A method for performing endothermic reactions in a reactor with reduced CO2 emissions

Abstract

The present invention relates to a method for conducting an endothermic reaction in a reactor, the method particularly comprising heating a combustible stream comprising NH3 to a temperature in the range of 25-850°C, wherein the heating comprises transferring heat of reaction from a chemical conversion process to the combustible stream; supplying the heated combustible gas stream to a combustion chamber through which a portion of the reactor passes; combusting the combustible gas stream with oxygen in the combustion chamber to heat the portion of the reactor passing through the combustion chamber to a temperature in the range of 500-2100°C; supplying a feed gas stream comprising one or more reactants to the heated reactor to conduct 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 conducting an endothermic reaction in a reactor, particularly comprising the steps of heating a combustible stream comprising NH3, optionally reforming the NH3 to obtain a gas stream comprising N2 and H2, combusting the heated combustible gas stream or the gas stream comprising N2 and H2 with oxygen in a combustion chamber to heat a portion of the reactor passing through the combustion chamber, and reacting a feed gas stream in the heated reactor to obtain a product gas stream, wherein the heating comprises transferring heat of reaction from a chemical conversion process to the combustible stream. [Background technology]

[0002] NH3 can be considered a future energy vector because it can chemically store significant amounts of H2. NH3 can be reformed into nitrogen and hydrogen (see Equation 1) to return the hydrogen to chemical processes or other uses. Furthermore, NH3 can be used in thermal heaters as a sustainable, carbon-free fuel. Generally, NH3 can be used directly or after reforming, and reforming can be partial or complete. The degree of NH3 reforming depends primarily on the needs of the combined fuel application, with higher hydrogen content typically being used to increase flame temperature. Additionally, NH3 can be used as a co-fuel, either directly or after reforming. For example, conventional natural gas-based thermal heaters can use NH3 as a co-fuel, either directly or after reforming. This allows for at least partial decarbonization of the thermal heater, depending on the amount of natural gas replaced by NH3-containing fuel. The NH3 reforming process is an endothermic reaction (+45.6 kJ / mol), requiring additional energy input. Also, evaporating NH3, which is normally a liquid, into a gas is an energy-intensive process (+23 kJ / mol).

[0003]

number

[0004] WO2019 / 038251A1 relates to an autothermal ammonia decomposition process, in particular a method for producing a product gas containing nitrogen and hydrogen from ammonia, the method comprising the steps of: generating a process gas containing nitrogen, water, a quantity of nitrogen oxides and residual ammonia by non-catalytic partial oxidation of ammonia with an oxygen-containing gas; decomposing at least a portion of the residual amount of ammonia in the process gas into hydrogen and nitrogen by contact with a nickel-containing catalyst, and simultaneously reducing the amount of nitrogen oxides to nitrogen and water by reaction with a portion of the hydrogen formed during the decomposition of the process gas by contacting the process gas with the nickel-containing catalyst; and removing the product gas containing hydrogen and nitrogen.

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

[0006] US8464515B2 discloses an NH3 burning internal combustion engine in which reformed gas reformed in a reformer is supplied into a combustion chamber.

[0007] US8691182B2 and US8961923B2 relate to a method for decomposing ammonia, which method comprises inter alia heating a gas stream comprising ammonia and a gas stream comprising oxygen in a heat exchanger, reacting said gas streams in a mixing burner to obtain a hydrogen-containing gas mixture, and cooling the obtained hydrogen-containing gas mixture in a heat exchanger.

[0008] Thus, there is a need to provide improved methods for conducting endothermic reactions that are relatively resource efficient and, in particular, that are carried out in a more sustainable manner. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] WO2019 / 038251A1 [Patent Document 2] US8464515B2 [Patent Document 3] US8691182B2 [Patent Document 4] US8961923B2 [Non-patent literature]

[0010] [Non-Patent Document 1] Banares-Alcantara et al., Applied Energy 2021,282,116009 Summary of the Invention [Problem to be solved by the invention]

[0011] It is therefore an object of the present invention to provide a new method for carrying out endothermic reactions, in particular with reduced CO2 emissions. NG = 47 MJ / kg) with, for example, 2.52 kg of NH3 (same energy content), we can assume that this will directly save 2.5-2.7 kg of CO2 emissions. This represents a significant reduction in CO2 emissions for energy-intensive endothermic high-temperature applications.

[0012] It has surprisingly been found that combining the heating of a combustible gas stream containing NH3 with heat transfer from a chemical conversion process provides an improved method for conducting endothermic reactions, said improvement being coupled with a reduction in CO2 emissions by replacing carbon-based energy carriers with NH3.

[0013] Heat transfer can be achieved, for example, by a heat exchanger. The energy required for heat transfer can be provided by excess heat used in exothermic reactions or high-temperature endothermic reactions. In either case, heat can be transferred via a hot outlet gas or fluid.

[0014] Hot NH3 can also be converted before its combustion, for example in an adiabatic reactor in the presence of a catalyst. The degree of conversion of NH3 depends on its temperature. The low heat value (LHV) of H2 (LHV H2 =120MJ / kg) is NH3(LHV NH3 = 18.6 MJ / kg), the degree of NH3 conversion or H2 concentration when the fuel burns is linked to the flame temperature. For example, higher temperatures can be achieved with higher hydrogen concentrations (or NH3 conversion).

[0015] Thus, it has been surprisingly discovered that NH3, whether converted or unconverted, can function as a sustainable, carbon-free fuel. Furthermore, it has been discovered that NH3 can be utilized as a co-fuel, particularly with natural gas. It has also been discovered that NH3-containing streams can be heated with excess heat from chemical processes. The degree of NH3 reforming and H2 concentration determine the flame temperature and its applications.

[0016] The unit bar (abs) means absolute pressure, and 1 bar is 10 5 Equivalent to Pa.

[0017] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the indicated dependencies and backward references. In particular, it should be noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "the method of any one of embodiments 1 to 4," all embodiments within this range are meant to be expressly disclosed for those skilled in the art, i.e., this expression means that those skilled in the art will understand that it is synonymous with "the method of any one of embodiments 1, 2, 3, and 4." Furthermore, it is expressly noted that the following set of embodiments represents a suitably structured part of the description directed to the general and preferred aspects of the present invention, rather than a set of claims determining the scope of protection. [Means for solving the problem]

[0018] The present invention therefore relates to a method for carrying out an endothermic reaction in a reactor, said method comprising the following steps: (i) providing a combustible stream comprising NH3, wherein the stream is a liquid or a gas; (ii) heating the combustible stream provided in (i) to a temperature in the range of 25 to 850°C to obtain a heated combustible gas stream; (iii) optionally feeding the heated combustible gas stream obtained in (ii) to 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 the combustion chamber contains a reactor; (v) burning the combustible gas stream obtained in (ii) or the gas stream obtained in (iii) with oxygen in a combustion chamber to heat a reactor contained in the combustion chamber to a temperature in the range of 500 to 2100°C, and obtaining an exhaust gas stream exiting 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 a heated reactor for carrying out an endothermic reaction; (viii) reacting said feed gas stream in a heated reactor to obtain a product gas stream. Including, the heating in (ii) comprises transferring heat of reaction from a chemical conversion process to the combustible stream provided in (i); and The exhaust gas stream obtained in (v) contains no more than 5% by volume of H2. [Brief explanation of the drawings]

[0019] [Figure 1] 1 shows a schematic representation of a combustion chamber containing a tubular reactor according to Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0020] In the sense of the present invention, the temperature of the reactor preferably means the temperature of the reactor wall.

[0021] Furthermore, in the sense of the present invention, the term "endothermic reaction" refers to any chemical conversion process and / or any physicochemical process that requires energy input, primarily in the form of heat, and is therefore endothermic. Regarding physicochemical processes that fall under the term "endothermic reaction" in the sense of the present invention, these range from the heating of a process stream to produce a heated process stream, to the at least partial conversion of elements or chemical compounds from one aggregate state to another, for example, the production of steam from a process stream containing water. In particular, in the sense of the present invention, the term "endothermic reaction" is not limited to chemical conversion processes. However, according to the present invention, the term "endothermic reaction" is preferably understood within the general meaning of this term as designating a chemical conversion process.

[0022] The combustible stream according to (i) preferably has a temperature in the range of 5 to 150°C, more preferably in the range of 15 to 120°C, more preferably in the range of 20 to 105°C, more preferably in the range of 40 to 80°C, more preferably in the range of 50 to 70°C.

[0023] The combustible stream according to (i) preferably has a pressure in the range of 0.5 to 110 bar (abs), more preferably in the range of 1 to 100 bar (abs), more preferably in the range of 30 to 70 bar (abs), more preferably in the range of 40 to 60 bar (abs).

[0024] Preferably, the combustible stream according to (i) contains 0-1% by volume O2, more preferably 0-0.1% by volume, more preferably 0-0.01% by volume O2.

[0025] Preferably, the combustible stream according to (i) comprises 98-100% by volume of NH3, more preferably 99-100% by volume, more preferably 99.9-100% by volume of NH3.

[0026] The combustible stream according to (i) preferably contains 0-2.0% by volume of H2O, more preferably 0.01-1.5% by volume, more preferably 0.1-1.0% by volume of H2O.

[0027] Preferably, 90-100% by volume of the combustible stream according to (i) consists of NH3 and H2O, more preferably 95-100% by volume, more preferably 99-100% by volume.

[0028] Preferably, the combustible stream is heated by (ii) to a temperature in the range of 50 to 850°C, more preferably in the range of 200 to 700°C, more preferably in the range of 300 to 600°C, more preferably in the range of 400 to 500°C.

[0029] Preferably, heating according to (ii) involves the transfer of heat using a heat exchanger.

[0030] The heat transferred by (ii) is preferably supplied by the exhaust gas stream exiting the combustion chamber by (v) and / or from the product gas stream by (viii).

[0031] Preferably, the heat transferred by (ii) is obtained from an exothermic reaction, or the heat transferred by (ii) is excess heat from that used to carry out an auto-exothermic or endothermic reaction.

[0032] When the heat transferred by (ii) is obtained from an exothermic reaction, it is preferred that the exothermic reaction comprises, more preferably consists of, one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and the selective oxidation of one or more of alkanes, alkenes, and alkynes, preferably the selective oxidation of one or more of alkanes, alkenes, and alkynes to acrolein or acrylic acid.

[0033] When the heat transferred by (ii) is excess heat of heat used to carry out an endothermic reaction or is heat of an endothermic reaction, the endothermic reaction preferably comprises, more preferably consists of, 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.

[0034] When the heat transferred by (ii) is excess heat to that used to carry out the autothermal reaction, the autothermal reaction preferably comprises, and more preferably consists of, one or more of autothermal reforming of natural gas and hydrocarbons, and partial oxidation of hydrocarbons (POx), and the hydrocarbons are selected from the group consisting of (C1 to C 10 ) alkanes, more preferably (C1-C8) alkanes, more preferably (C1-C7) alkanes.

[0035] In (iii), it is preferred that at least a portion of the NH3 contained in the heated combustible gas stream is converted to N2 and H2 in the ammonia reforming reactor, and more preferably, 0.1 to 99.9 vol%, more preferably 5 to 95 vol%, of the NH3 contained in the heated combustible gas stream is converted to N2 and H2 in the ammonia reforming reactor, relative to 100 vol% of NH3 contained in the heated combustible gas stream.

[0036] Preferably, the ammonia reforming reactor according to (iii) comprises a catalytic material, preferably a catalytic material as defined in any one of the particular preferred embodiments of the present invention.

[0037] The reactor according to (iii) is preferably an adiabatic reactor, an isothermal reactor, or a combination thereof.

[0038] In the sense of the present invention, an adiabatic or isothermal reactor is understood to be a reactor which operates in close proximity to a theoretical adiabatic or isothermal process.

[0039] The heated combustible gas stream supplied to the reactor by (iii) preferably 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.

[0040] The heated combustible gas stream supplied to the reactor by (iii) preferably has a temperature in the range of 100 to 1000°C, more preferably in the range of 200 to 900°C, more preferably in the range of 400 to 700°C, more preferably in the range of 500 to 600°C.

[0041] The heated combustible gas stream supplied to the reactor by (iii) preferably has a pressure in the range of 1 to 100 bar (abs), more preferably in the range of 10 to 35 bar (abs), more preferably in the range of 14 to 31 bar (abs), more preferably in the range of 18 to 27 bar (abs).

[0042] It is preferred that one or more co-fuels are fed to the combustion chamber together with the heated combustible gas stream obtained in (ii) or the gas stream obtained in (iii), and 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; 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; and more preferably the one or more co-fuels comprise, more preferably consist of CH4.

[0043] It is preferred that the reactor comprises, or more preferably consists of, a reaction chamber or a tubular reactor, the reactor preferably comprises, or more preferably consists of, a tubular reactor, and the tubular reactor preferably comprises, or more preferably consists of, 1 to 15,000 tubes, more preferably 100 to 11,000 tubes, and more preferably 500 to 5,000 tubes.

[0044] When the reactor comprises a tubular reactor, it is preferred that one or more tubes of the tubular reactor independently 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.

[0045] When the reactor comprises a tubular reactor, it is preferred that 1 to 100%, more preferably 30 to 70%, more preferably 40 to 60% of the length of the tubes of the tubular reactor pass through the combustion chambers independently of each other.

[0046] When the reactor comprises a tubular reactor, it is preferred that the tubes of the tubular reactor have, independently of one another, diameters 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.

[0047] (v) burning the flammable gas stream; (v.1) Mixing a combustible gas stream with oxygen; (v.2) burning the mixture obtained in (v.1) in a combustion chamber to obtain a gas stream having a temperature in the range of 500 to 2100°C. It is preferred that the compound contains:

[0048] When burning the combustible gas stream by (v) comprises (v.1) mixing the combustible gas stream with oxygen, it is preferred that the volume ratio of oxygen to NH3 contained in the mixture obtained by (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.

[0049] The exhaust gas stream obtained in (v) preferably contains 0-4 vol% H2, more preferably 0-3 vol%, more preferably 0-2 vol%, more preferably 0-1 vol%, more preferably 0-0.1 vol%, more preferably 0-0.01 vol% H2.

[0050] The exhaust gas stream obtained in (v) preferably 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.

[0051] Preferably, the one or more reactants comprised in the feed 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, HO, CO, CO, NH, ethylbenzene, methanol, dimethyl ether, and mixtures of two or more thereof.

[0052] The raw material gas stream supplied to the reactor heated by (vii) preferably 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.

[0053] The raw gas stream supplied to the reactor heated by (vii) preferably has a temperature in the range of 50 to 1500°C, more preferably in the range of 100 to 1400°C, more preferably in the range of 400 to 1100°C, more preferably in the range of 600 to 900°C.

[0054] The feed gas stream fed to the reactor heated by (vii) preferably has a pressure in the range of 0.5 to 110 bar (abs), more preferably in the range of 1 to 100 bar (abs), more preferably in the range of 30 to 70 bar (abs), more preferably in the range of 40 to 60 bar (abs).

[0055] The endothermic reaction is preferably selected from the group consisting of an NH3 reforming reaction, a steam cracking reaction, an alkane dehydrogenation reaction, more preferably an ethane dehydrogenation reaction, a propane dehydrogenation reaction, or a butane dehydrogenation reaction, a steam reforming reaction, a dry reforming reaction, a styrene production reaction, a methanol reforming reaction, a dimethyl ether reforming reaction, a reverse water-gas shift reaction, and an alcohol dehydration reaction.

[0056] When the endothermic reaction is an NH3 reforming reaction, the NH3 reforming reaction is preferably carried out in the presence of a catalytic material.

[0057] When the NH3 reforming reaction is carried out in the presence of a catalytic material, it is preferred that the catalytic material comprises a metal M1, where M1 is Ni, Co, or Ni and Co.

[0058] When the catalytic material comprises a metal M1 (M1 is Ni, Co, or Ni and Co), it is preferred that the catalytic material further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably K, Na, Cs, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably K, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, and more preferably M2 comprises Fe, Ru, or Fe and Ru, more preferably M2 comprises Ru, more preferably M2 is Ru.

[0059] Furthermore, independently thereof, it is preferred that the catalytic material further comprises one or more support materials on which the metal M1 or the metals M1 and M2 are supported, the one or more support materials being more preferably selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, and mixtures thereof, and more preferably the support material comprises Al2O3.

[0060] Furthermore, independently thereof, it is preferred that the catalyst material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, more preferably in the range of 0.5:99.5 to 75:25, more preferably in the range of 1:99 to 70:30, more preferably in the range of 5:95 to 65:35, more preferably in the range of 15:85 to 60:40, more preferably in the range of 30:70 to 55:45, and more preferably in the range of 40:60 to 50:50.

[0061] Furthermore, it is preferred that M2 comprises Fe, more preferably is Fe, and that the catalyst material exhibits an M2:M1 atomic ratio in the range of 1:99 to 80:20, more preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, and more preferably 40:60 to 50:50.

[0062] Furthermore, independently therefrom, it is preferred that M2 comprises Ru, more preferably is Ru, and that the catalytic material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 30:70, preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, and more preferably 5:95 to 6:94. Furthermore, independently therefrom, it is preferred that the catalytic material further comprises Al and O.

[0063] When the catalytic material further comprises Al and O, it is preferred that the catalytic material comprises Ni as the metal M1, and more preferably the metal M1 is Ni.

[0064] When the catalyst material contains Ni as the metal M1, it is preferable that the catalyst material further contains Mg, and the molar ratio of Ni:Mg:Al is 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).

[0065] Furthermore, independently of this, it is preferable that 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of the catalyst material consist of Ni, Mg, Al, and O.

[0066] Furthermore, independently of this, it is preferable that 95 to 100 mass%, more preferably 97 to 100 mass%, more preferably 98 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of the catalyst material consists of M2, Ni, Mg, Al, and O.

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

[0068] When the catalyst material contains Co as the metal M1, it is preferable that the catalyst material further contains La, and the molar ratio of Co:La:Al is 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).

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

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

[0071] According to the present invention, the endothermic reaction is preferably selected from the group consisting of a steam cracking reaction, an alkane dehydrogenation reaction, more preferably an ethane dehydrogenation reaction, a propane dehydrogenation reaction, or a butane dehydrogenation reaction, a steam reforming reaction, a dry reforming reaction, a styrene production reaction, a methanol reforming reaction, a dimethyl ether reforming reaction, a reverse water-gas shift reaction, and an alcohol dehydration reaction.

[0072] When the NH3 reforming reaction is carried out in the presence of a catalytic material, the catalytic material preferably comprises Ru and one or more support materials, wherein the Ru is supported on one or more support materials, and the one or more support materials are 20 m 2 / g or more, the BET specific surface area being preferably measured in accordance with ISO 9277:2010, and the catalyst material contains 1 mass % or less of Ni and Co, each calculated as an element relative to 100 mass % of the catalyst material.

[0073] When the catalytic material comprises Ru and one or more support materials, it is preferred that the catalytic material contain no more than 0.5%, more preferably no more than 0.1%, more preferably no more than 0.05%, more preferably no more than 0.01%, more preferably no more than 0.005%, and more preferably no more than 0.001%, by weight of Ni and Co, each calculated as the element relative to 100% by weight of the catalytic material.

[0074] Furthermore, it is preferred that the catalyst material contains no more than 1% by weight of Ni and Co, calculated as the element, relative to 100% by weight of the total contents of the reactor, more preferably no more than 0.5% by weight, more preferably no more than 0.1% by weight, more preferably no more than 0.05% by weight, more preferably no more than 0.01% by weight, more preferably no more than 0.005% by weight, and more preferably no more than 0.001% by weight.

[0075] Additionally, independently, one or more support materials may have a BET surface area of ​​30 to 800 m 2 / g, more preferably 40 to 500m 2 / g, more preferably 50 to 300m 2 / g, more preferably 60 to 200m 2 / g, more preferably 70 to 100m 2 / g, and more preferably 75 to 80 m 2 It is preferable that the range is / g.

[0076] Additionally, independently, one or more support materials may have a BET surface area of ​​20 m 2 / g over ~150m 2 / g, more preferably 21 to 100m 2 / g, more preferably 22 to 70 m 2 / g, more preferably 23 to 50m 2 / g, more preferably 24 to 40 m 2 / g, and more preferably 25 to 35 m 2 It is preferable that the range is / g.

[0077] Furthermore, independently, it is preferred that the one or more support materials exhibit a pore volume in the range of 0.2 to 3 ml / g, more preferably 0.4 to 1.5 ml / g, more preferably 0.6 to 1 ml / g, and more preferably 0.8 to 0.85 ml / g, the pore volume preferably being measured in accordance with ISO 15901-2:2022.

[0078] Furthermore, independently, the catalyst material has a BET surface area of ​​20 to 800 m 2 / g, more preferably 30 to 500m2 / g, more preferably 40 to 300m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, and more preferably 70 to 75 m 2 / g, the BET surface area being preferably measured according to ISO 9277:2010.

[0079] Furthermore, independently thereof, it is preferred that the catalyst material exhibits a pore volume in the range of 0.1 to 2 ml / g, more preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, and more preferably 0.3 to 0.35 ml / g, the pore volume preferably being measured in accordance with ISO 15901-2:2022.

[0080] Furthermore, independently of this, it is preferable that 90 to 100 mass%, more preferably 95 to 100 mass%, more preferably 99 to 100 mass%, more preferably 99.5 to 100 mass%, and more preferably 99.9 to 100 mass% of Ru, calculated as elemental Ru relative to 100 mass% of Ru contained in the catalyst material, be supported on one or more support materials contained in the catalyst material.

[0081] Furthermore, independently, it is preferred that Ru is supported on one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, the one or more ruthenium salts more preferably comprising Ru(NO)(NO3)3, and more preferably Ru(NO)(NO3)3 is used as the one or more ruthenium salts.

[0082] Furthermore, independently thereof, it is preferred that the one or more support materials are selected from the group consisting of metal oxides, and the metals of the metal oxides are more preferably Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, and rare earth metals, and combinations of two or more thereof, Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, and Nd, and combinations of two or more thereof, Al, Ti, Zr, Mg, Ca, and La, and combinations of two or more thereof, Al, Zr, and Mg, and combinations of two or more thereof. more preferably, the one or more support materials comprise one or more oxides selected from the group consisting of Al2O3, ZrO2, and spinel, and combinations of two or more thereof, preferably from the group consisting of ZrO2 and spinel, and combinations of two or more thereof; more preferably, the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2; more preferably, the one or more support materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0083] When the one or more support materials comprise ZrO2, it is preferred that the ZrO2 comprises one or more crystalline phases and / or is amorphous, and the one or more crystalline phases of ZrO2 are selected from the group consisting of monoclinic, tetragonal, and cubic phases of ZrO2, and mixtures of two or three thereof.

[0084] Furthermore, independently, it is preferred that the one or more support materials are substantially free of CaO and / or MgO, more preferably substantially free of CaO and MgO, more preferably substantially free of alkaline earth metal oxides, more preferably substantially free of Ca and / or Mg, more preferably substantially free of Ca and Mg, and more preferably substantially free of alkaline earth metals.

[0085] Furthermore, independently, it is preferred that the one or more support materials are substantially free of Al2O3 and / or SiO2, more preferably substantially free of Al2O3 and SiO2, more preferably substantially free of Al and / or Si, and more preferably substantially free of Al and Si.

[0086] Additionally, independently, it is preferred that the one or more support materials be substantially free of carbon nanotubes, more preferably substantially free of elemental carbon, and more preferably substantially free of carbon.

[0087] Furthermore, independently, it is preferred that the catalytic material comprises Ru in an amount in the range of 0.5 to 15 wt %, more preferably 1 to 10 wt %, more preferably 2 to 8 wt %, more preferably 3 to 6.5 wt %, more preferably 4 to 6 wt %, and more preferably 4.5 to 5.5 wt %, based on 100 wt % of the total amount of the one or more support materials.

[0088] Furthermore, independently, it is preferred that 95 to 100 mass %, more preferably 97 to 100 mass %, more preferably 98 to 100 mass %, more preferably 99 to 100 mass %, more preferably 99.5 to 100 mass %, and more preferably 99.9 to 100 mass % of the catalyst material consists of Ru and one or more support materials.

[0089] Furthermore, independently thereof, it is preferred that the catalytic material further comprises one or more alkali metal and / or alkaline earth metal hydroxides, which are supported on one or more support materials that support Ru, and the alkali metal and / or alkaline earth metal hydroxides are more preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH, and KOH, and mixtures of two or more thereof, more preferably Mg(OH)2, Ca(OH)2, LiOH, NaOH, and KOH, and mixtures of two or more thereof, more preferably LiOH, NaOH, and KOH, and mixtures of two or more thereof, and more preferably the catalytic material further comprises KOH and / or LiOH, preferably KOH.

[0090] Furthermore, independently, it is preferred that the catalyst material comprises one or more alkali metal hydroxides in an amount ranging from 0.5 to 15% by weight, more preferably from 1 to 10% by weight, more preferably from 2 to 8% by weight, more preferably from 3 to 6.5% by weight, more preferably from 4 to 6% by weight, and more preferably from 4.5 to 5.5% by weight, based on 100% by weight of the total amount of the one or more support materials.

[0091] Furthermore, independently thereof, it is preferred that 95 to 100 mass %, more preferably 97 to 100 mass %, more preferably 98 to 100 mass %, more preferably 99 to 100 mass %, more preferably 99.5 to 100 mass %, and more preferably 99.9 to 100 mass % of the catalyst material consists of Ru, one or more alkali metal hydroxides, and one or more support materials.

[0092] Furthermore, independently, it is preferred that the catalyst material is in the form of extrusions and / or powder, more preferably in the form of extrudates, and more preferably in the form of extrudates.

[0093] When the catalyst material is in the form of extrudates, it is preferred that the extrudates have a diameter in the range of from 0.5 to 10 mm, more preferably from 1 to 7 mm, more preferably from 1.5 to 5 mm, more preferably from 2 to 4 mm, and more preferably from 2.5 to 3.5 mm.

[0094] Furthermore, independently thereof, it is preferred that the extrudates are divided, and the catalyst material is in the form of extrudates with divided sieve fractions in the ranges 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 μm to 700 μm, and more preferably 300 to 500 μm.

[0095] According to the present invention, the endothermic reaction is preferably carried out at a temperature in the range of 200 to 1100°C, more preferably in the range of 400 to 900°C, more preferably in the range of 500 to 800°C.

[0096] Furthermore, the endothermic reaction is preferably carried out at a pressure in the range of 1 to 100 bar (abs), more preferably in the range of 30 to 70 bar (abs), and more preferably in the range of 40 to 60 bar (abs).

[0097] Furthermore, the endothermic reaction is preferably carried out in the presence of a catalytic or inert material.

[0098] Furthermore, it is preferred that the method be a continuous process.

[0099] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the indicated dependencies and backward references. In particular, it should be noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "the complex oxide of any one of embodiments 1 to 4," all embodiments within this range are expressly disclosed for those skilled in the art, that is, this expression of the term means that it is understood by those skilled in the art to be synonymous with "the complex oxide of any one of embodiments 1, 2, 3, and 4." Furthermore, it is expressly noted that the following set of embodiments represents a conveniently organized part of the description directed to the general and preferred aspects of the present invention, rather than a set of claims determining the scope of protection.

[0100] 1. A method for conducting an endothermic reaction in a reactor, comprising the steps of: (i) providing a combustible stream comprising NH3, wherein the stream is a liquid or a gas; (ii) heating the combustible stream provided in (i) to a temperature in the range of 25 to 850°C to obtain a heated combustible gas stream; (iii) optionally feeding the heated combustible gas stream obtained in (ii) to 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 the combustion chamber contains a reactor; (v) burning the combustible gas stream obtained in (ii) or the gas stream obtained in (iii) with oxygen in a combustion chamber to heat a reactor contained in the combustion chamber to a temperature in the range of 500 to 2100°C, and obtaining an exhaust gas stream exiting 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 a heated reactor for carrying out an endothermic reaction; (viii) reacting the feed gas stream in a heated reactor to obtain a product gas stream. Including, the heating in (ii) comprises transferring heat of reaction from a chemical conversion process to the combustible stream provided in (i); and The method wherein the exhaust gas stream obtained in (v) contains 5% by volume or less of H2.

[0101] 2. The process of embodiment 1, wherein the combustible stream from (i) has a temperature in the range of 5 to 150°C, preferably in the range of 15 to 120°C, more preferably in the range of 20 to 105°C, more preferably in the range of 40 to 80°C, more preferably in the range of 50 to 70°C.

[0102] 3. The process of embodiment 1 or 2, wherein the combustible stream according to (i) has a pressure in the range of 0.5 to 110 bar (abs), preferably in the range of 1 to 100 bar (abs), more preferably in the range of 30 to 70 bar (abs), more preferably in the range of 40 to 60 bar (abs).

[0103] 4. The method of any one of embodiments 1 to 3, wherein the combustible stream according to (i) comprises 0-1 vol.% O2, preferably 0-0.1 vol.%, more preferably 0-0.01 vol.% O2.

[0104] 5. The method of any one of embodiments 1 to 4, wherein the combustible stream according to (i) comprises 98-100% by volume of NH3, preferably 99-100% by volume, more preferably 99.9-100% by volume of NH3.

[0105] 6. The method of any one of embodiments 1 to 5, wherein the combustible stream according to (i) comprises 0-2.0 vol.% HO, preferably 0.01-1.5 vol.%, more preferably 0.1-1.0 vol.% HO.

[0106] 7. The process of any one of embodiments 1 to 6, wherein 90-100% by volume, preferably 95-100% by volume, more preferably 99-100% by volume of the combustible stream from (i) consists of NH3 and HO.

[0107] 8. The method of any one of embodiments 1 to 7, wherein the combustible stream is heated by (ii) to a temperature in the range of 50 to 850°C, preferably in the range of 200 to 700°C, more preferably in the range of 300 to 600°C, more preferably in the range of 400 to 500°C.

[0108] 9. The method of any one of embodiments 1 to 8, wherein the heating according to (ii) comprises transferring heat using a heat exchanger.

[0109] 10. The method of any one of embodiments 1 to 9, wherein the heat transferred by (ii) is supplied by an exhaust gas stream exiting the combustion chamber by (v) and / or from a product gas stream by (viii).

[0110] 11. The method of any one of embodiments 1 to 10, wherein the heat transferred by (ii) is obtained from an exothermic reaction, or the heat transferred by (ii) is excess heat from heat used to carry out an autothermic or endothermic reaction.

[0111] 12. The method of embodiment 11, wherein the exothermic reaction comprises, preferably consists of, one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and selective oxidation of one or more of alkanes, alkenes, and alkynes, preferably selective oxidation of one or more of alkanes, alkenes, and alkynes to acrolein or acrylic acid.

[0112] 13. The method of embodiment 11, wherein the endothermic reaction comprises, preferably consists of, 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.

[0113] 14. The autothermal reaction comprises, and preferably consists of, one or more of autothermal reforming of natural gas and hydrocarbons, and partial oxidation of hydrocarbons (POx), and the hydrocarbons are (C1 to C 1012. The method of embodiment 11, wherein the alkyl group is selected from the group consisting of (C1-C8)alkanes, more preferably (C1-C7)alkanes.

[0114] 15. The process of any one of embodiments 1 to 14, wherein in (iii), at least a portion of the NH3 contained in the heated combustible gas stream is converted to N2 and H2 in the ammonia reforming reactor, preferably 0.1 to 99.9 vol. % of the NH3 contained in the heated combustible gas stream, more preferably 5 to 95 vol. %, per 100 vol. % of NH3 contained in the heated combustible gas stream, is converted to N2 and H2 in the ammonia reforming reactor.

[0115] 16. The process 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.

[0116] 17. The process 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.

[0117] 18. The process of any one of embodiments 1 to 17, wherein the heated combustible gas stream supplied to the reactor by (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.

[0118] 19. The process of any one of embodiments 1 to 18, wherein the heated combustible gas stream supplied to the reactor by (iii) has a temperature in the range of 100 to 1000°C, preferably in the range of 200 to 900°C, more preferably in the range of 400 to 700°C, more preferably in the range of 500 to 600°C.

[0119] 20. The process of any one of embodiments 1 to 19, wherein the heated combustible gas stream supplied to the reactor by (iii) has a pressure in the range of 1 to 100 bar (abs), preferably in the range of 10 to 35 bar (abs), more preferably in the range of 14 to 31 bar (abs), more preferably in the range of 18 to 27 bar (abs).

[0120] 21. The method of any one of embodiments 1 to 20, wherein one or more co-fuels are fed to the combustion chamber together with the heated combustible gas stream obtained in (ii) or the gas stream obtained in (iii), 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, and 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, and more preferably the one or more co-fuels comprise, more preferably consist of CH4.

[0121] 22. The process 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, and 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.

[0122] 23. The process of embodiment 22, wherein one or more tubes of the tubular reactor have, independently of one another, 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.

[0123] 24. The process of embodiment 22 or 23, wherein 1 to 100%, preferably 30 to 70%, more preferably 40 to 60% of the length of the tubes of the tubular reactor pass through the combustion chamber independently of each other.

[0124] 25. The process of any one of embodiments 22 to 24, wherein the tubes of the tubular reactor have diameters, independently of one another, 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.

[0125] 26. (v) Burning a flammable gas stream by (v.1) Mixing a combustible gas stream with oxygen; (v.2) burning the mixture obtained in (v.1) in a combustion chamber to obtain a gas stream having a temperature in the range of 500 to 2100°C. 26. The method of any one of embodiments 1 to 25, comprising:

[0126] 27. The process of embodiment 26, wherein the volume ratio of oxygen to NH3 contained in the mixture obtained with (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.

[0127] 28. The process of any one of embodiments 1 to 27, wherein the exhaust gas stream obtained in (v) contains 0-4 vol% H2, preferably 0-3 vol%, more preferably 0-2 vol%, more preferably 0-1 vol%, more preferably 0-0.1 vol%, more preferably 0-0.01 vol% H2.

[0128] 29. The process of any one of embodiments 1 to 28, wherein the exhaust gas stream obtained in (v) has a temperature in the range of 850 to 2100°C, preferably in the range of 950 to 1700°C, more preferably in the range of 1000 to 1400°C.

[0129] 30. The method of any one of embodiments 1 to 29, wherein the one or more reactants comprised in the feed 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.

[0130] 31. The process of any one of embodiments 1 to 30, wherein the feed gas stream fed to the reactor heated in (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.

[0131] 32. The process of any one of embodiments 1 to 31, wherein the feed gas stream supplied to the reactor heated by (vii) has a temperature in the range of 50 to 1500°C, preferably in the range of 100 to 1400°C, more preferably in the range of 400 to 1100°C, more preferably in the range of 600 to 900°C.

[0132] 33. The process of any one of embodiments 1 to 32, wherein the feed gas stream supplied to the reactor heated by (vii) has a pressure in the range of 0.5 to 110 bar (abs), preferably in the range of 1 to 100 bar (abs), more preferably in the range of 30 to 70 bar (abs), more preferably in the range of 40 to 60 bar (abs).

[0133] 34. The method of any one of embodiments 1 to 33, wherein the endothermic reaction is selected from the group consisting of an NH3 reforming reaction, a steam cracking reaction, an alkane dehydrogenation reaction, preferably an ethane dehydrogenation reaction, a propane dehydrogenation reaction, or a butane dehydrogenation reaction, a steam reforming reaction, a dry reforming reaction, a styrene production reaction, a methanol reforming reaction, a dimethyl ether reforming reaction, a reverse water-gas shift reaction, and an alcohol dehydration reaction.

[0134] 35. The method of embodiment 34, wherein the endothermic reaction is an NH3 reforming reaction, and the NH3 reforming reaction is carried out in the presence of a catalytic material.

[0135] 36. The method of embodiment 35, wherein the catalytic material comprises a metal M1, and M1 is Ni, Co, or Ni and Co.

[0136] 37. The method of embodiment 36, wherein the catalytic material preferably further comprises a metal M2 selected from the group consisting of alkali metals, alkaline earth metals, Mo, Fe, Ru, and mixtures of two or more thereof, preferably Li, K, Na, Cs, Mg, Ca, Sr, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably K, Na, Cs, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, more preferably K, Ba, Mo, Fe, Ru, and mixtures of two or more thereof, wherein M2 more preferably comprises Fe, Ru, or Fe and Ru, more preferably M2 comprises Ru, and more preferably M2 is Ru.

[0137] 38. The method of embodiment 36 or 37, wherein the catalytic material further comprises one or more support materials on which the metal M1 or the metals M1 and M2 are supported, the one or more support materials preferably being selected from the group consisting of Al2O3, SiO2, ZrO2, CeO2, MgO, CaO, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, ZrO2, CeO2, and mixtures of two or more thereof, more preferably from the group consisting of Al2O3, SiO2, and mixtures thereof, and more preferably the support material comprises Al2O3.

[0138] 39. The method of any one of embodiments 36 to 38, wherein the catalyst material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 80:20, preferably in the range of 0.5:99.5 to 75:25, more preferably in the range of 1:99 to 70:30, more preferably in the range of 5:95 to 65:35, more preferably in the range of 15:85 to 60:40, more preferably in the range of 30:70 to 55:45, and more preferably in the range of 40:60 to 50:50.

[0139] 40. The method of embodiment 39, wherein M2 comprises Fe, preferably is Fe, and the catalytic material exhibits an M2:M1 atomic ratio in the range of 1:99 to 80:20, preferably 5:95 to 75:25, more preferably 10:90 to 70:30, more preferably 20:80 to 65:35, more preferably 30:70 to 60:40, more preferably 35:65 to 55:45, and more preferably 40:60 to 50:50.

[0140] 41. The method of embodiment 39 or 40, wherein M2 comprises Ru, preferably is Ru, and the catalytic material exhibits an M2:M1 atomic ratio in the range of 0.1:99.9 to 30:70, preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, more preferably 3:97 to 10:90, and more preferably 5:95 to 6:94.

[0141] 42. The method of any one of embodiments 39 to 41, wherein the catalytic material further comprises Al and O.

[0142] 43. The method of embodiment 42, wherein the catalytic material comprises Ni as the metal M1, and preferably the metal M1 is Ni.

[0143] 44. The method of embodiment 43, wherein the catalyst material further comprises Mg, and the molar ratio of Ni:Mg:Al 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).

[0144] 45. The method of embodiment 43 or 44, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst material consists of Ni, Mg, Al, and O.

[0145] 46. ​​The method of embodiment 43 or 44, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst material consists of M2, Ni, Mg, Al, and O.

[0146] 47. The method of embodiment 42, wherein the catalytic material comprises Co as the metal M1, and preferably the metal M1 is Co.

[0147] 48. The method of embodiment 47, wherein the catalytic material further comprises La, and the molar ratio of Co:La:Al is preferably in the range of 1:(0.1-8):(1-50), more preferably 1:(0.5-5):(3-30), more preferably 1:(0.8-3):(5-20), more preferably 1:(1-2):(8-15), and more preferably 1:(1.3-1.7):(10-12).

[0148] 49. The method of embodiment 47 or 48, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst material consists of Co, La, Al, O.

[0149] 50. The method of embodiment 47 or 48, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst material consists of M2, Co, La, Al, and O.

[0150] 51. The method of any one of embodiments 1 to 50, wherein the endothermic reaction is selected from the group consisting of a steam cracking reaction, an alkane dehydrogenation reaction, preferably an ethane dehydrogenation reaction, a propane dehydrogenation reaction, or a butane dehydrogenation reaction, a steam reforming reaction, a dry reforming reaction, a styrene production reaction, a methanol reforming reaction, a dimethyl ether reforming reaction, a reverse water-gas shift reaction, and an alcohol dehydration reaction.

[0151] 52. The catalytic material comprises Ru and one or more support materials, wherein Ru is supported on one or more support materials, and the one or more support materials are 20 m 2 / g or more, the BET specific surface area preferably being measured according to ISO 9277:2010, and the catalytic material contains not more than 1% by weight of Ni and Co, each calculated as the element relative to 100% by weight of the catalytic material.

[0152] 53. The method of embodiment 52, wherein the catalytic material contains 0.5% by weight or less, preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, and more preferably 0.001% by weight or less of Ni and Co, each calculated as the element relative to 100% by weight of the catalytic material.

[0153] 54. The method of embodiment 52 or 53, wherein the catalyst material contains no more than 1%, preferably no more than 0.5%, more preferably no more than 0.1%, more preferably no more than 0.05%, more preferably no more than 0.01%, more preferably no more than 0.005%, and more preferably no more than 0.001%, by weight of Ni and Co, each calculated as the element relative to 100% by weight of the total contents of the reactor.

[0154] 55. One or more support materials have a BET surface area between 30 and 800 m 2 / g, preferably 40 to 500m 2 / g, more preferably 50 to 300m 2 / g, more preferably 60 to 200m 2 / g, more preferably 70 to 100m 2 / g, and more preferably 75 to 80 m 2 55. The method of any one of embodiments 52 to 54, wherein the range of 1 / g is

[0155] 56. One or more support materials have a BET surface area of ​​20 m 2 / g over ~150m 2 / g, preferably 21 to 100m 2 / g, more preferably 22 to 70 m 2 / g, more preferably 23 to 50m 2 / g, more preferably 24 to 40 m 2 / g, and more preferably 25 to 35 m 2 56. The method of any one of embodiments 52 to 55, wherein the range of 1 / g is

[0156] 57. The method of any one of embodiments 52 to 56, wherein the one or more support materials exhibit a pore volume in the range of 0.2 to 3 ml / g, preferably 0.4 to 1.5 ml / g, more preferably 0.6 to 1 ml / g, and more preferably 0.8 to 0.85 ml / g, the pore volume preferably being measured according to ISO15901-2:2022.

[0157] 58. The catalyst material has a BET surface area of ​​20 to 800 m 2 / g, preferably 30 to 500m 2 / g, more preferably 40 to 300m 2 / g, more preferably 50 to 200m 2 / g, more preferably 60 to 100m 2 / g, and more preferably 70 to 75 m 2 58. The method of any one of embodiments 52 to 57, wherein the BET surface area is preferably in the range of / g, and is measured according to ISO 9277:2010.

[0158] 59. The method of any one of embodiments 52 to 58, wherein the catalytic material exhibits a pore volume in the range of 0.1 to 2 ml / g, preferably 0.15 to 1.2 ml / g, more preferably 0.2 to 0.8 ml / g, more preferably 0.25 to 0.5 ml / g, and more preferably 0.3 to 0.35 ml / g, the pore volume preferably being measured according to ISO 15901-2:2022.

[0159] 60. The method of any one of embodiments 52 to 59, wherein 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, calculated as element, relative to 100 wt. % of Ru contained in the catalytic material is supported on one or more support materials contained in the catalytic material.

[0160] 61. The method of any one of embodiments 52 to 60, wherein Ru is supported on one or more support materials by an impregnation technique using an aqueous solution of one or more ruthenium salts, the one or more ruthenium salts preferably comprising Ru(NO)(NO3)3, more preferably Ru(NO)(NO3)3 is used as the one or more ruthenium salts.

[0161] 62. The one or more support materials are selected from the group consisting of metal oxides, and the metal of the metal oxide is preferably selected from the group consisting of Al, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, alkaline earth metals, and rare earth metals, and combinations of two or more thereof, Al, Si, Ti, Zr, Mg, Ca, La, Ce, Pr, and Nd, and combinations of two or more thereof, Al, Ti, Zr, Mg, Ca, and La, and combinations of two or more thereof, Al, Zr, and Mg, and combinations of two or more thereof, and 62. The method of any one of embodiments 52 to 61, wherein the one or more support materials comprise one or more oxides selected from the group consisting of Al2O3, ZrO2, and spinel, and combinations of two or more thereof, preferably from the group consisting of ZrO2 and spinel, and combinations of two or more thereof; more preferably, the one or more support materials comprise ZrO2 and / or MgAl2O4, preferably ZrO2; more preferably, the one or more support materials consist of ZrO2 and / or MgAl2O4, preferably ZrO2.

[0162] 63. The method of embodiment 62, wherein the ZrO2 comprises one or more crystalline phases and / or is amorphous, and the one or more crystalline phases of ZrO2 are selected from the group consisting of the monoclinic, tetragonal, and cubic phases of ZrO2, and mixtures of two or three thereof.

[0163] 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.

[0164] 65. The method of any one of embodiments 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.

[0165] 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.

[0166] 67. The method of any one of embodiments 52 to 66, wherein the catalytic material comprises Ru in an amount ranging from 0.5 to 15 wt%, preferably 1 to 10 wt%, more preferably 2 to 8 wt%, more preferably 3 to 6.5 wt%, more preferably 4 to 6 wt%, and more preferably 4.5 to 5.5 wt%, based on 100 wt% of the total amount of the one or more support materials.

[0167] 68. The method of any one of embodiments 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 catalyst material consists of Ru and one or more support materials.

[0168] 69. The method of any one of embodiments 52 to 68, wherein the catalytic material further comprises one or more alkali metal and / or alkaline earth metal hydroxides, wherein the one or more alkali metal and / or alkaline earth metal hydroxides are supported on one or more support materials that support Ru, and wherein the alkali metal and / or alkaline earth metal hydroxides are preferably selected from the group consisting of Mg(OH)2, Ca(OH)2, Ba(OH)2, Sr(OH)2, LiOH, NaOH, and KOH, and mixtures of two or more thereof, more preferably from the group consisting of Mg(OH)2, Ca(OH)2, LiOH, NaOH, and KOH, and mixtures of two or more thereof, more preferably from the group consisting of LiOH, NaOH, and KOH, and mixtures of two or more thereof, and more preferably wherein the catalytic material further comprises KOH and / or LiOH, preferably KOH.

[0169] 70. The method of any one of embodiments 52 to 69, wherein the catalytic material comprises 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 100 wt% of the total amount of the one or more support materials.

[0170] 71. The method of any one of embodiments 52 to 70, wherein 95 to 100% by weight, preferably 97 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the catalyst material consists of Ru, one or more alkali metal hydroxides, and one or more support materials.

[0171] 72. The method of any one of embodiments 52 to 71, wherein the catalyst material is in the form of a molding and / or a powder, preferably in the form of a molding, and more preferably in the form of an extrudate.

[0172] 73. The method of embodiment 72, wherein the extrudate has a diameter in the range of 0.5 to 10 mm, preferably 1 to 7 mm, more preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and more preferably 2.5 to 3.5 mm.

[0173] 74. The process of embodiment 72 or 73, wherein the extrudates are divided and the catalyst material is in the form of extrudates of a divided sieve fraction 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 μm to 700 μm, and more preferably 300 to 500 μm.

[0174] 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 to 1100°C, preferably in the range of 400 to 900°C, more preferably in the range of 500 to 800°C.

[0175] 76. The process 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 (abs), preferably in the range of 30 to 70 bar (abs), more preferably in the range of 40 to 60 bar (abs).

[0176] 77. The method of any one of embodiments 1 to 76, wherein the endothermic reaction is carried out in the presence of a catalytic material or an inert material.

[0177] 78. The method of any one of embodiments 1 to 77, which is a continuous process.

[0178] The present invention is further illustrated by the following examples and comparative examples. [Example]

[0179] Experimental Section Example 1: Method for conducting an endothermic reaction in a reactor As shown in Figure 1, a combustion chamber is provided. The chamber can be heated by burning a combustible stream with oxygen therein. The combustible stream includes NH3, a portion of which can be reformed prior to combustion in the combustion chamber. The combustible stream can further include a co-fuel. The NH3-containing combustible stream can be considered a blend of conventional fuels and NH3, having an energy content of 7-8 MW.

[0180] Prior to combustion, the combustible stream was heated by transferring heat of reaction from a chemical conversion process. The heat can be obtained from an exothermic reaction or can be excess heat used to carry out an autothermic or endothermic reaction. For example, water and / or steam can be used to transfer heat from the chemical conversion process to the combustible stream.

[0181] Furthermore, the tubular reactor passes through a combustion chamber, as shown in Figure 1. In the reactor, an endothermic reaction takes place. The endothermic reaction can be, for example, a steam cracking process.

[0182] BRIEF DESCRIPTION OF THE DRAWINGS Figure 1: Schematic representation of a combustion chamber containing a tubular reactor according to Example 1. The reactor passes through the combustion chamber.

[0183] References -Banares-Alcantara et al., Applied Energy 2021,282,116009 -US8464515B2 -WO2019 / 038251A1 -US8691182B2 -US8961923B2

Claims

1. 1. A method for conducting an endothermic reaction in a reactor, comprising the steps of: (i) NH ３ providing a combustible stream comprising: (ii) heating the combustible stream provided in (i) to a temperature in the range of 25 to 850°C to obtain a heated combustible gas stream; (iii) optionally, feeding the heated combustible gas stream obtained in (ii) to an ammonia reforming reactor to produce N ２ and H ２ obtaining a gas stream comprising: (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) burning 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 to 2100°C, and obtaining an exhaust gas stream exiting the combustion chamber; (vi) preparing a feed gas stream comprising one or more reactants for an endothermic reaction; (vii) supplying said feed gas stream to a heated reactor for carrying out said endothermic reaction; (viii) reacting the feed gas stream in a heated reactor to obtain a product gas stream. Including, the heating in (ii) comprises transferring heat of reaction from a chemical conversion process to the combustible stream provided in (i); and (v) wherein the exhaust gas stream obtained in (v) contains not more than 5% by volume of H ２ A method comprising:

2. (i) the combustible stream contains 0 to 1% by volume of O ２ The method of claim 1 , comprising:

3. (i) the combustible stream is 98-100% by volume of NH ３ 3. The method of claim 1 or 2, comprising:

4. (i) the combustible stream is 0 to 2.0% by volume H ２ The method of claim 1 or 2, comprising:

5. 3. The method of claim 1 or 2, wherein the heating according to (ii) comprises transferring heat using a heat exchanger.

6. 3. The method of claim 1 or 2, wherein the heat transferred by (ii) is supplied by the exhaust gas stream exiting the combustion chamber by (v) and / or from the product gas stream by (viii).

7. 3. The method of claim 1 or 2, wherein the heat transferred by (ii) is obtained from an exothermic reaction or the heat transferred by (ii) is excess heat from heat used to carry out an auto-exothermic or endothermic reaction.

8. 3. The process of claim 1 or 2, wherein the reactor according to (iii) is an adiabatic reactor, an isothermal reactor, or a combination thereof.

9. (v) combusting the flammable gas stream by (v.1) mixing the combustible gas stream with oxygen; (v.2) burning the mixture obtained in (v.1) in said combustion chamber to obtain a gas stream having a temperature in the range of 500 to 2100°C.

3. The method of claim 1 or 2, comprising:

10. The endothermic reaction is NH ３ It is a reforming reaction, and the NH ３ 3. The process of claim 1 or 2, wherein the reforming reaction is carried out 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 catalytic material comprises Ru and one or more support materials, the Ru being supported on the one or more support materials, and the one or more support materials are 20 m ２ 11. The method of claim 10, wherein the catalytic material exhibits a BET specific surface area of ​​1 / g or more, and the catalytic material contains 1% by mass or less of Ni and Co, each calculated as an element relative to 100% by mass of the catalytic material.

13. 13. The method of claim 12, wherein the catalytic material further comprises one or more alkali metal and / or alkaline earth metal hydroxides, and the one or more alkali metal and / or alkaline earth metal hydroxides are supported on the one or more support materials that support Ru.

14. 2. The method of claim 1, wherein the endothermic reaction is carried out at a temperature in the range of 200 to 1100°C.

15. The method of claim 1 , wherein the endothermic reaction is carried out in the presence of a catalytic or inert material.

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