050] (i.2) feeding the intermediate stream obtained in (i.1) into the second reactor;

[0051] (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 (absolute) and at a temperature in the range of 50° C. to 700° C.;

[0052] To obtain the product stream comprising H2, N2, NH3 and optionally H2O.

[0053] In the case where the reactor unit comprises two or more reactors, it is preferred that the catalytic material is contained by one or both of the two reactors, wherein the catalytic material is more preferably contained by the first reactor and the second reactor.

[0054] Additionally and independently thereof, it is preferred that feeding the intermediate stream into the second reactor according to (i.2) is carried out at a pressure in the range of 1 to 100 bar (absolute), more preferably in the range of 5 to 50 bar (absolute).

[0055] Additionally and independently thereof, it is preferred that feeding the intermediate stream into the second reactor according to (i.2) is carried out at a temperature in the range of 250 to 650 °C, more preferably in the range of 400 to 600 °C.

[0056] Additionally and independently thereof, it is preferred that the feeding of the intermediate stream into the second reactor according to (i.2) is carried out at the same pressure and at the same temperature as the feeding of the feed stream into the first reactor according to (i.1).

[0057] In addition and independently thereof, it is preferred that the contacting according to one or both of (ii.1) and (ii.2) is carried out at a pressure in the range of 5 to 80 bar (absolute pressure), more preferably in the range of 10 to 60 bar (absolute pressure), more preferably in the range of 15 to 45 bar (absolute pressure), 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 (absolute pressure).

[0058] In addition and independently thereof, it is preferred that the contacting according to one or both of (ii.1) and (ii.2) is carried out at a temperature in the range of 100°C to 750°C, more preferably in the range of 160°C to 650°C, more preferably in the range of 170°C to 580°C, more preferably in the range of 180°C to 570°C, more preferably in the range of 190°C to 560°C, more preferably in the range of 200°C to 550°C, more preferably in the range of 210°C to 540°C, more preferably in the range of 220°C to 530°C, more preferably in the range of 230°C to 520°C, more preferably in the range of 240°C to 510°C, more preferably in the range of 250°C to 500°C.

[0059] Additionally and independently thereof, it is preferred that the contacting according to one or both of (ii.1) and (ii.2) comprises increasing the temperature from the reactor inlet to the reactor outlet.

[0060] In the case where the contacting according to one or both of (ii.1) and (ii.2) comprises increasing the temperature from the reactor inlet to the reactor outlet, it is preferred that the temperature is 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 is 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.

[0061] Additionally and independently thereof, it is preferred that the contacting according to one or both of (ii.1) and (ii.2) comprises transferring heat from a reaction of the chemical conversion process, wherein transferring heat is performed using a heat exchanger or a heat pump.

[0062] In the case where the contacting according to one or both of (ii.1) and (ii.2) includes transferring heat from a reaction of a chemical conversion process, wherein the heat is transferred using a heat exchanger or a heat pump, preferably, the heat transferred is obtained from an exothermic reaction, or wherein the heat transferred is excess heat to the heat used to carry out an autothermal reaction or an endothermic reaction.

[0063] In the case where the heat transferred is obtained from an exothermic reaction, preferably, the exothermic reaction includes one or more of the following: methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and selective oxidation of one or more of alkanes, alkenes and alkynes (more preferably selective oxidation of one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid).

[0064] In the case where the heat transferred is excess heat to that used to carry out an endothermic reaction, preferably 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.

[0065] In the case where the heat transferred is excess heat to the heat used to carry out the autothermal reaction, preferably the autothermal reaction is selected from the group consisting of: autothermal reforming of natural gas and hydrocarbons, including partial oxidation (POx) of hydrocarbons, wherein the hydrocarbons are selected from (C1-C 10 )alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0066] Additionally and independently thereof, it is preferred that the reactor unit comprises two or more reactors, wherein the reactor unit further comprises one or more heaters, wherein the heater is arranged between two reactors.

[0067] In the case where the reactor unit comprises two or more reactors, it is preferred that the reactor unit comprises two reactors, wherein the reactor unit further comprises a heater, wherein the heater is arranged downstream of the first reactor and upstream of the second reactor for heating the intermediate stream.

[0068] According to the present invention, it is preferred that the reactor unit comprises one or more reactors, wherein the catalytic material is contained by one or more of the one or more reactors.

[0069] Preferably, the catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

[0070] In the case where the catalytic material comprises a metal M1 (wherein M1 is Ni, Co, or Ni and Co), preferably, the catalytic material further comprises a metal M2, which is selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably selected from the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably selected from the group consisting of K, Ba, Mo, Fe, Ru and mixtures of two or more thereof, wherein M2 more preferably comprises Fe, Ru, or Fe and Ru, wherein more preferably M2 comprises Ru, wherein more preferably M2 is Ru.

[0071] In addition and independently thereof, it is preferred that the catalytic material further comprises one or more carrier materials on which the metal M1 or the metal M1 and M2 are loaded, wherein the one or more carrier materials are more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2 and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2 and a mixture thereof, wherein more preferably the carrier material comprises Al2O3.

[0072] In addition and independently thereof, it is preferred that the catalytic material shows 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.

[0073] In addition and independently thereof, it is preferred that M2 comprises Fe, more preferably is Fe, and wherein the catalytic material shows 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.

[0074] In addition and independently thereof, it is preferred that M2 comprises Ru, more preferably is Ru, and wherein the catalytic material shows 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.

[0075] Additionally and independently thereof, it is preferred that the catalytic material further comprises Al and O.

[0076] In the case where the catalytic material further contains Al and O, it is preferred that the catalytic material contains Ni as the metal M1, wherein more preferably the metal M1 is Ni.

[0077] In the case where the catalytic material comprises Ni as the metal M1, it is preferred that the catalytic material further comprises Mg, wherein the Ni:Mg:Al molar ratio is more preferably in the range of 1:(0.1–12):(0.5–20), more preferably 1:(0.5–8):(1–12), more preferably 1:(1–5):(3–8), more preferably 1:(1.5–3):(3.5–5), and more preferably 1:(2.0–2.4):(4.0–4.4).

[0078] In addition and independently thereof, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ni, Mg, Al and O.

[0079] In addition and independently thereof, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Ni, Mg, Al and O.

[0080] In the case where the catalytic material further comprises Al and O, it is preferred that the catalytic material comprises Co as the metal M1, wherein the metal M1 is more preferably Co.

[0081] In the case where the catalytic material comprises Co as the metal M1, it is preferred that the catalytic material further comprises La, wherein the Co:La:Al molar ratio is more preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), and more preferably 1:(1.3-1.7):(10-12).

[0082] In addition and independently thereof, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Co, La, Al and O.

[0083] In addition and independently thereof, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Co, La, Al and O.

[0084] According to the present invention, it is preferred that the catalytic material comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, wherein the one or more support materials show 20m 2 / g or more BET surface area, wherein the BET surface area is preferably determined according to ISO 9277:2010, and wherein the catalytic material contains 1 wt.-% or less Ni and Co, calculated as the respective elements and based on 100 wt.-% of the catalytic material.

[0085] In the case where the catalytic material comprises Ru and one or more support materials, it is preferred that the catalytic material contains 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, and more preferably 0.001 wt.-% or less of Ni and Co, calculated as the respective elements and based on 100 wt.-% of the catalytic material.

[0086] In the case where the catalytic material comprises Ru and one or more support materials, it is also preferred that the reactor unit contains Ni and Co in an amount of 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less and more preferably 0.001 wt.-% or less, calculated as the respective elements and in a total content based on 100 wt.-% of the reactor.

[0087] Additionally and independently thereof, it is preferred that the one or more support materials exhibit a relative humidity 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 The BET surface area is in the range of 1000 Å / g.

[0088] Additionally and independently thereof, it is preferred that the one or more support materials exhibit a range of from 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 35m 2 The BET surface area is in the range of 1000 Å / g.

[0089] Additionally and independently thereof, it is preferred that the one or more support materials show a pore volume in the range of 0.2 to 3 ml / g, more preferably 0.4 to 1.5 ml / g, more preferably 0.6 to 1 ml / g, and more preferably 0.8 to 0.85 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0090] Additionally and independently thereof, it is preferred that the catalytic material exhibits a temperature range of 20 to 800 m 2 / g, more preferably 30 to 500m 2 / g, more preferably 40 to 300m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, and more preferably 70 to 75m 2The BET surface area is preferably in the range of 1000 Å / g, wherein the BET surface area is preferably determined according to ISO 9277:2010.

[0091] In addition and independently thereof, it is preferred that the catalytic material shows a pore volume in the range of 0.1 to 2 ml / g, more preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, and more preferably 0.3 to 0.35 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0092] In addition and independently thereof, it is preferred that, calculated as element and based on 100 wt.-% of Ru contained in the catalytic material, 90 to 100 wt.-%, more preferably 95 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of Ru is supported on the one or more support materials contained in the catalytic material.

[0093] In addition and independently thereof, it is preferred that Ru is loaded on the one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, wherein the one or more ruthenium salts more preferably include Ru(NO)(NO3)3, wherein Ru(NO)(NO3)3 is more preferably used as the one or more ruthenium salts.

[0094] Additionally and independently thereof, it is preferred that the one or more support materials are selected from the group consisting of metal oxides, wherein the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals and rare earth metals (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca and La (including combinations of two or more thereof), more preferably selected from the group consisting of A group consisting of Al, Zr and Mg (including combinations of two or more thereof), wherein more preferably the one or more carrier materials contain one or more metal oxides, and the one or more metal oxides are selected from the group consisting of Al2O3, ZrO2 and spinel (including mixtures of two or more thereof), preferably selected from the group consisting of ZrO2 and spinel (including mixtures of two or more thereof), wherein more preferably the one or more carrier materials contain ZrO2 and / or MgAl2O4, preferably ZrO2, wherein more preferably the one or more carrier materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0095] In the case where the one or more support materials comprise ZrO2, preferably, the ZrO2 comprises one or more crystalline phases and / or is amorphous, wherein the one or more crystalline phases of ZrO2 are selected from the group consisting of: monoclinic, tetragonal and cubic phases of ZrO2 (including mixtures of two or three thereof).

[0096] Additionally and independently thereof, 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.

[0097] Additionally and independently thereof, 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.

[0098] Additionally and independently thereof, it is preferred that the one or more support materials are substantially free of carbon nanotubes, more preferably substantially free of elemental carbon, and more preferably substantially free of carbon.

[0099] In addition and independently thereof, 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.-%, based on a total amount of 100 wt.-% of the one or more support materials.

[0100] In addition and independently thereof, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ru and the one or more support materials.

[0101] In addition and independently thereof, it is preferred that the catalytic material further comprises one or more alkali metal hydroxides and / or alkaline earth metal hydroxides, wherein the one or more alkali metal hydroxides and / or alkaline earth metal hydroxides are loaded on the one or more support materials loaded with Ru, wherein the alkali metal hydroxide and / or alkaline earth metal hydroxide is more preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH and KOH (including mixtures of two or more thereof), more preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH and KOH (including mixtures of two or more thereof), more preferably selected from the group consisting of LiOH, NaOH and KOH (including mixtures of two or more thereof), wherein more preferably the catalytic material further comprises KOH and / or LiOH, preferably KOH.

[0102] In case where the catalytic material further comprises one or more alkali metal hydroxides 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 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.-%, based on a total amount of 100 wt.-% of the one or more support materials.

[0103] In addition and independently thereof, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ru, the one or more alkali metal hydroxides and the one or more support materials.

[0104] Additionally and independently thereof, it is preferred that the catalytic material is in the form of a molding and / or in the form of a powder, more preferably in the form of a molding, and more preferably in the form of an extrudate.

[0105] Where the catalytic material is in the form of extrudates, it is preferred that the extrudates have a diameter in the range of 0.5 to 10 mm, more preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and more preferably 2.5 to 3.5 mm.

[0106] According to the present invention, it is further preferred that the catalytic material comprises Ni, Ru and a promoter metal M1', wherein the catalytic material shows a Ru:Ni weight ratio in the range of 0.0001:1 to 0.5:1, wherein the promoter metal M1' is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr and Ba (including mixtures of two or more thereof), and wherein the catalytic material further comprises one or more support materials on which Ni, Ru and the promoter metal M1' are respectively loaded.

[0107] In cases where the catalytic material comprises Ni, Ru and a promoter metal M1', it is preferred that the catalytic material shows a Ru:Ni weight 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.

[0108] In addition and independently thereof, it is preferred that the promoter metal M1' is selected from the group consisting of Li, K, Na, Cs, Mg and Ca (including mixtures of two or more thereof), more preferably selected from the group consisting of Li, K, Na and Cs (including mixtures of two or more thereof), more preferably selected from the group consisting of Li, K and Na (including mixtures of two or more thereof), wherein more preferably the promoter metal M1' is Li, K, or Li and K, wherein more preferably the promoter metal M1' is K, wherein more preferably the promoter metal M1' consists of Li, K, or Li and K, wherein more preferably the promoter metal M1' consists of K.

[0109] In addition and independently thereof, it is preferred that the catalytic material shows 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.

[0110] Additionally and independently thereof, it is preferred that the one or more support materials are selected from the group consisting of metal oxides, wherein the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals and rare earth metals (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca and La (including combinations of two or more thereof), and more preferably selected from the group consisting of Al, Zr and Mg (including combinations of two or more thereof), wherein more preferably The one or more support materials comprise one or more metal oxides, and the one or more metal oxides are selected from the group consisting of Al2O3, ZrO2 and spinel (including mixtures of two or more thereof), preferably selected from the group consisting of ZrO2 and spinel (including mixtures of two or more thereof), more preferably selected from the group consisting of ZrO2, NiMgO2 and MgAl2O4 (including mixtures of two or more thereof), wherein more preferably the one or more support materials comprise MgAl2O4, preferably NiMgO2 and MgAl2O4, wherein more preferably the one or more support materials consist of MgAl2O4, or consist of NiMgO2 and MgAl2O4, preferably consist of NiMgO2 and MgAl2O4.

[0111] In addition and independently thereof, it is preferred that 90 to 100 wt.-%, more preferably 95 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of Ni and Ru, calculated as the respective elements and based on 100 wt.-% of Ni and Ru contained in the catalytic material, are supported on the one or more support materials contained in the catalytic material.

[0112] In addition and independently thereof, it is preferred that 90 to 100 wt.-%, more preferably 95 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of Ni, Ru and promoter metal M1', calculated as the respective elements and based on 100 wt.-% of Ni, Ru and promoter metal M1' contained in the catalytic material, are supported on the one or more support materials contained in the catalytic material.

[0113] In addition and independently thereof, it is preferred that the catalytic material comprises Ni in an amount in the range of 1 to 75 wt.-%, more preferably 3 to 60 wt.-%, more preferably 5 to 40 wt.-%, more preferably 10 to 25 wt.-%, more preferably 12 to 18 wt.-%, and more preferably 14 to 16 wt.-%, calculated as the element and based on 100 wt.-% of the catalytic material.

[0114] In addition and independently thereof, it is preferred that the catalytic material contains Ru in an amount in the range of 0.01 to 5 wt.-%, more preferably 0.05 to 2.5 wt.-%, more preferably 0.1 to 1.5 wt.-%, more preferably 0.2 to 1 wt.-%, more preferably 0.3 to 0.8 wt.-%, and more preferably 0.4 to 0.6 wt.-%, calculated as the element and based on 100 wt.-% of the catalytic material.

[0115] In addition and independently thereof, it is preferred that the catalytic material comprises the promoter metal M1' in an amount in the range of 0.05 to 25 wt.-%, more preferably 0.1 to 15 wt.-%, more preferably 0.5 to 10 wt.-%, more preferably 1 to 8 wt.-%, more preferably 2 to 5 wt.-%, and more preferably 3 to 4 wt.-%, calculated as the element and based on 100 wt.-% of the catalytic material.

[0116] In addition and independently thereof, it is preferred that 95 to 100 wt.-%, more preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ni, Ru, the promoter metal M1' and the one or more support materials, wherein Ni, Ru and the promoter metal M1' may be present as elements, oxides and / or salts, respectively.

[0117] In addition and independently thereof, it is preferred that the catalytic material comprises the one or more promoter metals M1' as hydroxides, bicarbonates and / or carbonates, more preferably as hydroxides and / or bicarbonates, and more preferably as hydroxides, wherein more preferably the promoter metal M1 is contained in the catalytic material as its hydroxide salt.

[0118] In addition and independently thereof, it is preferred that Ru is loaded on the one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, wherein the one or more ruthenium salts more preferably include Ru(NO)(NO3)3, wherein Ru(NO)(NO3)3 is more preferably used as the one or more ruthenium salts.

[0119] Additionally and independently thereof, it is preferred that the catalytic material is in the form of a molding, in the form of an extrudate, and / or in the form of a powder, more preferably in the form of a molding or an extrudate, and more preferably in the form of a molding.

[0120] Where the catalytic material is in the form of extrudates, it is preferred that the extrudates have a diameter in the range of 0.5 to 10 mm, more preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and more preferably 2.5 to 3.5 mm.

[0121] In the case where the catalytic material is in the form of a molded article, it is preferred that the molded article has a diameter in the range of 1 to 20 mm, more preferably in the range of 1 to 15 mm.

[0122] Additionally and independently thereof, it is preferred that the molding has a quadrilobe shape.

[0123] According to the present invention, it is preferred that the separation according to (iii) is carried out in a first separator, wherein the first separator is arranged downstream of the reactor unit.

[0124] Preferably, the separation according to (iii) comprises cooling the product stream to a temperature in the range of 0 to 100°C, more preferably in the range of 30 to 70°C, more preferably in the range of 45 to 55°C.

[0125] Preferably, the separation according to (iii) comprises compressing the product stream to a pressure in the range of 5 to 100 bara, more preferably in the range of 20 to 50 bara, more preferably in the range of 25 to 35 bara.

[0126] Preferably, the separation according to (iv) is carried out in a second separator, wherein the second separator is arranged downstream of the reactor unit or downstream of the first separator.

[0127] Preferably, separation according to (iv) comprises heating the product stream or the dehydrated product stream to a temperature in the range of -180°C to 0°C, more preferably in the range of -100°C to -50°C, more preferably in the range of -85°C to -75°C.

[0128] Preferably, the separation according to (iv) comprises compressing the product stream or the dehydrated product stream to a pressure in the range of 10 to 100 bara, more preferably in the range of 35 to 65 bara, more preferably in the range of 45 to 55 bara.

[0129] Preferably, the process of the present invention further comprises heating the NH3 obtained in (iv) to a temperature in the range of 50°C to 750°C, more preferably in the range of 175°C to 575°C, more preferably in the range of 300°C to 550°C, after (iv) and before (v).

[0130] It is also preferred that the process of the present invention further comprises expanding the NH3 obtained in (iv) to a pressure in the range of 1 to 50 bar (absolute pressure), more preferably in the range of 1 to 35 bar (absolute pressure), more preferably in the range of 1 to 30 bar (absolute pressure), after (iv) and before (v).

[0131] The unit bar (absolute pressure) refers to absolute pressure, where 1 bar is equal to 10 5 Pa.

[0132] The present invention is further illustrated by the following group of embodiments and the combination of embodiments obtained by the dependencies and back-references as shown. In particular, it should be noted that in each case where a series of embodiments is mentioned, for example, in the context of a term such as "a method as described in any one of embodiments 1 to 4", each embodiment in this series is intended to be clearly disclosed to the technician, that is, the wording of this term should be understood by the technician as synonymous with "a method as described in any one of embodiments 1, 2, 3 and 4". In addition, it is explicitly pointed out that the following group of embodiments is not a group of claims that determine the scope of protection, but represents an appropriate structural part of this specification related to the general and preferred aspects of the present invention.

[0133] 1. A method for NH3 reforming, the method comprising

[0134] (i) feeding a feed stream comprising NH3 into a reactor unit, wherein the reactor unit has a reactor unit inlet and a reactor unit outlet, wherein the reactor unit comprises a catalytic material;

[0135] (ii) contacting the feed stream with the catalytic material in the reactor unit to obtain a product stream comprising H2, N2, NH3 and optionally H2O, wherein the contacting is carried out at a pressure in the range of 1 to 100 bara and at a temperature in the range of 50°C to 750°C;

[0136] (iii) optionally separating H2O in the product stream obtained in (ii) to obtain a dehydrated product stream comprising H2, N2 and NH3;

[0137] (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;

[0138] (v) recycling the separated NH3 obtained in (iv) to (i).

[0139] 2. The process of embodiment 1, wherein 90 to 100 vol.-%, preferably 93 to 100 vol.-%, more preferably 95 to 100 vol.-% of the feed stream according to (i) consists of NH3.

[0140] 3. The method of embodiment 1 or 2, wherein the feed stream is fed to the reactor unit according to (i) at a rate of 400 to 40,000 h. -1 In the range of 2,000 to 12,000 h -1 The reaction is carried out at a gas hourly space velocity within the range of .

[0141] 4. A method as described in any one of Examples 1 to 3, wherein the feeding of the feed stream into 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.

[0142] 5. A method as described in any of Examples 1 to 4, wherein the feed stream is fed into the reactor unit according to (i) 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.

[0143] 6. The method of any one of embodiments 1 to 5, wherein the feed stream is fed into the reactor unit according to (i) at a rate of 250 to 55000 m 3 In the range of 5000 to 45000 m / h, preferably in the range of 5000 to 45000 m / h 3 In the range of 9250 to 41250 m / h, more preferably in the range of 9250 to 41250 m / h 3 The flow rate is within the range of 200 ℃ and 100 ℃.

[0144] 7. The method of any one of embodiments 1 to 6, wherein the feed stream is in the range of 50 to 2500 m 3 In the range of 250 to 1000 m / h, preferably in the range of 250 to 1000 m / h 3 In the range of 400 to 725 m / h, more preferably in the range of 400 to 725 m / h 3 The flow rate is within the range of 200 ℃ and 100 ℃.

[0145] 8. The process of any one of embodiments 1 to 7, wherein the feed stream further comprises H2O, wherein the feed stream preferably comprises 0 to 1 vol-%, preferably 0 to 0.5 vol-%, more preferably 0 to 0.21 vol-% H2O.

[0146] 9. The method of any one of embodiments 1 to 8, wherein the feed stream further comprises H2, wherein the feed stream preferably comprises 0 to 1 volume-%, more preferably 0 to 0.1 volume-%, more preferably 0 to 0.01 volume-% H2.

[0147] 10. The method of any one of embodiments 1 to 9, wherein the feed stream further comprises N2, wherein the feed stream preferably comprises 0 to 5 volume-%, more preferably 0 to 1 volume-%, more preferably 0 to 0.5 volume-% N2.

[0148] 11. The method 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 (absolute pressure), preferably in the range of 10 to 50 bar (absolute pressure), more preferably in the range of 15 to 45 bar (absolute pressure), 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 (absolute pressure).

[0149] 12. The method 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°C to 750°C, more preferably in the range of 160°C to 650°C, more preferably in the range of 170°C to 580°C, more preferably in the range of 180°C to 570°C, more preferably in the range of 190°C to 560°C, more preferably in the range of 200°C to 550°C, more preferably in the range of 210°C to 540°C, more preferably in the range of 220°C to 530°C, more preferably in the range of 230°C to 520°C, more preferably in the range of 240°C to 510°C, more preferably in the range of 250°C to 500°C.

[0150] 13. The method of any one of embodiments 1 to 12, wherein contacting according to (ii) comprises increasing the temperature from the reactor unit inlet to the reactor unit outlet.

[0151] 14. The method of embodiment 13, wherein the temperature is increased from 175°C, preferably 200°C, more preferably 225°C at the inlet of the reactor unit to 350°C, preferably 375°C, more preferably 400°C at the outlet of the reactor unit.

[0152] 15. The method of embodiment 13, wherein the temperature is increased from 375°C, preferably 400°C, more preferably 425°C at the inlet of the reactor unit to 550°C, preferably 575°C, more preferably 600°C at the outlet of the reactor unit.

[0153] 16. The method of any one of embodiments 1 to 15, wherein the contacting according to (ii) comprises transferring heat from a reaction of the chemical conversion process, wherein transferring heat is performed using a heat exchanger or a heat pump.

[0154] 17. The method of embodiment 16, wherein the heat transferred is obtained from an exothermic reaction, or wherein the heat transferred is excess heat to the heat used to carry out an autothermal reaction or an endothermic reaction.

[0155] 18. A method as described in Example 17, wherein the exothermic reaction includes one or more of the following: 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 selectively oxidizing one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid).

[0156] 19. A method as described in Example 17, wherein the endothermic reaction includes one or more of the following: 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.

[0157] 20. The method of embodiment 17, wherein the autothermal reaction is selected from the group consisting of: autothermal reforming of natural gas and hydrocarbons, including partial oxidation (POx) of hydrocarbons, wherein the hydrocarbons are selected from (C1-C 10 )alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0158] 21. The method of any one of embodiments 1 to 20, wherein the reactor unit comprises one or more reactors, wherein the catalytic material is contained in the one or more reactors.

[0159] 22. The method of embodiment 21, wherein each of the one or more reactors is independently selected from the group consisting of a polyvariable reactor, a two-stage reactor, an adiabatic reactor, and a combination of a polyvariable reactor and an adiabatic reactor.

[0160] 23. A method as described in Example 21 or 22, wherein each of the one or more reactors is tubular independently of each other, wherein the tubular reactor preferably comprises, more preferably consists of: 1 to 15,000 tubes, more preferably 100 to 12,000 tubes, and more preferably 500 to 5,000 tubes, wherein each of these tubes independently of each other 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.

[0161] 24. The method of any one of embodiments 21 to 23, wherein each of the one or more reactors independently 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.

[0162] 25. The method of any one of Embodiments 21 to 24, wherein each of the one or more reactors independently 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.

[0163] 26. The method of any one of embodiments 21 to 25, wherein each of the one or more reactors independently has a temperature in the range of 0.5 to 150 m 3 In the range of 1 to 80 m 3 In the range of 2 to 50 m 3 In the range of 3 to 30 m 3 In the range of 4 to 20 m 3 In the range of 5.0 to 16.5 m 3 volume within the range of .

[0164] 27. The method of any one of embodiments 21 to 26, wherein the reactor unit comprises, preferably consists of, one reactor, wherein the reactor unit inlet is the reactor inlet and wherein the reactor unit outlet is the reactor outlet.

[0165] 28. The method of any one of embodiments 21 to 26, wherein 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, wherein the first reactor is arranged upstream of the second reactor, wherein the first reactor has a first reactor inlet and a first reactor outlet, wherein the reactor unit inlet is the first reactor inlet, and wherein the reactor unit outlet is the second reactor outlet,

[0166] wherein the feeding according to (i) and the contacting according to (ii) comprise

[0167] (i.1) feeding the feed stream comprising NH3 into the first reactor to obtain an intermediate stream;

[0168] (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 (absolute) and at a temperature in the range of 50° C. to 750° C.;

[0169] (i.2) feeding the intermediate stream obtained in (i.1) into the second reactor;

[0170] (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 (absolute) and at a temperature in the range of 50° C. to 700° C.;

[0171] To obtain the product stream comprising H2, N2, NH3 and optionally H2O.

[0172] 29. The method of embodiment 28, wherein the catalytic material is contained by one or both of the two reactors, wherein the catalytic material is preferably contained by the first reactor and the second reactor.

[0173] 30. The process of embodiment 28 or 29, wherein feeding the intermediate stream into the second reactor according to (i.2) is carried out at a pressure in the range of 1 to 100 bar (absolute), preferably in the range of 5 to 50 bar (absolute).

[0174] 31. The process of any one of embodiments 28 to 30, wherein feeding the intermediate stream into the second reactor according to (i.2) is carried out at a temperature in the range of 250°C to 650°C, preferably in the range of 400°C to 600°C.

[0175] 32. The process of any one of embodiments 28 to 31, wherein feeding the intermediate stream into the second reactor according to (i.2) is carried out at the same pressure and the same temperature as feeding the feed stream into the first reactor according to (i.1).

[0176] 33. A method as described in any of Examples 28 to 32, wherein the contacting according to one or both of (ii.1) and (ii.2) is carried out at a pressure in the range of 5 to 80 bar (absolute pressure), preferably in the range of 10 to 60 bar (absolute pressure), more preferably in the range of 15 to 45 bar (absolute pressure), 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 (absolute pressure).

[0177] 34. The method of any one of embodiments 28 to 33, wherein the contacting according to one or both of (ii.1) and (ii.2) is carried out at a temperature in the range of 100°C to 750°C, more preferably in the range of 160°C to 650°C, more preferably in the range of 170°C to 580°C, more preferably in the range of 180°C to 570°C, more preferably in the range of 190°C to 560°C, more preferably in the range of 200°C to 550°C, more preferably in the range of 210°C to 540°C, more preferably in the range of 220°C to 530°C, more preferably in the range of 230°C to 520°C, more preferably in the range of 240°C to 510°C, more preferably in the range of 250°C to 500°C.

[0178] 35. The method of any one of embodiments 28 to 34, wherein contacting according to one or both of (ii.1) and (ii.2) comprises increasing the temperature from the reactor inlet to the reactor outlet.

[0179] 36. The method 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.

[0180] 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.

[0181] 38. The method of any one of embodiments 28 to 37, wherein the contacting according to one or both of (ii.1) and (ii.2) comprises transferring heat from a reaction of the chemical conversion process, wherein the transferring heat is performed using a heat exchanger or a heat pump.

[0182] 39. The method of embodiment 38, wherein the heat transferred is obtained from an exothermic reaction, or wherein the heat transferred is excess heat to the heat used to carry out an autothermal reaction or an endothermic reaction.

[0183] 40. A method as described in Example 39, wherein the exothermic reaction includes one or more of the following: 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 selectively oxidizing one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid).

[0184] 41. A method as described in Example 39, wherein the endothermic reaction includes one or more of the following: 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.

[0185] 42. The method of embodiment 39, wherein the autothermal reaction is selected from the group consisting of: autothermal reforming of natural gas and hydrocarbons, including partial oxidation (POx) of hydrocarbons, wherein the hydrocarbons are selected from (C1-C 10 )alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0186] 43. The method of any one of embodiments 28 to 42, preferably embodiment 42, wherein the reactor unit comprises two or more reactors, wherein the reactor unit further comprises one or more heaters, wherein the heater is arranged between two reactors.

[0187] 44. The method of embodiment 43, wherein the reactor unit comprises two reactors, wherein the reactor unit further comprises a heater, wherein the heater is arranged downstream of the first reactor and upstream of the second reactor for heating the intermediate stream.

[0188] 45. The method of any one of embodiments 1 to 44, wherein the reactor unit comprises one or more reactors, and wherein the catalytic material is contained by one or more of the one or more reactors.

[0189] 46. ​​The method of any one of embodiments 1 to 45, wherein the catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

[0190] 47. A method as described in Example 46, wherein the catalytic material further comprises a metal M2, which is selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru (including mixtures of two or more thereof), preferably selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably selected from the group consisting of K, Na, Cs, Ba, Mo, Fe, Ru (including mixtures of two or more thereof), more preferably selected from the group consisting of K, Ba, Mo, Fe, Ru and mixtures of two or more thereof, wherein M2 more preferably comprises Fe, Ru, or Fe and Ru, wherein more preferably M2 comprises Ru, wherein more preferably M2 is Ru.

[0191] 48. A method as described in Example 46 or 47, wherein the catalytic material further comprises one or more carrier materials on which metal M1 or metal M1 and M2 are loaded, wherein the one or more carrier materials are preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2 and a mixture of two or more thereof, more preferably selected from the group consisting of Al2O3, SiO2 and a mixture thereof, wherein more preferably the carrier material comprises Al2O3.

[0192] 49. A method as described in any of Examples 47 or 48, wherein the catalytic material shows an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, preferably 0.5:99.5 to 75:25, more preferably 1:99 to 70:30, more preferably 5:95 to 65:35, more preferably 15:85 to 60:40, more preferably 30:70 to 55:45, and more preferably 40:60 to 50:50.

[0193] 50. The method of any one of embodiments 47 to 49, wherein M2 comprises Fe, preferably Fe, and wherein the catalytic material shows 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.

[0194] 51. A method as described in any of Examples 47 to 50, wherein M2 comprises Ru, preferably Ru, and wherein the catalytic material shows 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.

[0195] 52. The method of any one of embodiments 46 to 51, wherein the catalytic material further comprises Al and O.

[0196] 53. The method of embodiment 52, wherein the catalytic material comprises Ni as the metal M1, wherein preferably the metal M1 is Ni.

[0197] 54. A method as described in Example 53, wherein the catalytic material further comprises Mg, wherein the Ni:Mg:Al molar ratio is preferably in the range of 1:(0.1-12):(0.5-20), more preferably 1:(0.5-8):(1-12), more preferably 1:(1-5):(3-8), more preferably 1:(1.5-3):(3.5-5), and more preferably 1:(2.0-2.4):(4.0-4.4).

[0198] 55. A method as described in Example 53 or 54, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ni, Mg, Al and O.

[0199] 56. A method as described in Example 53 or 54, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Ni, Mg, Al and O.

[0200] 57. The method of embodiment 52, wherein the catalytic material comprises Co as the metal M1, wherein preferably the metal M1 is Co.

[0201] 58. A method as described in Example 57, wherein the catalytic material further comprises La, wherein the Co:La:Al molar ratio is preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), and more preferably 1:(1.3-1.7):(10-12).

[0202] 59. A method as described in Example 57 or 58, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material is composed of Co, La, Al and O.

[0203] 60. A method as described in Example 58 or 59, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Co, La, Al and O.

[0204] 61. The method of any one of embodiments 1 to 45, wherein the catalytic material comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, wherein the one or more support materials show a 20 m 2 / g or more BET surface area, wherein the BET surface area is preferably determined according to ISO 9277:2010, and wherein the catalytic material contains 1 wt.-% or less Ni and Co, calculated as the respective elements and based on 100 wt.-% of the catalytic material.

[0205] 62. A method as described in Example 61, wherein the catalytic material contains 0.5 wt.-% or less, preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, and more preferably 0.001 wt.-% or less of Ni and Co, calculated as corresponding elements and based on 100 wt.-% of the catalytic material.

[0206] 63. A method as described in Example 61, wherein the reactor unit contains Ni and Co, calculated as the corresponding elements and based on 100 wt.-% of the reactor, in a total content of 1 wt.-% or less, preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, and more preferably 0.001 wt.-% or less.

[0207] 64. The method of any one of embodiments 61 to 63, wherein the one or more support materials show a relative humidity of 30 to 800 m / s. 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 The BET surface area is in the range of 1000 Å / g.

[0208] 65. The method of any one of embodiments 61 to 64, wherein the one or more support materials show a relative humidity of 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 35m 2 The BET surface area is in the range of 1000 Å / g.

[0209] 66. A method as described in any of Examples 61 to 65, wherein the one or more support materials show a pore volume in the range of 0.2 to 3 ml / g, preferably 0.4 to 1.5 ml / g, more preferably 0.6 to 1 ml / g, and more preferably 0.8 to 0.85 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0210] 67. The method of any one of embodiments 61 to 66, wherein the catalytic material shows a relative humidity 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 75m 2 The BET surface area is preferably in the range of 1000 Å / g, wherein the BET surface area is preferably determined according to ISO 9277:2010.

[0211] 68. A method as described in any of Examples 61 to 67, wherein the catalytic material shows a pore volume in the range of 0.1 to 2 ml / g, preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, and more preferably 0.3 to 0.35 ml / g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

[0212] 69. A method as described in any of Examples 61 to 68, wherein, calculated as element and based on 100 wt.-% of Ru contained in the catalytic material, 90 to 100 wt.-%, preferably 95 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of Ru is loaded on the one or more support materials contained in the catalytic material.

[0213] 70. A method as described in any one of Examples 61 to 69, wherein Ru is loaded on the one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, wherein the one or more ruthenium salts preferably include Ru(NO)(NO3)3, wherein Ru(NO)(NO3)3 is more preferably used as the one or more ruthenium salts.

[0214] 71. The method of any one of embodiments 61 to 70, wherein the one or more support materials are selected from the group consisting of metal oxides, wherein the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals and rare earth metals (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca and La (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca and La (including combinations of two or more thereof), more preferably selected from the group consisting of Preferably selected from the group consisting of Al, Zr and Mg (including combinations of two or more thereof), wherein more preferably the one or more carrier materials contain one or more metal oxides, the one or more metal oxides are selected from the group consisting of Al2O3, ZrO2 and spinel (including mixtures of two or more thereof), preferably selected from the group consisting of ZrO2 and spinel (including mixtures of two or more thereof), wherein more preferably the one or more carrier materials contain ZrO2 and / or MgAl2O4, preferably ZrO2, wherein more preferably the one or more carrier materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0215] 72. A method as described in Example 71, wherein ZrO2 contains one or more crystalline phases and / or is amorphous, wherein the one or more crystalline phases of ZrO2 are selected from the group consisting of: monoclinic phase, tetragonal phase and cubic phase (including mixtures of two or three thereof) of ZrO2.

[0216] 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.

[0217] 74. A method as described in any of Examples 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.

[0218] 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.

[0219] 76. A method as described in any of Embodiments 61 to 75, wherein the catalytic material contains 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.-%, based on a total amount of 100 wt.-% of the one or more carrier materials.

[0220] 77. A method as described in any of Examples 61 to 76, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ru and the one or more support materials.

[0221] 78. A method as described in any one of Examples 61 to 77, wherein the catalytic material further comprises one or more alkali metal hydroxides and / or alkaline earth metal hydroxides, wherein the one or more alkali metal hydroxides and / or alkaline earth metal hydroxides are loaded on the one or more support materials loaded with Ru, wherein the alkali metal hydroxide and / or alkaline earth metal hydroxide are preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH and KOH (including mixtures of two or more thereof), more preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH and KOH (including mixtures of two or more thereof), more preferably selected from the group consisting of LiOH, NaOH and KOH (including mixtures of two or more thereof), wherein more preferably the catalytic material further comprises KOH and / or LiOH, preferably KOH.

[0222] 79. A method as described in Example 78, wherein the catalytic material contains the one or more alkali metal hydroxides in an amount ranging from 0.5 to 15 wt.-%, preferably 1 to 10 wt.-%, more preferably 2 to 8 wt.-%, more preferably 3 to 6.5 wt.-%, more preferably 4 to 6 wt.-%, and more preferably 4.5 to 5.5 wt.-%, based on a total amount of 100 wt.-% of the one or more carrier materials.

[0223] 80. A method as described in any of Examples 61 to 79, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Ru, the one or more alkali metal hydroxides and the one or more support materials.

[0224] 81. The method of any one of embodiments 61 to 80, wherein the catalytic material is in the form of a molded article and / or in the form of a powder, preferably in the form of a molded article, and more preferably in the form of an extrudate.

[0225] 82. A method as described in Example 81, wherein the extrudates have a diameter in the range of 0.5 to 10 mm, preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and more preferably 2.5 to 3.5 mm.

[0226] 83. A method as described in any one of embodiments 1 to 45, wherein the catalytic material comprises Ni, Ru and a promoter metal M1', wherein the catalytic material shows a Ru:Ni weight ratio in the range of 0.0001:1 to 0.5:1, wherein the promoter metal M1' is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr and Ba (including mixtures of two or more thereof), and wherein the catalytic material further comprises one or more support materials on which Ni, Ru and the promoter metal M1' are respectively loaded.

[0227] 84. A method as described in Example 83, wherein the catalytic material shows a Ru:Ni weight 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.

[0228] 85. A method as described in Example 83 or 84, wherein the promoter metal M1' is selected from the group consisting of Li, K, Na, Cs, Mg and Ca (including mixtures of two or more thereof), preferably selected from the group consisting of Li, K, Na and Cs (including mixtures of two or more thereof), more preferably selected from the group consisting of Li, K and Na (including mixtures of two or more thereof), wherein more preferably the promoter metal M1' is Li, K, or Li and K, wherein more preferably the promoter metal M1' is K, wherein more preferably the promoter metal M1' consists of Li, K, or Li and K, wherein more preferably the promoter metal M1' consists of K.

[0229] 86. The method of any one of Embodiments 83 to 85, wherein the catalytic material shows 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.

[0230] 87. The method of any one of embodiments 83 to 86, wherein the one or more support materials are selected from the group consisting of metal oxides, wherein the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals and rare earth metals (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd (including combinations of two or more thereof), more preferably selected from the group consisting of Al, Ti, Zr, Mg, Ca and La (including combinations of two or more thereof), and more preferably selected from the group consisting of Al, Zr and Mg (including combinations of two or more thereof), wherein More preferably, the one or more carrier materials comprise one or more metal oxides, the one or more metal oxides are selected from the group consisting of Al2O3, ZrO2 and spinel (including mixtures of two or more thereof), preferably selected from the group consisting of ZrO2 and spinel (including mixtures of two or more thereof), more preferably selected from the group consisting of ZrO2, NiMgO2 and MgAl2O4 (including mixtures of two or more thereof), wherein more preferably the one or more carrier materials comprise MgAl2O4, preferably NiMgO2 and MgAl2O4, wherein more preferably the one or more carrier materials consist of MgAl2O4, or consist of NiMgO2 and MgAl2O4, preferably consist of NiMgO2 and MgAl2O4.

[0231] 88. A method as described in any of Embodiments 83 to 87, wherein, calculated as the corresponding elements and based on 100 wt.-% of Ni and Ru contained in the catalytic material, 90 to 100 wt.-%, preferably 95 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of Ni and Ru are loaded on the one or more carrier materials contained in the catalytic material.

[0232] 89. A method as described in any of Embodiments 83 to 88, wherein, calculated as corresponding elements and based on 100 wt.-% of Ni, Ru and promoter metal M1' contained in the catalytic material, 90 to 100 wt.-%, preferably 95 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of Ni, Ru and promoter metal M1' are loaded on the one or more support materials contained in the catalytic material.

[0233] 90. A method as described in any of Embodiments 83 to 89, wherein the catalytic material contains Ni in an amount calculated as an element and based on 100 wt.-% of the catalytic material in the range of 1 to 75 wt.-%, preferably 3 to 60 wt.-%, more preferably 5 to 40 wt.-%, more preferably 10 to 25 wt.-%, more preferably 12 to 18 wt.-%, and more preferably 14 to 16 wt.-%.

[0234] 91. A method as described in any of Examples 83 to 90, wherein the catalytic material contains Ru in an amount calculated as an element and in the range of 0.01 to 5 wt.-%, preferably 0.05 to 2.5 wt.-%, more preferably 0.1 to 1.5 wt.-%, more preferably 0.2 to 1 wt.-%, more preferably 0.3 to 0.8 wt.-%, and more preferably 0.4 to 0.6 wt.-%, based on 100 wt.-% of the catalytic material.

[0235] 92. A method as described in any of Examples 83 to 91, wherein the catalytic material contains a promoter metal M1' in an amount calculated as an element and in the range of 0.05 to 25 wt.-%, preferably 0.1 to 15 wt.-%, more preferably 0.5 to 10 wt.-%, more preferably 1 to 8 wt.-%, more preferably 2 to 5 wt.-%, and more preferably 3 to 4 wt.-%, based on 100 wt.-% of the catalytic material.

[0236] 93. A method as described in any of Examples 83 to 92, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material is composed of Ni, Ru, promoter metal M1' and the one or more support materials, wherein Ni, Ru and promoter metal M1' can be present as elements, oxides and / or salts, respectively.

[0237] 94. A method as described in any one of embodiments 83 to 93, wherein the catalytic material contains the one or more promoter metals M1' as hydroxides, bicarbonates and / or carbonates, preferably as hydroxides and / or bicarbonates, and more preferably as hydroxides, wherein more preferably the promoter metal M1 is contained in the catalytic material as its hydroxide salt.

[0238] 95. A method as described in any one of Examples 83 to 94, wherein Ru is loaded on the one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, wherein the one or more ruthenium salts preferably include Ru(NO)(NO3)3, wherein Ru(NO)(NO3)3 is more preferably used as the one or more ruthenium salts.

[0239] 96. A method as described in any of Examples 83 to 95, wherein the catalytic material is in the form of a molded article, in the form of an extrudate, and / or in the form of a powder, preferably in the form of a molded article or an extrudate, and more preferably in the form of a molded article.

[0240] 97. A method as described in Example 96, wherein the extrudates have a diameter in the range of 0.5 to 10 mm, preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and more preferably 2.5 to 3.5 mm.

[0241] 98. A method as described in embodiment 96, wherein the molded article has a diameter in the range of 1 to 20 mm, preferably in the range of 1 to 15 mm.

[0242] 99. The method of any one of embodiments 96 or 98, wherein the molded article is in the shape of a quadrilobate.

[0243] 100. The method of any one of embodiments 1 to 99, wherein the separation according to (iii) is performed in a first separator, wherein the first separator is arranged downstream of the reactor unit.

[0244] 101. The method of any one of embodiments 1 to 100, wherein the separation according to (iii) comprises cooling the product stream to a temperature in the range of 0°C to 100°C, preferably in the range of 30°C to 70°C, more preferably in the range of 45°C to 55°C.

[0245] 102. A method as described in any of Examples 1 to 101, wherein the separation according to (iii) includes compressing the product stream to a pressure in the range of 5 to 100 bar (absolute pressure), preferably in the range of 20 to 50 bar (absolute pressure), and more preferably in the range of 25 to 35 bar (absolute pressure).

[0246] 103. The method of any one of embodiments 1 to 102, wherein the separation according to (iv) is performed in a second separator, wherein the second separator is arranged downstream of the reactor unit or downstream of the first separator as defined in embodiment 101.

[0247] 104. A method as described in any one of Examples 1 to 103, wherein the separation according to (iv) includes heating the product stream or the dehydrated product stream to a temperature in the range of -180°C to 0°C, preferably in the range of -100°C to -50°C, and more preferably in the range of -85°C to -75°C.

[0248] 105. A method as described in any of Examples 1 to 104, wherein the separation according to (iv) includes compressing the product stream or the dehydrated product stream to a pressure in the range of 10 to 100 bar (absolute pressure), preferably in the range of 35 to 65 bar (absolute pressure), and more preferably in the range of 45 to 55 bar (absolute pressure).

[0249] 106. The method of any one of embodiments 1 to 105, further comprising heating the NH3 obtained in (iv) to a temperature in the range of 50°C to 750°C, preferably in the range of 175°C to 575°C, more preferably in the range of 300°C to 550°C, after (iv) and before (v).

[0250] 107. A method as described in any one of embodiments 1 to 106, further comprising expanding the NH3 obtained in (iv) to a pressure in the range of 1 to 50 bar (absolute pressure), preferably in the range of 1 to 35 bar (absolute pressure), more preferably in the range of 1 to 30 bar (absolute pressure), after (iv) and before (v).

[0251] The present invention is further illustrated by the following Reference Examples, Examples and Comparative Examples.

[0252] Examples

[0253] The following examples were simulated using Aspen Plus software version 12.

[0254] Reference Example 1: Ru-containing catalytic material

[0255] A low temperature active NH3 reforming catalytic material is provided.

[0256] A catalyst comprising Ru (5 wt.-%) and KOH (5 wt.-%) supported on ZrO2 was used. The catalyst was prepared as follows. A 5 g sample of the 5 wt.-% Ru on ZrO2 extrudate obtained from Example 1 was impregnated with a KOH solution. To this end, 5 g of the extrudate obtained from Example 1 was segmented to form fractions ranging from 315 to 500 microns and then impregnated via incipient wetness impregnation with 0.25 g of KOH dissolved in 1.65 ml of water. The sample was then dried at 120°C and subsequently calcined at 500°C under an inert atmosphere for 2 hours. …

[0257] Furthermore, a kinetic model was developed for the provided Ru-containing catalytic materials, allowing for appropriate simulation of turnover numbers taking into account the boundaries and concepts described herein (see Fig. . . ).

[0258] Reference Example 2: Providing a feed stream containing NH3

[0259] For the simulation of the NH3 reforming process with recycle, a reference scenario was defined in which about 10 t / h NH3 was used as feed stream. In addition, the pressure and temperature of the feed stream were set as indicated in the corresponding example. The feed stream containing NH3 consisted of 99 to 99.9 volume-% NH3 and 0.1 to 1 volume-% H2O.

[0260] Example 1: Process for reforming NH3 in a polyvariable reactor with recirculation of unconverted NH3

[0261] A reactor unit was set up, which included a single polytropic and heated reactor containing a Ru-containing catalytic material according to Reference Example 1. The reactor dimensions were fixed at 5 m length and 2 m diameter. The feed stream according to Reference Example 2 was provided. NH3 reforming of the polytropic reactor was simulated at a pressure of 1 bar (absolute) and at an initial temperature of 250°C, which increased along the reactor bed length to reach 350°C at the outlet. The resulting conversion curves are shown in Figure 2 and the characteristics of the individual process streams are given in the following Tables 1a and 1b, respectively.

[0262] Table 1a:

[0263] Characteristics of the various process streams determined from the simulations according to Example 1 (Part 1).

[0264]

[0265]

[0266] Table 1b:

[0267] Characteristics of the various process streams determined from the simulations according to Example 1 (Part 2).

[0268]

[0269] From the results shown in Tables 1a and 1b it can be determined that the conversion at the reactor outlet under steady state recycle conditions is 60%. In the separation step, the residual NH3 in the H2-containing product stream is reduced to 1000 ppm.

[0270] Example 2: Process for reforming NH3 in a polyvariable reactor with recirculation of unconverted NH3

[0271] A reactor unit was set up, which included a single polytropic and heated reactor containing a Ru-containing catalytic material according to Reference Example 1. The reactor dimensions were fixed at 5 m length and 2 m diameter. A feed stream according to Reference Example 2 was provided. NH3 reforming of the polytropic reactor was simulated at a pressure of 1 bar (absolute) and at an initial temperature of 450°C, which increased along the reactor bed length to reach 550°C at the outlet. The resulting conversion curves are shown in Figure 3, and the characteristics of the individual process streams are given in the following Tables 2a and 2b, respectively.

[0272] Table 2a:

[0273] Characteristics of the various process streams determined from the simulations for Example 2 (Part 1).

[0274]

[0275]

[0276] Table 2b:

[0277] Characteristics of the various process streams determined from the simulations for Example 2 (Section 2).

[0278]

[0279] From the results shown in Tables 2a and 2b, it can be determined that the conversion at the reactor outlet under steady-state recycle conditions is 92%. From these results, it can be concluded that the increase in the temperature profile is beneficial for the overall conversion. Therefore, compared with the process according to Example 1, relatively less NH3 is available for recycle. In the separation step, the residual NH3 in the H2-containing product stream is reduced to 1000 ppm.

[0280] Example 3: Process for reforming NH3 in a polyvariable reactor with recirculation of unconverted NH3

[0281] A reactor unit was set up, comprising a single polytropic and heated reactor containing a Ru-containing catalytic material according to Reference Example 1. The reactor dimensions were fixed at 5 m length and 2 m diameter. A feed stream according to Reference Example 2 was provided. NH3 reforming of the polytropic reactor was simulated at an elevated pressure of 30 bar (absolute) and at an initial temperature of 250°C, which increased along the reactor bed length to reach 350°C at the outlet. The resulting conversion curves are shown in FIG4 and the characteristics of the individual process streams are given in the following Tables 3a and 3b, respectively.

[0282] Table 3a:

[0283] Characteristics of the various process streams determined from the simulations for Example 3 (Part 1).

[0284]

[0285]

[0286] Table 3b:

[0287] Characteristics of the various process streams determined from the simulations for Example 3 (Part 2).

[0288]

[0289] From the results shown in Table 3, it can be determined that the conversion at the reactor outlet under steady-state recycle conditions is 15%.

[0290] Example 4: Process for reforming NH3 in an adiabatic reactor with recirculation of unconverted NH3

[0291] A reactor unit was set up, which included a single adiabatic reactor containing a Ru-containing catalytic material according to Reference Example 1. The reactor dimensions were fixed at 5 m length and 2 m diameter. A feed stream according to Reference Example 2 was provided. The reforming of NH3 of the polytropic reactor was simulated at a pressure of 1 bar (absolute pressure) and at an initial temperature of 500°C. The resulting conversion curve is shown in Figure 5, and the characteristics of the individual process streams are given in the following Tables 4a and 4b, respectively.

[0292] Table 4a:

[0293] Characteristics of the various process streams determined from the simulations according to Example 4 (Part 1).

[0294]

[0295] Table 4b:

[0296] Characteristics of the various process streams determined from the simulations according to Example 4 (Part 2).

[0297]

[0298] From the results shown in Tables 4a and 4b, it can be determined that the conversion at the reactor outlet under steady-state recycle conditions is 35%. In the separation step, the residual NH3 in the H2-containing product stream is reduced to 1000 ppm.

[0299] Example 5: Process for reforming NH3 in a reactor cascade containing two adiabatic reactors with recirculation of unconverted NH3

[0300] A reactor unit is provided, which includes two adiabatic reactors arranged in series, wherein a heater is arranged between the reactors for heating the outlet flow of the upstream reactor. Both reactors contain a Ru-containing catalytic material according to Reference Example 1. Each reactor has a length of 5 m and a diameter of 2 m. A feed stream according to Reference Example 2 is provided. The NH3 reforming of the reactor cascade is simulated at a pressure of 1 bar (absolute pressure), and the initial temperature of each reactor is 500°C. The resulting conversion curve is shown in Figure 6, and the characteristics of each process stream are given in the following Tables 5a and 5b, respectively.

[0301] Table 5a:

[0302] Characteristics of the various process streams determined from the simulations for Example 5 (Part 1).

[0303]

[0304] Table 5b:

[0305] Characteristics of the various process streams determined from the simulations for Example 5 (Part 2).

[0306]

[0307] From the results shown in Tables 5a and 5b, it can be obtained that the conversion at the outlet of the reactor unit under steady-state recycle conditions is 54%. In particular, the conversion after the first reactor is 35%, which is comparable to the conversion obtained according to Example 4. In the separation step, the residual amount of NH3 in the H2-containing product stream is reduced to 1000 ppm. BRIEF DESCRIPTION OF THE DRAWINGS

[0308] Figure 1 : A parity plot showing the simulation values ​​and experimental values ​​of the Ru-containing low-temperature NH3 reforming catalytic material according to a reference example.

[0309] References:

[0310] -US 8961923 B2

[0311] -US 8691182 B2

[0312] -US 8464515 B2

[0313] -WO 2019 / 038251 A1

[0314] -Banares-Alcantara et al.in Applied Energy 2021,282,116009

Claims

1. A method for NH3 reforming, the method comprising (i) feeding a feed stream comprising NH3 into a reactor unit, wherein the reactor unit has a reactor unit inlet and a reactor unit outlet, wherein the reactor unit comprises a catalytic material; (ii) contacting the feed stream with the catalytic material in the reactor unit to obtain a product stream comprising H2, N2, NH3 and optionally H2O, wherein the contacting is carried out at a pressure in the range of 1 to 100 bara and at a temperature in the range of 50°C to 750°C; (iii) optionally separating H2O in the product stream obtained in (ii) to obtain a dehydrated product stream comprising H2, N2 and NH3; (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) recycling the separated NH3 obtained in (iv) to (i).

2. The method of claim 1, wherein: 90 to 100 vol.-% of the feed stream according to (i) consists of NH 3 .

3. The method according to claim 1 or 2, wherein: The feed stream is fed to the reactor unit according to (i) at a temperature between 400 and 40,000 h. -1 The reaction is carried out at a gas hourly space velocity within the range of .

4. The method according to any one of claims 1 to 3, wherein: The contacting according to (ii) comprises transferring heat from the reaction of the chemical conversion process, wherein the transferring heat is performed using a heat exchanger or a heat pump.

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

6. The method according to any one of claims 1 to 5, wherein: The reactor unit comprises one or more reactors, wherein the catalytic material is contained in the one or more reactors.

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

8. The method according to claim 6 or 7, wherein: Each of the one or more reactors is independently tubular.

9. The method according to any one of claims 6 to 8, wherein: The reactor unit comprises, wherein the reactor unit inlet is the reactor inlet and wherein the reactor unit outlet is the reactor outlet.

10. The method according to any one of claims 6 to 9, wherein: the reactor unit comprises two or more reactors, the two reactors being a first reactor and a second reactor, wherein the first reactor is arranged upstream of the second reactor, wherein the first reactor has a first reactor inlet and a first reactor outlet, wherein the reactor unit inlet is the first reactor inlet, and wherein the reactor unit outlet is the second reactor outlet, wherein the feeding according to (i) and the contacting according to (ii) comprise (i.1) feeding the feed stream comprising NH3 into 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 (absolute) and at a temperature in the range of 50° C. 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 (absolute) and at a temperature in the range of 50° C. to 700° C.; To obtain the product stream comprising H2, N2, NH3 and optionally H2O.

11. The method according to any one of claims 1 to 10, wherein: The reactor unit comprises one or more reactors, and wherein the catalytic material is contained by one or more of the one or more reactors.

12. The method according to any one of claims 1 to 11, wherein: The catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

13. The method according to any one of claims 1 to 12, wherein: The catalytic material comprises Ru and one or more support materials, wherein Ru is supported on the one or more support materials, wherein the one or more support materials show 20m 2 / g or more BET surface area, and wherein the catalytic material contains 1 wt.-% or less of Ni and Co calculated as the respective elements and based on 100 wt.-% of the catalytic material.

14. The method according to any one of claims 1 to 13, wherein: The catalytic material comprises Ni, Ru and a promoter metal M1', wherein the catalytic material shows a Ru:Ni weight ratio in the range of 0.0001:1 to 0.5:1, wherein the promoter metal M1' is selected from the group consisting of Li, K, Na, Cs, Mg, Ca, Sr and Ba - including mixtures of two or more thereof, and wherein the catalytic material further comprises one or more support materials on which Ni, Ru and the promoter metal M1' are respectively loaded.

15. The method according to any one of claims 1 to 14, further comprising expanding the NH3 obtained in (iv) after (iv) and before (v).

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