Method for carrying out endothermic reactions in reactor with less CO2 emissions

Abstract

The invention relates to a method for carrying out an endothermic reaction in a reactor, the method comprising in particular heating a combustible stream comprising NH3 to a temperature in the range of 25 DEG C to 850 DEG C, where the heating comprises transferring reaction heat from a chemical conversion process to the combustible stream; feeding the heated combustible gas stream into a combustion chamber, wherein a portion of the reactor passes through the combustion chamber; combusting the flow of combustible gas in the combustion chamber with oxygen to heat the portion of the reactor passing through the combustion chamber to a temperature in the range of 500 DEG C to 2100 DEG C; feeding a feed gas stream comprising one or more reactants to the heated reactor to perform the endothermic reaction; and reacting the feed gas stream in the heated reactor.

Description

Technical Field

[0001] The present invention relates to a method for carrying out an endothermic reaction in a reactor, the method comprising in particular the steps of heating a combustible stream comprising NH3, optionally reforming NH3 to obtain a gas stream comprising N2 and H2, burning the heated combustible gas stream or the gas stream comprising N2 and H2 with oxygen in a combustion chamber to heat the portion of the reactor passing through the combustion chamber, and reacting a raw gas stream in the heated reactor to obtain a product gas stream, wherein the heating comprises transferring reaction heat from a chemical conversion process to the combustible stream. Background Art

[0002] NH3 can be regarded as a future energy carrier because it can store a large amount of H2 chemically. In order to include hydrogen back into a chemical process or another application, NH3 can be reformed into nitrogen and hydrogen (see equation 1). In addition, NH3 can also be used as a sustainable carbon-free fuel in an open-fire heater. Generally speaking, NH3 can be used directly or reformed, wherein the reforming can be carried out partially or completely. The degree of NH3 reforming depends fundamentally on the needs of the combined fuel application, wherein a higher hydrogen content is typically used to increase the flame temperature. In addition, NH3 can also be used as a co-fuel as is or after reforming. For example, a conventional natural gas-based open-fire heater can be co-burned with NH3 as is or after reforming. This enables the open-fire heater to be at least partially decarbonized, which depends on the amount of natural gas replaced by NH3-containing fuel. Since the NH3 reforming step is an endothermic reaction (+45.6kJ / mol), additional energy must be invested. In addition, evaporating NH3, which is usually liquid, into gaseous NH3 is also an energy-consuming step (+23kJ / mol).

[0003] (1)

[0004] WO 2019 / 038251 A1 relates to an autothermal ammonia cracking method, in particular to a method for producing a product gas containing nitrogen and hydrogen from ammonia, the method comprising the following steps: non-catalytically partially oxidizing ammonia with a gas containing oxygen to form a process gas containing nitrogen, water, a certain amount of nitrogen oxides and a residual amount of ammonia; cracking at least a portion of the residual amount of ammonia in the process gas into hydrogen and nitrogen by contacting with a nickel-containing catalyst, and at the same time, reducing a certain amount of nitrogen oxides to nitrogen and water by contacting the process gas with a nickel-containing catalyst to react with a portion of the hydrogen formed during the cracking of the process gas; and removing a product gas containing hydrogen and nitrogen.

[0005] Banares-Alcantara et al., Applied Energy, 2021, 282, 116009, disclose predictions for ammonia as an energy carrier, particularly its role in combined cycle gas turbines for power generation.

[0006] US 8464515 B2 discloses an NH3 burning internal combustion engine in which reformed gas reformed at a reformer is fed into a combustion chamber.

[0007] US 8691182 B2 and US 8961923 B2 relate to processes for cracking ammonia, which processes comprise, inter alia, heating a gas stream comprising ammonia and a gas stream comprising oxygen in a heat exchanger, reacting the gas streams in a mixing burner to obtain a hydrogen-containing gas mixture, and cooling the hydrogen-containing gas mixture obtained in a heat exchanger.

[0008] Therefore, there is a need to provide an improved process for carrying out endothermic reactions, wherein the process is carried out in a relatively resource efficient, in particular more sustainable, manner. DETAILED DESCRIPTION

[0009] The object of the present invention is therefore to provide a novel method for carrying out an endothermic reaction, wherein in particular CO2 emissions are reduced. It can be assumed that 1 kg of natural gas (LHV NG =47MJ / kg) is replaced by, for example, 2.52kg NH3 (same energy content), directly saving 2.5-2.7kg CO2 emissions. This is a significant reduction in CO2 emissions for energy-intensive endothermic high-temperature applications.

[0010] Surprisingly, it has been found that incorporating a step of heating a combustible gas stream containing NH3 by heat transfer from a chemical conversion process results in an improved method for carrying out an endothermic reaction. The improvement is combined with a reduction in CO2 emissions by replacing carbon-based energy carriers with NH3.

[0011] Heat transfer can be achieved, for example, by a heat exchanger. The energy required for heat transfer can be provided by excess heat from an exothermic reaction or heat for a high temperature endothermic reaction. In both cases, heat can be transferred via a hot outlet gas or fluid.

[0012] Hot NH3 can also be converted before it is burned, for example in an adiabatic reactor, and the conversion can also be carried out in the presence of a catalyst. The degree of conversion of NH3 depends on its temperature. Due to the low heating value (LHV) (LHV H2 =120MJ / kg) than NH3(LHV NH3=18.6MJ / kg) is much higher, so when burning fuel, the NH3 conversion or H2 concentration is related to the temperature of the flame. For example, high temperature can be achieved with a higher hydrogen concentration (or NH3 conversion rate).

[0013] Thus, it has been unexpectedly found that converted or unconverted NH3 can serve as a sustainable carbon-free fuel. Furthermore, it has been found that it can be used as a co-fuel with natural gas in particular. Also, it has been found that the NH3-containing stream can be heated by excess heat from chemical processes. The NH3 reforming degree and H2 concentration determine the flame temperature and its application.

[0014] The unit bar (absolute pressure) refers to absolute pressure, where 1 bar is equal to 10 5 Pa.

[0015] 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.

[0016] Therefore, the present invention relates to a method for carrying out an endothermic reaction in a reactor, the method comprising

[0017] (i) providing a combustible stream comprising NH3, wherein the stream is in a liquid or gaseous state;

[0018] (ii) heating the combustible gas stream provided in (i) to a temperature in the range of 25° C. to 850° C. to obtain a heated combustible gas stream;

[0019] (iii) optionally feeding the heated combustible gas stream obtained in (ii) into an ammonia reforming reactor to obtain a gas stream comprising N2 and H2;

[0020] (iv) feeding the heated combustible gas stream obtained in (ii) or the gas stream obtained in (iii) into a combustion chamber, wherein a reactor is contained in the combustion chamber;

[0021] (v) combusting the combustible gas stream obtained in (ii) or the gas stream obtained in (iii) with oxygen in the combustion chamber to heat the reactor contained in the combustion chamber to a temperature in the range of 500° C. to 2100° C. and obtaining an exhaust gas stream leaving the combustion chamber;

[0022] (vi) preparing a feed gas stream comprising one or more reactants for an endothermic reaction;

[0023] (vii) feeding the feed gas stream into the heated reactor to carry out the endothermic reaction;

[0024] (viii) reacting the feed gas stream in the heated reactor to obtain a product gas stream;

[0025] wherein the heating in (ii) comprises transferring reaction heat from a chemical conversion process to the combustible stream provided in (i), and

[0026] wherein the exhaust gas stream obtained in (v) contains 5 vol-% or less H2.

[0027] The temperature of the reactor within the meaning of the present invention preferably means the temperature of the reactor wall.

[0028] Furthermore, within the meaning of the present invention, the term "endothermic reaction" primarily denotes any chemical conversion process and / or any physicochemical process which requires an input of energy in the form of heat and is therefore endothermic. For physicochemical processes that fall within the meaning of the term "endothermic reaction" within the meaning of the present invention, these processes may range from heating a process stream to provide a heated process stream, to converting an element or compound at least partially from one state of aggregation to another state of aggregation (such as producing steam from a process stream comprising water). In particular, within the meaning of the present invention, the term "endothermic reaction" is not limited to chemical conversion processes. However, according to the present invention, it is preferred that the term "endothermic reaction" within the ordinary meaning of the term be understood as meaning a chemical conversion process.

[0029] Preferably, the combustible stream according to (i) has a temperature in the range of 5°C to 150°C, more preferably in the range of 15°C to 120°C, more preferably in the range of 20°C to 105°C, more preferably in the range of 40°C to 80°C, more preferably in the range of 50°C to 70°C.

[0030] Preferably, the combustible stream according to (i) has a pressure in the range of 0.5 to 110 bar (absolute pressure), more preferably in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 30 to 70 bar (absolute pressure), more preferably in the range of 40 to 60 bar (absolute pressure).

[0031] Preferably, the combustible stream according to (i) comprises 0 to 1 vol-% O2, more preferably 0 to 0.1 vol-%, more preferably 0 to 0.01 vol-% O2.

[0032] Preferably, the combustible stream according to (i) comprises 98 to 100 vol-% NH3, more preferably 99 to 100 vol-%, more preferably 99.9 to 100 vol-% NH3.

[0033] Preferably, the combustible stream according to (i) comprises 0 to 2.0 vol-% H2O, more preferably 0.01 to 1.5 vol-%, more preferably 0.1 to 1.0 vol-% H2O.

[0034] Preferably, 90 to 100 vol-%, more preferably 95 to 100 vol-%, more preferably 99 to 100 vol-% of the combustible stream according to (i) consists of NH3 and H2O.

[0035] Preferably, the combustible stream is heated according to (ii) to a temperature in the range of 50°C to 850°C, more preferably in the range of 200°C to 700°C, more preferably in the range of 300°C to 600°C, more preferably in the range of 400°C to 500°C.

[0036] Preferably, heating according to (ii) comprises transferring heat using a heat exchanger.

[0037] Preferably, the heat transferred according to (ii) is provided by the exhaust gas stream leaving the combustion chamber according to (v) and / or by the product gas stream according to (viii).

[0038] Preferably, the heat transferred according to (ii) is obtained from an exothermic reaction, or wherein the heat transferred according to (ii) is excess heat to the heat used to carry out the autothermal reaction or the endothermic reaction.

[0039] In the case where the heat transferred according to (ii) is obtained from an exothermic reaction, preferably, the exothermic reaction comprises one or more of the following, more preferably consists of 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 selective oxidation of one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid).

[0040] In the case where the heat transferred according to (ii) is excess heat to the heat used to carry out the endothermic reaction, preferably, the endothermic reaction comprises one or more of the following, more preferably consists of 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.

[0041] In the case where the heat transferred according to (ii) is excess heat to the heat used to carry out the autothermal reaction, preferably the autothermal reaction comprises one or more of the following, more preferably consists of one or more of the following: autothermal reforming of natural gas and hydrocarbons, and 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.

[0042] Preferably, in (iii), at least a portion of the NH3 contained in the heated combustible gas stream is converted into N2 and H2 in an ammonia reforming reactor, wherein more preferably, based on 100 volume-% of NH3 contained in the heated combustible gas stream, 0.1 to 99.9 volume-%, more preferably 5 to 95 volume-% of the NH3 contained in the heated combustible gas stream is converted into N2 and H2 in the ammonia reforming reactor.

[0043] Preferably, the ammonia reforming reactor according to (iii) comprises a catalytic material, preferably a catalytic material as defined in any of the specific and preferred embodiments of the invention.

[0044] Preferably, the reactor according to (iii) is an adiabatic reactor, an isothermal reactor or a combination thereof.

[0045] Within the meaning of the present invention, an adiabatic or isothermal reactor is understood to be a reactor which is operated close to a theoretical adiabatic or isothermal process.

[0046] Preferably, the heated combustible gas stream fed into the reactor according to (iii) has a gas hourly space velocity in the range of 50 to 30,000 / h, more preferably in the range of 150 to 25,000 / h, more preferably in the range of 200 to 20,000 / h, more preferably in the range of 4,000 to 16,000 / h, more preferably in the range of 8,000 to 12,000 / h.

[0047] Preferably, the heated combustible gas stream fed into the reactor according to (iii) has a temperature in the range of 100°C to 1000°C, more preferably in the range of 200°C to 900°C, more preferably in the range of 400°C to 700°C, more preferably in the range of 500°C to 600°C.

[0048] Preferably, the heated combustible gas stream fed into the reactor according to (iii) has a pressure in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 10 to 35 bar (absolute pressure), more preferably in the range of 14 to 31 bar (absolute pressure), more preferably in the range of 18 to 27 bar (absolute pressure).

[0049] Preferably, one or more co-fuels are fed into the combustion chamber together with the heated combustible gas stream obtained in (ii) or the gas stream obtained in (iii), wherein the one or more co-fuels are more preferably selected from the group consisting of naphtha, hydrogen, gasoline, crude oil, pyrolysis oil, gasification products of biomass, (bio)ethanol, alkanes and mixtures of two or more thereof, wherein the one or more co-fuels more preferably comprise, more preferably consist of: (C1-C4) alkanes and mixtures thereof, more preferably (C1-C3) alkanes and mixtures thereof, more preferably (C1-C2) alkanes and mixtures thereof, wherein more preferably the one or more co-fuels more preferably comprise CH4, more preferably consist of CH4.

[0050] Preferably, the reactor comprises, more preferably consists of, a reaction chamber or a tubular reactor, wherein the reactor preferably comprises, more preferably consists of, a tubular reactor, wherein the tubular reactor preferably comprises, more preferably consists of, 1 to 15,000 tubes, more preferably 100 to 11,000 tubes, and more preferably 500 to 5,000 tubes.

[0051] In the case where the reactor comprises a tubular reactor, it is preferred that, independently of each other, the one or more tubes of the tubular reactor have a length in the range of 1 to 30 m, more preferably in the range of 9 to 21 m, and more preferably in the range of 13 to 17 m.

[0052] In the case where the reactor comprises a tubular reactor, it is preferred that, independently of one another, 1 to 100%, more preferably 30 to 70%, more preferably 40 to 60% of the length of the tube of the tubular reactor passes through the combustion chamber.

[0053] In case where the reactor comprises a tubular reactor, it is preferred that, independently of each other, the tubes of the tubular reactor have a diameter in the range of 0.01 to 10 m, more preferably in the range of 2 to 8 m and more preferably in the range of 4 to 6 m.

[0054] Preferably, combusting the combustible gas stream according to (v) comprises

[0055] (v.1) mixing a combustible gas stream with oxygen;

[0056] (v.2) combusting the mixture obtained in (v.1) in the combustion chamber to obtain a gas stream having a temperature in the range of 500°C to 2100°C.

[0057] In the case where burning the combustible gas flow according to (v) includes (v.1) mixing the combustible gas flow with oxygen, preferably, the volume ratio of oxygen to NH3 contained in the mixture obtained in (v.1) is in the range of 1:10 to 9:1, more preferably in the range of 1:5 to 1.8:1, and more preferably in the range of 1:2 to 1.0:1.

[0058] Preferably, the exhaust gas stream obtained in (v) contains 0 to 4 vol-% H2, more preferably 0 to 3 vol-%, more preferably 0 to 2 vol-%, more preferably 0 to 1 vol-%, more preferably 0 to 0.1 vol-%, more preferably 0 to 0.01 vol-% H2.

[0059] Preferably, the exhaust gas stream obtained in (v) has a temperature in the range of 850 to 2100°C, more preferably in the range of 950 to 1700°C, more preferably in the range of 1000 to 1400°C.

[0060] Preferably, the one or more reactants contained in the raw gas stream according to (vi) are selected from the group consisting of naphtha, hydrogen, oxygen, gasoline, crude oil, pyrolysis oil, gasification products of biomass, (bio)ethanol, methane, ethane, propane, butane, H2O, CO2, CO, NH3, ethylbenzene, methanol, dimethyl ether and mixtures of two or more thereof.

[0061] Preferably, the feed gas stream fed to the heated reactor according to (vii) has a gas hourly space velocity in the range of 50 to 300,000 / h, more preferably in the range of 150 to 250,000 / h, more preferably in the range of 200 to 200,000 / h, more preferably in the range of 500 to 100,000 / h, more preferably in the range of 2,000 to 50,000 / h.

[0062] Preferably, the feed gas stream fed to the heated reactor according to (vii) has a temperature in the range of 50°C to 1500°C, more preferably in the range of 100°C to 1400°C, more preferably in the range of 400°C to 1100°C, more preferably in the range of 600°C to 900°C.

[0063] Preferably, the raw gas stream fed to the heated reactor according to (vii) has a pressure in the range of 0.5 to 110 bar (absolute pressure), more preferably in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 30 to 70 bar (absolute pressure), more preferably in the range of 40 to 60 bar (absolute pressure).

[0064] Preferably, the endothermic reaction is selected from the group consisting of: NH3 reforming reaction, steam cracking reaction, alkane dehydrogenation reaction (more preferably ethane dehydrogenation reaction, propane dehydrogenation reaction or butane dehydrogenation reaction), steam reforming reaction, dry reforming reaction, styrene production reaction, methanol reforming reaction, dimethyl ether reforming reaction, reverse water gas shift reaction and alcohol dehydration reaction.

[0065] In the case where the endothermic reaction is an NH 3 reforming reaction, it is preferred that the NH 3 reforming reaction be performed in the presence of a catalytic material.

[0066] In the case where the NH 3 reforming reaction is carried out in the presence of a catalytic material, it is preferred that the catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] Furthermore, 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.

[0071] Additionally and independently thereof, it is preferred that M2 comprises Ru, more preferably is Ru, and wherein the catalytic material shows an atomic ratio of M2:M1 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. Additionally and independently thereof, it is preferred that the catalytic material further comprises Al and O.

[0072] 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.

[0073] 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 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).

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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 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).

[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 Co, La, 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, Co, La, Al and O.

[0080] According to the present invention, preferably, the endothermic reaction is selected from the group consisting of: steam cracking reaction, alkane dehydrogenation reaction (more preferably ethane dehydrogenation reaction, propane dehydrogenation reaction or butane dehydrogenation reaction), steam reforming reaction, dry reforming reaction, styrene production reaction, methanol reforming reaction, dimethyl ether reforming reaction, reverse water gas shift reaction and alcohol dehydration reaction.

[0081] In the case where the NH3 reforming reaction is carried out in the presence of a catalytic material, 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.

[0082] 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.

[0083] Furthermore, it is preferred that the catalytic material 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] In addition 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 more 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), Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd (including combinations of two or more thereof), Al, Ti, Zr, Mg, Ca and La (including combinations of two or more thereof), Al, Zr and Mg (including combinations of two or more thereof). (including combinations of two or more thereof), wherein more preferably the one or more carrier 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), wherein more preferably the one or more carrier materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2, wherein more preferably the one or more carrier materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0092] 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).

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] In addition and independently thereof, 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.

[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, the one or more alkali metal hydroxides and the one or more support materials.

[0101] 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.

[0102] 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.

[0103] In addition and independently thereof, it is preferred that the extrudate is segmented and the catalytic material is in the form of an extrudate having a segmented sieve fraction in the range of 50 μm to 2.5 mm, more preferably 100 μm to 1.5 mm, more preferably 200 μm to 1 mm, more preferably 250 to 700 μm, and more preferably 300 to 500 μm.

[0104] According to the present invention, it is preferred that the endothermic reaction is carried out at a temperature in the range of 200°C to 1100°C, more preferably in the range of 400°C to 900°C, more preferably in the range of 500°C to 800°C.

[0105] Furthermore, it is preferred that the endothermic reaction is carried out at a pressure in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 30 to 70 bar (absolute pressure), more preferably in the range of 40 to 60 bar (absolute pressure).

[0106] It is still further preferred that the endothermic reaction is carried out in the presence of a catalytic material or an inert material.

[0107] Still further preferred, the process is a continuous process.

[0108] The present invention is further illustrated by the following groups of examples and the combination of examples obtained by the dependencies and back-references as shown. In particular, it should be noted that in each case where a series of examples is mentioned, for example in the context of terms such as "composite oxides as described in any one of Examples 1 to 4", each example in this series is intended to be disclosed clearly to the skilled person, that is, the wording of this term should be understood by the skilled person as synonymous with "composite oxides as described in any one of Examples 1, 2, 3 and 4". In addition, it is explicitly pointed out that the following group of examples is not a group of claims that determines the scope of protection, but represents an appropriate structural part of this specification relating to the general and preferred aspects of the present invention.

[0109] 1. A method for carrying out an endothermic reaction in a reactor, the method comprising

[0110] (i) providing a combustible stream comprising NH3, wherein the stream is in a liquid or gaseous state;

[0111] (ii) heating the combustible gas stream provided in (i) to a temperature in the range of 25° C. to 850° C. to obtain a heated combustible gas stream;

[0112] (iii) optionally feeding the heated combustible gas stream obtained in (ii) into an ammonia reforming reactor to obtain a gas stream comprising N2 and H2;

[0113] (iv) feeding the heated combustible gas stream obtained in (ii) or the gas stream obtained in (iii) into a combustion chamber, wherein a reactor is contained in the combustion chamber;

[0114] (v) combusting the combustible gas stream obtained in (ii) or the gas stream obtained in (iii) with oxygen in the combustion chamber to heat the reactor contained in the combustion chamber to a temperature in the range of 500° C. to 2100° C. and obtaining an exhaust gas stream leaving the combustion chamber;

[0115] (vi) preparing a feed gas stream comprising one or more reactants for an endothermic reaction;

[0116] (vii) feeding the feed gas stream into the heated reactor to carry out the endothermic reaction;

[0117] (viii) reacting the feed gas stream in the heated reactor to obtain a product gas stream;

[0118] wherein the heating in (ii) comprises transferring reaction heat from a chemical conversion process to the combustible stream provided in (i), and

[0119] wherein the exhaust gas stream obtained in (v) contains 5 vol-% or less H2.

[0120] 2. A method as described in Example 1, wherein the combustible stream according to (i) has a temperature in the range of 5°C to 150°C, preferably in the range of 15°C to 120°C, more preferably in the range of 20°C to 105°C, more preferably in the range of 40°C to 80°C, more preferably in the range of 50°C to 70°C.

[0121] 3. A method as described in Example 1 or 2, wherein the combustible stream according to (i) has a pressure in the range of 0.5 to 110 bar (absolute pressure), preferably in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 30 to 70 bar (absolute pressure), and more preferably in the range of 40 to 60 bar (absolute pressure).

[0122] 4. The method of any one of embodiments 1 to 3, wherein the combustible stream according to (i) contains 0 to 1 volume-% O2, preferably 0 to 0.1 volume-%, more preferably 0 to 0.01 volume-% O2.

[0123] 5. The method of any one of embodiments 1 to 4, wherein the combustible stream according to (i) comprises 98 to 100 volume-% NH3, preferably 99 to 100 volume-%, more preferably 99.9 to 100 volume-% NH3.

[0124] 6. The method of any one of embodiments 1 to 5, wherein the combustible stream according to (i) comprises 0 to 2.0 vol-% H2O, preferably 0.01 to 1.5 vol-%, more preferably 0.1 to 1.0 vol-% H2O.

[0125] 7. A method as described in any of Examples 1 to 6, wherein 90 to 100 volume-%, preferably 95 to 100 volume-%, more preferably 99 to 100 volume-% of the combustible stream according to (i) consists of NH3 and H2O.

[0126] 8. A method as described in any one of Examples 1 to 7, wherein the combustible stream is heated to a temperature in the range of 50°C to 850°C, preferably in the range of 200°C to 700°C, more preferably in the range of 300°C to 600°C, more preferably in the range of 400°C to 500°C according to (ii).

[0127] 9. The method of any one of embodiments 1 to 8, wherein heating according to (ii) comprises transferring heat using a heat exchanger.

[0128] 10. The method of any one of embodiments 1 to 9, wherein the heat transferred according to (ii) is provided by the exhaust gas stream leaving the combustion chamber according to (v) and / or by the product gas stream according to (viii).

[0129] 11. The method of any one of embodiments 1 to 10, wherein the heat transferred according to (ii) is obtained from an exothermic reaction, or wherein the heat transferred according to (ii) is excess heat to the heat used to carry out an autothermal reaction or an endothermic reaction.

[0130] 12. A method as described in Example 11, wherein the exothermic reaction includes one or more of the following, preferably consists of 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 selective oxidation of one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid).

[0131] 13. A method as described in Example 11, wherein the endothermic reaction includes one or more of the following, and preferably consists of 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.

[0132] 14. The method of embodiment 11, wherein the autothermal reaction comprises one or more of, preferably consists of, autothermal reforming of natural gas and hydrocarbons, and 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.

[0133] 15. A method as described in any one of Examples 1 to 14, wherein in (iii), at least a portion of the NH3 contained in the heated combustible gas stream is converted into N2 and H2 in an ammonia reforming reactor, wherein preferably, based on 100 volume-% of NH3 contained in the heated combustible gas stream, 0.1 to 99.9 volume-%, more preferably 5 to 95 volume-% of the NH3 contained in the heated combustible gas stream is converted into N2 and H2 in the ammonia reforming reactor.

[0134] 16. The method of any one of embodiments 1 to 15, wherein the ammonia reforming reactor according to (iii) comprises a catalytic material, preferably a catalytic material as defined in any one of embodiments 36 to 74.

[0135] 17. The method of any one of embodiments 1 to 16, wherein the reactor according to (iii) is an adiabatic reactor, an isothermal reactor, or a combination thereof.

[0136] 18. A method as described in any one of Examples 1 to 17, wherein the heated combustible gas stream fed into the reactor according to (iii) has a gas hourly space velocity in the range of 50 to 30,000 / h, preferably in the range of 150 to 25,000 / h, more preferably in the range of 200 to 20,000 / h, more preferably in the range of 4,000 to 16,000 / h, more preferably in the range of 8,000 to 12,000 / h.

[0137] 19. A method as described in any one of Examples 1 to 18, wherein the heated combustible gas stream fed into the reactor according to (iii) has a temperature in the range of 100°C to 1000°C, preferably in the range of 200°C to 900°C, more preferably in the range of 400°C to 700°C, more preferably in the range of 500°C to 600°C.

[0138] 20. A method as described in any one of Examples 1 to 19, wherein the heated combustible gas stream fed into the reactor according to (iii) has a pressure in the range of 1 to 100 bar (absolute pressure), preferably in the range of 10 to 35 bar (absolute pressure), more preferably in the range of 14 to 31 bar (absolute pressure), and more preferably in the range of 18 to 27 bar (absolute pressure).

[0139] 21. A method as described in any one of Examples 1 to 20, wherein, preferably, one or more co-fuels are fed into the combustion chamber together with the heated combustible gas stream obtained in (ii) or the gas stream obtained in (iii), wherein the one or more co-fuels are preferably selected from the group consisting of naphtha, hydrogen, gasoline, crude oil, pyrolysis oil, gasification products of biomass, (bio)ethanol, alkanes and mixtures of two or more thereof, wherein the one or more co-fuels more preferably comprise, more preferably consist of: (C1-C4) alkanes and mixtures thereof, more preferably (C1-C3) alkanes and mixtures thereof, more preferably (C1-C2) alkanes and mixtures thereof, wherein more preferably the one or more co-fuels more preferably comprise CH4, more preferably consist of CH4.

[0140] 22. The method of any one of embodiments 1 to 21, wherein the reactor comprises, preferably consists of, a reaction chamber or a tubular reactor, wherein the reactor preferably comprises, more preferably consists of, a tubular reactor, wherein the tubular reactor preferably comprises, more preferably consists of: 1 to 15,000 tubes, more preferably 100 to 11,000 tubes, and more preferably 500 to 5,000 tubes.

[0141] 23. A method as described in Example 22, wherein, independently of each other, the one or more tubes of the tubular reactor have a length in the range of 1 to 30 m, more preferably in the range of 9 to 21 m, and more preferably in the range of 13 to 17 m.

[0142] 24. The method of embodiment 22 or 23, wherein, independently of one another, 1% to 100%, preferably 30% to 70%, more preferably 40% to 60% of the length of the tube of the tubular reactor passes through the combustion chamber.

[0143] 25. The method of any one of embodiments 22 to 24, wherein, independently of each other, the tubes of the tubular reactor have a diameter in the range of 0.01 to 10 m, more preferably in the range of 2 to 8 m, and more preferably in the range of 4 to 6 m.

[0144] 26. The method of any one of embodiments 1 to 25, wherein combusting the combustible gas stream according to (v) comprises

[0145] (v.1) mixing the combustible gas stream with oxygen;

[0146] (v.2) combusting the mixture obtained in (v.1) in the combustion chamber to obtain a gas stream having a temperature in the range of 500°C to 2100°C.

[0147] 27. A method as described in Example 26, wherein the volume ratio of oxygen to NH3 contained in the mixture obtained in (v.1) is in the range of 1:10 to 9:1, preferably in the range of 1:5 to 1.8:1, and more preferably in the range of 1:2 to 1.0:1.

[0148] 28. A method as described in any of Examples 1 to 27, wherein the exhaust gas stream obtained in (v) contains 0 to 4 volume-% H2, preferably 0 to 3 volume-%, more preferably 0 to 2 volume-%, more preferably 0 to 1 volume-%, more preferably 0 to 0.1 volume-%, more preferably 0 to 0.01 volume-% H2.

[0149] 29. A method as described in any one of Examples 1 to 28, wherein the exhaust gas stream obtained in (v) has a temperature in the range of 850°C to 2100°C, preferably in the range of 950°C to 1700°C, and more preferably in the range of 1000°C to 1400°C.

[0150] 30. A method as described in any one of embodiments 1 to 29, wherein the one or more reactants contained in the raw gas stream according to (vi) are selected from the group consisting of: naphtha, hydrogen, oxygen, gasoline, crude oil, pyrolysis oil, gasification products of biomass, (bio)ethanol, methane, ethane, propane, butane, H2O, CO2, CO, NH3, ethylbenzene, methanol, dimethyl ether and mixtures of two or more thereof.

[0151] 31. A method as described in any of Examples 1 to 30, wherein the raw gas stream fed to the heated reactor according to (vii) has a gas hourly space velocity in the range of 50 to 300,000 / h, preferably in the range of 150 to 250,000 / h, more preferably in the range of 200 to 200,000 / h, more preferably in the range of 500 to 100,000 / h, more preferably in the range of 2,000 to 50,000 / h.

[0152] 32. A method as described in any one of Examples 1 to 31, wherein the raw gas stream fed to the heated reactor according to (vii) has a temperature in the range of 50°C to 1500°C, preferably in the range of 100°C to 1400°C, more preferably in the range of 400°C to 1100°C, and more preferably in the range of 600°C to 900°C.

[0153] 33. A method as described in any of Examples 1 to 32, wherein the raw gas stream fed to the heated reactor according to (vii) has a pressure in the range of 0.5 to 110 bar (absolute pressure), preferably in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 30 to 70 bar (absolute pressure), and more preferably in the range of 40 to 60 bar (absolute pressure).

[0154] 34. A method as described in any one of Examples 1 to 33, wherein the endothermic reaction is selected from the group consisting of: NH3 reforming reaction, steam cracking reaction, alkane dehydrogenation reaction (preferably ethane dehydrogenation reaction, propane dehydrogenation reaction or butane dehydrogenation reaction), steam reforming reaction, dry reforming reaction, styrene production reaction, methanol reforming reaction, dimethyl ether reforming reaction, reverse water gas shift reaction and alcohol dehydration reaction.

[0155] 35. A method as described in Example 34, wherein the endothermic reaction is an NH3 reforming reaction, wherein the NH3 reforming reaction is preferably carried out in the presence of a catalytic material.

[0156] 36. The method of embodiment 35, wherein the catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

[0157] 37. A method as described in Example 36, 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.

[0158] 38. A method as described in Example 36 or 37, 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.

[0159] 39. A method as described in any of Examples 36 to 38, 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.

[0160] 40. A method as described in Example 39, 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.

[0161] 41. A method as described in Example 39 or 40, 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.

[0162] 42. The method of any one of embodiments 39 to 41, wherein the catalytic material further comprises Al and O.

[0163] 43. The method of embodiment 42, wherein the catalytic material comprises Ni as the metal M1, wherein preferably the metal M1 is Ni.

[0164] 44. A method as described in Example 43, 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).

[0165] 45. A method as described in Example 43 or 44, 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.

[0166] 46. ​​A method as described in Example 43 or 44, 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.

[0167] 47. The method of embodiment 42, wherein the catalytic material comprises Co as the metal M1, wherein preferably the metal M1 is Co.

[0168] 48. A method as described in Example 47, 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).

[0169] 49. A method as described in Example 47 or 48, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of Co, La, Al and O.

[0170] 50. A method as described in Example 47 or 48, wherein 95 to 100 wt.-%, preferably 97 to 100 wt.-%, more preferably 98 to 100 wt.-%, more preferably 99 to 100 wt.-%, more preferably 99.5 to 100 wt.-%, and more preferably 99.9 to 100 wt.-% of the catalytic material consists of M2, Co, La, Al and O.

[0171] 51. A method as described in any one of Examples 1 to 50, wherein the endothermic reaction is selected from the group consisting of: steam cracking reaction, alkane dehydrogenation reaction (preferably ethane dehydrogenation reaction, propane dehydrogenation reaction or butane dehydrogenation reaction), steam reforming reaction, dry reforming reaction, styrene production reaction, methanol reforming reaction, dimethyl ether reforming reaction, reverse water gas shift reaction and alcohol dehydration reaction.

[0172] 52. The method of embodiment 35, 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, 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.

[0173] 53. A method as described in Example 52, 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.

[0174] 54. A method as described in Example 52 or 53, wherein the catalytic material contains Ni and Co in an amount 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, calculated as the corresponding elements and based on 100 wt.-% of the reactor.

[0175] 55. The method of any one of embodiments 52 to 54, 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.

[0176] 56. The method of any one of embodiments 52 to 55, 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.

[0177] 57. A method as described in any of Examples 52 to 56, 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.

[0178] 58. The method of any one of embodiments 52 to 57, 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.

[0179] 59. A method as described in any of Examples 52 to 58, 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.

[0180] 60. A method as described in any of Examples 52 to 59, 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.

[0181] 61. A method as described in any one of Examples 52 to 60, 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.

[0182] 62. The method of any one of embodiments 52 to 61, 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), Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr and Nd (including combinations of two or more thereof), Al, Ti, Zr, Mg, Ca and La (including combinations of two or more thereof), 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 being selected from the group consisting of Al2O3, ZrO2 and spinel (including mixtures of two or more thereof), preferably selected from the group consisting of ZrO2 and spinel (including mixtures of two or more thereof), wherein more preferably the one or more carrier materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2, wherein more preferably the one or more carrier materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0183] 63. A method as described in Example 62, 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.

[0184] 64. The method of any one of Embodiments 52 to 63, 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.

[0185] 65. A method as described in any of Examples 52 to 64, 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.

[0186] 66. The method of any one of embodiments 52 to 65, 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.

[0187] 67. A method as described in any of Examples 52 to 66, 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.

[0188] 68. A method as described in any of Examples 52 to 67, 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.

[0189] 69. A method as described in any one of Examples 52 to 68, 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 a mixture of two or more thereof), more preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH and KOH (including a mixture of two or more thereof), more preferably selected from the group consisting of LiOH, NaOH and KOH (including a mixture of two or more thereof), wherein more preferably the catalytic material further comprises KOH and / or LiOH, preferably KOH.

[0190] 70. A method as described in any of Embodiments 52 to 69, wherein the catalytic material comprises 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 support materials.

[0191] 71. A method as described in any of Examples 52 to 70, 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.

[0192] 72. The method of any one of embodiments 52 to 71, 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.

[0193] 73. A method as described in Example 72, 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.

[0194] 74. A method as described in Example 72 or 73, wherein the extrudates are segmented and the catalytic material is in the form of extrudates having segmented sieve fractions in the range of 50 μm to 2.5 mm, preferably 100 μm to 1.5 mm, more preferably 200 μm to 1 mm, more preferably 250 to 700 μm, and more preferably 300 to 500 μm.

[0195] 75. The method of any one of embodiments 1 to 74, wherein the endothermic reaction is carried out at a temperature in the range of 200°C to 1100°C, preferably in the range of 400°C to 900°C, more preferably in the range of 500°C to 800°C.

[0196] 76. The method of any one of embodiments 1 to 75, wherein the endothermic reaction is carried out at a pressure in the range of 1 to 100 bar (absolute pressure), preferably in the range of 30 to 70 bar (absolute pressure), more preferably in the range of 40 to 60 bar (absolute pressure).

[0197] 77. The method of any one of embodiments 1 to 76, wherein the endothermic reaction is performed in the presence of a catalytic material or an inert material.

[0198] 78. The method of any one of embodiments 1 to 77, wherein the method is a continuous method.

[0199] The present invention is further illustrated by the following examples and comparative examples.

[0200] Experimental Section

[0201] Example 1: Method for carrying out an endothermic reaction in a reactor

[0202] like Figure 1 As shown in FIG. 1 , a combustion chamber is provided, which can be heated by burning a combustible stream therein with oxygen. The combustible stream contains NH3, part of which can be reformed before being burned in the combustion chamber. The combustible stream can additionally contain a co-fuel. The combustible stream containing NH3 can be regarded as a blend of conventional fuel and NH3, which has an energy content of 7-8 MW.

[0203] Prior to combustion, the combustible stream is heated by transferring the heat of reaction from the chemical conversion process. The heat may be obtained from an exothermic reaction, or it may be excess heat for heat from an autothermal reaction or an endothermic reaction. For example, water and / or steam may be used to transfer the heat from the chemical conversion process to the combustible stream.

[0204] In addition, if Figure 1 As shown in FIG. 1 , a tubular reactor passes through a combustion chamber. In the reactor, an endothermic reaction occurs. The endothermic reaction may be, for example, a steam cracking process. BRIEF DESCRIPTION OF THE DRAWINGS

[0205] Figure 1 : Schematically shows a combustion chamber comprising a tubular reactor according to Example 1, wherein the reactor passes through the combustion chamber.

[0206] References:

[0207] -Banares-Alcantara et al.in Applied Energy 2021,282,116009

[0208] -US 8464515 B2

[0209] -WO 2019 / 038251 A1

[0210] -US 8691182 B2

[0211] -US 8961923 B2

Claims

1. A method for carrying out an endothermic reaction in a reactor, the method comprising (i) providing a combustible stream comprising NH3, wherein the stream is in a liquid or gaseous state; (ii) heating the combustible gas stream provided in (i) to a temperature in the range of 25° C. to 850° C. to obtain a heated combustible gas stream; (iii) optionally feeding the heated combustible gas stream obtained in (ii) into an ammonia reforming reactor to obtain a gas stream comprising N2 and H2; (iv) feeding the heated combustible gas stream obtained in (ii) or the gas stream obtained in (iii) into a combustion chamber, wherein a reactor is contained in the combustion chamber; (v) combusting the combustible gas stream obtained in (ii) or the gas stream obtained in (iii) with oxygen in the combustion chamber to heat the reactor contained in the combustion chamber to a temperature in the range of 500° C. to 2100° C. and obtaining an exhaust gas stream leaving the combustion chamber; (vi) preparing a feed gas stream comprising one or more reactants for an endothermic reaction; (vii) feeding the feed gas stream into the heated reactor to carry out the endothermic reaction; (viii) reacting the feed gas stream in the heated reactor to obtain a product gas stream; wherein the heating in (ii) comprises transferring reaction heat from a chemical conversion process to the combustible stream provided in (i), and wherein the exhaust gas stream obtained in (v) contains 5 vol-% or less H2.

2. The method of claim 1, wherein: The combustible stream according to (i) contains 0 to 1 vol-% O2.

3. The method according to claim 1 or 2, wherein: The combustible stream according to (i) comprises 98 to 100 vol-% NH 3 .

4. The method according to any one of claims 1 to 3, wherein: The combustible stream according to (i) comprises 0 to 2.0 vol-% H2O.

5. The method according to any one of claims 1 to 4, wherein: The heating according to (ii) comprises transferring heat using a heat exchanger.

6. The method according to any one of claims 1 to 5, wherein: The heat transferred according to (ii) is provided by the exhaust gas stream leaving the combustion chamber according to (v) and / or by the product gas stream according to (viii).

7. The method according to any one of claims 1 to 6, wherein: The heat transferred according to (ii) is obtained from an exothermic reaction, or wherein the heat transferred according to (ii) is excess heat to the heat used to carry out the autothermal reaction or the endothermic reaction.

8. The method according to any one of claims 1 to 7, wherein: The reactor according to (iii) is an adiabatic reactor, an isothermal reactor or a combination thereof.

9. The method according to any one of claims 1 to 8, wherein: Combusting the combustible gas stream according to (v) comprises (v.1) mixing the combustible gas stream with oxygen; (v.2) combusting the mixture obtained in (v.1) in the combustion chamber to obtain a gas stream having a temperature in the range of 500°C to 2100°C.

10. The method according to any one of claims 1 to 9, wherein: The endothermic reaction is an NH 3 reforming reaction, wherein the NH 3 reforming reaction is performed in the presence of a catalytic material.

11. The method of claim 10, wherein: The catalytic material comprises a metal M1, wherein M1 is Ni, Co, or Ni and Co.

12. The method according to claim 10 or 11, 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.

13. The method of claim 12, 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 supported on the one or more support materials supporting Ru.

14. The method according to any one of claims 1 to 13, wherein: This endothermic reaction proceeds at a temperature in the range of 200°C to 1100°C.

15. The method according to any one of claims 1 to 14, wherein: This endothermic reaction is carried out in the presence of a catalytic material or an inert material.

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