Methanol to on-demand hydrogen

Abstract

A reactor system and method for conducting a methanol decomposition reaction to react a feedstock containing methanol into synthesis gas is provided, wherein heat for the endothermic methanol decomposition reaction is provided by resistive heating.

Description

[Technical Field]

[0001] Technical field The present invention provides a reactor and method for producing hydrogen from a feedstock containing methanol in the presence of a catalyst under methanol decomposition reaction conditions, wherein the heat for the methanol decomposition reaction is provided by resistance heating. [Background technology]

[0002] background Hydrogen tanks are a typical solution for storing hydrogen when needed occasionally or to meet various demands. However, storing hydrogen in such tanks poses a risk of fire and explosion. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] PCT / EP2019 / 062424 [Overview of the project] [Problems that the invention aims to solve]

[0004] There is a need for on-demand hydrogen production in smaller plants that use easily storable reactants for hydrogen production and employ relatively simple production setups that minimize operator input.

[0005] A system and method for carrying out an endothermic catalytic reaction are described in the jointly filed patent application PCT / EP2019 / 062424. [Means for solving the problem]

[0006] overview Therefore, in a first embodiment, the present invention provides a reactor system for producing hydrogen from a feedstock containing methanol under methanol decomposition reaction conditions in the presence of a catalyst, the reactor system comprising the following: - Supply of feedstock containing methanol and water; - A structural catalyst arranged to catalyze the reaction of the supply material; wherein the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supporting a ceramic coating, and the ceramic coating supporting a catalytically active material. - A pressure shell housing the structural catalyst; wherein the pressure shell comprises an inlet for introducing the feed material and an outlet for discharging the product gas, the inlet being positioned such that the feed material enters the structural catalyst from a first end of the structural catalyst and the product gas exits the structural catalyst from a second end of the structural catalyst. - An insulating layer between the structural catalyst and the pressure shell; - At least two conductors electrically connected to the structural catalyst and a power supply located outside the pressure shell; wherein the power supply is sized to heat at least a portion of the structural catalyst to a temperature of at least 150°C by passing an electric current through the macrostructure, and preferably the at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and the structural catalyst is configured to carry an electric current substantially from one conductor to the second end of the structural catalyst and back to the second conductor of the at least two conductors. - Outlet for hydrogen-containing product flow.

[0007] In a further embodiment, a method is provided for reacting a feedstock comprising methanol and water with hydrogen under methanol decomposition reaction conditions in the presence of a catalyst, wherein the reactor system includes a pressure shell housing a structural catalyst arranged to catalyze the methanol decomposition reaction of the feedstock, the structural catalyst comprising a macrostructure of a conductive material, the macrostructure supporting a ceramic coating, the ceramic coating supporting a catalytically active material; the reactor system comprising thermal insulation between the structural catalyst and the pressure shell; and the method comprising the following steps: - The step of pressurizing the feedstock - Supplying the pressurized feedstock to the pressure shell through an inlet arranged such that the feedstock enters the structured catalyst at a first end of the structured catalyst, subjecting the feedstock to a methanol decomposition reaction on the structured catalyst, discharging product gas from the pressure shell, and the product gas exiting the structured catalyst from a second end of the structured catalyst; - Supplying power through one or more electrical conductors connecting a power source arranged outside the pressure shell to the structured catalyst, enabling an electric current to flow through the macrostructure, thereby heating at least a part of the structured catalyst to a temperature of at least 150 °C. Preferably, the at least two conductors are connected to the structured catalyst at a position on the structured catalyst closer to the first end of the structured catalyst than the second end of the structured catalyst, and the structured catalyst is configured such that an electric current flows from one conductor substantially to the second end of the structured catalyst and returns to a second conductor of the at least two conductors, thereby heating at least a part of the structured catalyst to a temperature sufficient for the feedstock to undergo a methanol decomposition reaction on the structured catalyst, and thereby heating at least a part of the structured catalyst to a temperature sufficient for the feedstock to undergo a methanol decomposition reaction on the structured catalyst; - The step of discharging product gas containing hydrogen from the reactor system.

[0008] In a further aspect, a method is provided for rapidly switching a metal-catalyzed methanol decomposition reaction of a feedstock containing methanol and water in the reactor system described herein from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or vice versa, the method comprising the following steps; Under the first steady-state reaction condition (A) - Supplying the feedstock to the reactor system at a first total flow rate, and - Supplying first power through an electrical conductor connecting a power source arranged outside the pressure shell to the structured catalyst, thereby allowing a first electric current to flow through the conductive material, Thereby, at least a part of the structural catalyst is heated to a first temperature, and at this temperature, the feedstock is converted on the structural catalyst to a first product gas mixture under the first steady-state reaction conditions (A); and discharging the first product gas from the reactor system, and under the second steady-state reaction conditions (B) - feeding the feedstock to the reactor system at a second total flow rate, and, - supplying a second power through an electrical conductor connecting a power source disposed outside the pressure shell to the structural catalyst, thereby causing a second current to flow through the conductive material, thereby heating at least a part of the structural catalyst to a second temperature; at this temperature, the feedstock is converted on the structural catalyst to a second product gas mixture under the second steady-state reaction conditions (B); discharging the second product gas from the reactor system; where the second power is greater than the first power; and / or the second total flow rate is greater than the first total flow rate, where the reactor system is such that the second power is greater than the first power, and / or the second total flow rate is higher than the first flow rate.

[0009] A further aspect of the present invention is described in the following detailed description, examples and appended claims.

[0010] Legend Regarding the Drawings

Brief Description of the Drawings

[0011] FIG. 1a shows a cross-section of an embodiment of a reactor system of the present invention comprising a structural catalyst including an array of macrostructures. FIG. 1b shows a state in which a part of the pressure shell and the heat insulation layer are removed from the reactor system of FIG. 1a.

[0012] FIG. 2 is an enlarged view showing a part of the reactor system.

[0013] Figures 3a and 3b are schematic cross-sectional views through one embodiment of the reactor system of the present invention, including a structural catalyst.

[0014] Figures 4 and 5 show embodiments of a structural catalyst with an arrangement of macrostructures, viewed from above and the side, respectively.

[0015] Figure 6 shows one embodiment of the structural catalyst of the present invention.

[0016] Figures 7 and 8 show embodiments of a structural catalyst having a connector.

[0017] Figure 9 shows the equilibrium composition of CH3OH, H2O, H2, CO2, and CO at 29 barg as a function of temperature, using feedstocks of 56% CH3OH and 44% H2O. [Modes for carrying out the invention]

[0018] Detailed disclosure Electrothermal methanol decomposition provides a means for rapidly heating methanol decomposition catalysts to produce hydrogen on demand. This allows for the rapid production of hydrogen needed for starting up or shutting down other catalyst layers, for example, in a chemical plant. Hydrogen is often required in chemical plants during trip planning when a plant safety shutdown is triggered and sensitive equipment and materials need to be protected in a protective atmosphere. Examples of sensitive materials include catalyst materials. Furthermore, this method enables on-demand hydrogen production in small-scale plants using reactants that are easy to store for hydrogen production and a relatively simple production setup that minimizes operator input. This method also provides a means for producing hydrogen on demand in response to the fluctuating availability of electrical energy from renewable power sources such as wind and solar power.

[0019] This technology demonstrates a method for producing hydrogen from methanol on demand in a compact design using an electrically heated reactor.

[0020] The decomposition reaction of methanol can be summarized as follows: [ka] And each of these is ΔH R = 41 kJ / mol and ΔH R = 91 kJ / mol

[0021] These reactions are usually accompanied by a water-gas shift reaction. [ka]

[0022] Typically, catalysts containing copper (Cu) are used as catalytic active materials. However, other catalytic active materials are also possible.

[0023] Compact electroreactors using monolithic catalysts are easy to operate and enable the production of hydrogen as needed, when and in the required quantities, with a simple starting principle. This results in a relatively inexpensive plant that produces only the required amount of hydrogen, requires little to no hydrogen storage, and reduces or eliminates hydrogen transport entirely. The simple reactor and easy-to-operate methanol decomposition process offer advantages for hydrogen production in non-localized plants, reducing the risks associated with handling hydrogen.

[0024] Furthermore, because it uses electricity as a heat source, it can be started and stopped very quickly (in minutes). In this way, it can switch almost instantly from standby mode to hydrogen production, or vice versa, thus reducing the need for hydrogen storage.

[0025] Furthermore, the present invention can also be used for the continuous production of hydrogen-containing gases.

[0026] Therefore, a reactor system is provided for producing hydrogen from a feedstock containing methanol in the presence of a catalyst under methanol decomposition reaction conditions, the reactor system comprising the following: - Supply of feedstock containing methanol and water (which can be either water (I) or water vapor (g)) - A structural catalyst arranged to catalyze the methanol decomposition reaction of the supply material; wherein the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supporting a ceramic coating, and the ceramic coating supporting a catalytically active material. - A pressure shell housing the structural catalyst; wherein the pressure shell comprises an inlet for introducing the feed material and an outlet for discharging the product gas, the inlet being positioned such that the feed material enters the structural catalyst from a first end of the structural catalyst and the product gas exits the structural catalyst from a second end of the structural catalyst. - An insulating layer between the structural catalyst and the pressure shell; - At least two conductors electrically connected to the structural catalyst and a power supply located outside the pressure shell; wherein the power supply is sized to heat at least a portion of the structural catalyst to a temperature of at least 150°C by passing an electric current through the macrostructure, and preferably the at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and the structural catalyst is configured to carry an electric current substantially from one conductor to the second end of the structural catalyst and back to the second conductor of the at least two conductors. - Outlet for hydrogen-containing product flow.

[0027] The reactor system layout allows pressurized feedstock to be supplied to the reactor system at the inlet, and this gas to be guided into the reactor system's pressure shell. Inside the pressure shell, the configuration of insulating layers and inert materials is arranged so that the feedstock passes through the structural catalyst, into contact with the catalytic material, and the catalytically active material promotes the methanol decomposition reaction. Furthermore, heating of the structural catalyst supplies the heat necessary for the endothermic reaction. The product gas from the heated structural catalyst is guided to the outlet of the reactor system.

[0028] Because the catalytic active material and the conductive material are in close proximity, the catalytic active material can be efficiently heated by close-range heat conduction from the resistively heated conductive material. Thus, a key feature of the resistance heating process is that energy is supplied from within the material itself, rather than from an external heat source through conduction, convection, or radiation. Furthermore, the hottest part of the reactor system is located within the pressure shell of the reactor system. Preferably, the power supply and structural catalyst are sized so that at least a portion of the structural catalyst reaches a temperature of at least 150°C, preferably at least 300°C. The surface area of ​​the conductive material, the proportion of conductive material coated with ceramic coating, the type and structure of the ceramic coating, and the amount and composition of the catalytic active material can be adjusted to suit a specific reaction under given operating conditions.

[0029] The conductive material is preferably a macrostructure. As used herein, the term “macrostructure” means a structure large enough to be visible to the naked eye without a magnifying device. The dimensions of the macrostructure are typically in the range of centimeters or even meters. The dimensions of the macrostructure are advantageously made to correspond at least partially to the internal dimensions of the pressure shell housing the structural catalyst, thus saving space for the insulation layer and conductor. Two or more macrostructures may be linked together to provide an array of macrostructures having at least one external dimension in the range of meters, such as 2m or 5m. Such two or more macrostructures may be referred to as an “array of macrostructures.” In this case, the dimensions of the array of macrostructures are advantageously manufactured to correspond at least partially to the internal dimensions of the pressure shell housing the structural catalyst (saving space for the insulation layer). Possible arrays of macrostructures range from 0.1 to 10m 3It can occupy a volume of or greater than that. The structural catalyst may include a single macrostructure or an array of macrostructures, and the macrostructure (or multiple macrostructures) may support a ceramic coating that supports the catalytically active material. In an array of macrostructures, the macrostructures may be electrically connected to each other, but alternatively, the macrostructures may not be electrically connected to each other. Thus, the structural catalyst may consist of two or more macrostructures arranged adjacent to each other. The macrostructure (or multiple macrostructures) may be extruded and sintered structures, or 3D printed structures. 3D printed macrostructures may or may not be provided with subsequent sintering.

[0030] The physical dimensions of the macrostructure may be any suitable dimensions; therefore, the height may be less than the width of the macrostructure, or vice versa.

[0031] The macrostructure supports the ceramic coating, and the ceramic coating supports the catalytic material. The term "macrostructure supporting a ceramic coating" means that at least a portion of the surface of the macrostructure is covered by the ceramic coating. Therefore, this term does not mean that the entire surface of the macrostructure is covered by the ceramic coating, and in particular, portions of the macrostructure that are electrically connected to at least a conductor do not have the coating on them. The coating is a ceramic material with pores in its structure, which allows the catalytic material to be supported on and within the coating. Advantageously, the catalytic material contains catalytic particles having a size in the range of about 2 nm to about 250 nm.

[0032] Preferably, the macrostructure is manufactured by extruding a mixture of powdered metal particles and a binder into an extruded structure, and then sintering the extruded structure, thereby providing a material with a high geometric surface area per unit volume. Preferably, the extruded structure is sintered in a reducing atmosphere to provide the macrostructure. Alternatively, the macrostructure is 3D printed in a metal addition manufacturing process that does not require subsequent sintering, i.e., a 3D printing process, such as powder bed melting or direct energy deposition processes. Examples of such powder bed melting or direct energy deposition processes include laser beam, electron beam, or plasma 3D printing processes. Another option is that the macrostructure is manufactured as a 3D metal structure by a binder-based metal addition manufacturing process and then sintered at a first temperature T1 (T1 > 1000°C) in a non-oxidizing atmosphere to provide the macrostructure.

[0033] Before the second sintering in an oxidizing atmosphere, a ceramic coating containing catalytically active material is applied to the macrostructure to form a chemical bond between the ceramic coating and the macrostructure. Alternatively, the catalytically active material can be impregnated into the ceramic coating after the second sintering. Once a chemical bond is formed between the ceramic coating and the macrostructure, the thermal conductivity between the electrically heated macrostructure and the catalytically active material supported by the ceramic coating becomes particularly high, allowing the heat source and the catalytically active material of the structural catalyst to come into close and almost direct contact. Because the heat source and the catalytically active material are in close proximity, heat transfer occurs effectively, and the structural catalyst can be heated very efficiently. Therefore, in terms of gas processing capacity per unit reactor system volume, the reactor system can be made compact, and thus the reactor system housing the structural catalyst can also be made compact.

[0034] As used herein, the terms “3D printing” and “3D printing” refer to metal additive manufacturing processes. Such metal additive manufacturing processes include 3D printing processes that create three-dimensional objects by bonding materials to a structure under computer control, where the structure is solidified, for example, by sintering to provide a macrostructure. Furthermore, such metal additive manufacturing processes also include 3D printing processes that do not require subsequent sintering, such as powder bed fusion processes and direct energy deposition processes. Examples of such powder bed fusion or direct energy deposition processes include laser beam, electron beam, or plasma 3D printing processes.

[0035] Since the reactor system does not require a furnace, the overall size of the reactor can be significantly reduced.

[0036] The conductive material includes Fe, Ni, Cu, Co, Cr, Al, Si, or alloys thereof. Such alloys may contain further elements such as Mn, Y, Zr, C, Co, Mo, or combinations thereof. Preferably, the conductive material includes Fe, Cr, Al, or alloys thereof. Such alloys may contain further elements such as Si, Mn, Y, Zr, C, Co, Mo, or combinations thereof. Preferably, the catalytic active material is particles having a size of 2 nm to 250 nm. Preferably, the conductor and the conductive material are made of different materials from the conductive material. The conductor may be, for example, iron, nickel, aluminum, copper, silver, or alloys thereof. The ceramic coating is an electrical insulating material and will typically have a thickness of about 100 μm, for example, in the range of 10 to 500 μm.

[0037] Conductive materials are advantageously coherent or consistently internally connected materials in order to achieve electrical conductivity throughout the material, thereby achieving thermal conductivity throughout the structural catalyst, and especially to provide heating of the catalyst material. Coherent or consistently internally connected materials make it possible to ensure a uniform distribution of current within the conductive material, and consequently, a uniform distribution of heat within the structural catalyst. Throughout this text, the term "coherent" is synonymous with cohesiveness and therefore refers to a material that is consistently internally connected or consistently bonded. The effect of the structural catalyst being a coherent or consistently internally connected material is that it provides connectivity within the material of the structural catalyst, and consequently, control over the conductivity of the conductive material. Note that even if further improvements are made to the conductive material, such as providing slits in part of the conductive material or implementing insulating material within the conductive material, the conductive material is still referred to as a coherent or consistently internally connected material.

[0038] The gas flow on the structural catalyst may have an axial or coaxial direction with respect to the current path passing through the structural catalyst, a direction perpendicular to the current path, or another suitable direction relative to the current path.

[0039] The methanol decomposition reaction is endothermic. Temperatures typically exceeding 150–300°C are required to achieve an acceptable conversion rate of the methanol being supplied.

[0040] The feedstock may be in liquid or gaseous form, but gaseous feedstock is preferred. Preferably, the feedstock is pressurized in a liquid state before evaporation, and then the gaseous feedstock is supplied to the reactor. This configuration requires less compression energy.

[0041] The feedstock for the methanol decomposition reaction is, in one embodiment, a substantially pure stream of methanol with a small amount of water from the atmosphere for hydration. In a preferred embodiment, the feedstock is a mixture of methanol and water vapor, with a methanol-to-water vapor ratio of 1:1. In another embodiment, this ratio is 1:0.2, 1:3, or any of those. In yet another embodiment, the feedstock includes, in addition to methanol, other alcohols, such as ethanol, propanol, and / or butanol. Typically, the concentration of such other alcohols in the feedstock can be less than 10% by volume, e.g., less than 5% by volume, or less than 2% by volume. Other oxygenated substances, such as aldehydes, ethers, and / or ketones, etc., can also be present in the feedstock, typically at a concentration of less than 2% by volume, e.g., less than 0.5% by volume.

[0042] The term "conductivity" refers to 10 at 20°C. -5 ~10 -8 This means indicating a material that has an electrical resistivity in the range of Ω·m. Therefore, electrically conductive materials are metals such as copper, silver, aluminum, chromium, iron, nickel, or alloys of metals. Furthermore, the term "electrically insulating" refers to an electrical resistivity greater than 10 Ω·m at 20°C, for example, 10 at 20°C. 9 ~10 25 This means that the material is within the range of Ω·m.

[0043] When the reactor system includes a thermal insulation layer between the structural catalyst and the pressure shell, appropriate thermal and electrical insulation between the structural catalyst and the pressure shell can be obtained. The presence of a thermal insulation layer between the pressure shell and the structural catalyst avoids excessive heating of the pressure shell and can reduce heat loss to the surroundings. The temperature of the structural catalyst may reach up to about 1300 °C at least in part, but by using a thermal insulation layer between the structural catalyst and the pressure shell, the temperature of the pressure shell can be maintained at a significantly lower temperature, such as 300 °C, 200 °C, 100 °C or 50 °C, which is advantageous since typical construction steel materials are generally not suitable for pressure applications at temperatures exceeding 1000 °C. Further, the thermal insulation layer between the pressure shell and the structural catalyst aids in controlling the current within the reactor system since the thermal insulation layer is also electrically insulating. The thermal insulation layer can be one or more layers of solid materials such as ceramics, inert materials, fibrous materials, bricks, or gas barriers, or combinations thereof. Thus, it is also conceivable that a purge gas or a confined gas constitutes or forms part of the thermal insulation layer.

[0044] <> Furthermore, it should be noted that the term "thermal insulation material" refers to materials having a thermal conductivity of about 10 W·m -1 ·K -1 or less. Examples of thermal insulation materials are ceramics, bricks, alumina-based materials, zirconia-based materials, and the like.

[0045] Advantageously, the relevant gaps (gaps) between the structural catalyst, the thermal insulation layer, the pressure shell, and / or other components within the reactor system are filled in the form of an inert material, such as inert pellets. Such gaps are, for example, the gap between the lower side of the structural catalyst and the bottom of the pressure shell, and the gap between the side of the structural catalyst and the thermal insulation layer covering the inside of the pressure shell. The inert material may be, for example, a ceramic material in the form of pellets or tiles. The inert material aids in controlling the gas distribution through the reactor system and the gas flow through the structural catalyst. Further, the inert material typically has the effect of blocking heat.

[0046] The pressure shell preferably has a design pressure between 2 bar and 30 bar. The actual operating pressure is determined by the endothermic reaction, the size of the plant, etc. Since the hottest part of the reactor system is made of electrically conductive material, surrounded by an insulating layer, and located within the pressure shell of the reactor system, the temperature of the pressure shell can be kept considerably lower than the maximum process temperature (maximum process temperature). This allows the structural catalyst to have a maximum process temperature of up to 300°C, or 1100°C, or 1300°C, while the design temperature of the pressure shell can be relatively low, at 150°C or 100°C, preferably 100°C or 50°C, even though this is not a requirement of the method. This provides an advantage when designing a chemical reactor. Preferably, the pressure shell has a design pressure between 2 bar and 30 bar, or between 30 and 200 bar. Around 30 bar is preferred as a compromise between process economics and thermodynamic limitations.

[0047] The resistivity of the conductive material is preferably 10 -5 Ω·m~10 -7 It is between Ω·m. Materials with resistivity in this range can efficiently heat structural catalysts when energized by a power supply. Graphite is approximately 10 at 20°C. -5 Ω·m, Kanthal is approximately 10 at 20℃ -6 Ω·m, stainless steel is approximately 10 at 20℃ -7 It has a resistivity of Ω·m. Conductive materials, for example, have a resistivity of about 1.5·10 at 20℃. -6 It can be made from an FeCr alloy with a resistivity of Ω·m.

[0048] Typically, the pressure shell has an inlet for introducing process gases and an outlet for discharging product gases, with the inlet located near a first end of the pressure shell and the outlet near a second end, and at least two conductors are both connected to the structural catalyst at a position closer to the inlet than to the outlet. Since the inlet gas has a lower temperature than the product gases, at least two conductors can be placed in a substantially cool part of the reactor system, and the feed material supplied through the inlet can cool at least two conductors before the conductive material cools at its upstream end due to the heat consumed by the progress of the chemical reaction and before being further heated by the heated structural catalyst along the gas path on the heated structural catalyst. To protect the connections between the conductors and the structural catalyst, it is advantageous to keep the temperature of all conductive elements except the conductive material low. When the temperatures of the conductors and other conductive elements except the conductive material are relatively low, there are few restrictions on the materials suitable for the conductors and other conductive elements except the conductive material. As the temperature of the conductive elements rises, their resistivity increases, so it is desirable to avoid unnecessarily heating parts of the reactor system other than the conductive material. The term "conductive elements excluding conductive materials" means that, excluding the conductive structural catalyst itself, it refers to the related conductive elements that are arranged to connect a power source to the structural catalyst.

[0049] It should be noted that the system of the present invention may include any suitable number of power sources and any suitable number of conductors for connecting the power sources (or multiple power sources) to the conductive material (or multiple conductive material) of the structural catalyst.

[0050] Preferably, at least two conductors are led through a pressure shell within a fitting such that at least two conductors are electrically insulated from the pressure shell. The fitting may be, in part, plastic and / or ceramic material. The term “fitting” means a device that can mechanically connect two pieces of hardware in a pressure-resistant configuration so that pressure can be maintained within the pressure shell despite at least two conductors being led through it. Non-limiting examples of fittings may be electrical insulation fittings, dielectric fittings, power compression seals, compression fittings, or flanges. A pressure shell typically consists of side walls, end walls, flanges, and possibly further components. The term “pressure shell” means covering any of these components.

[0051] The pressure shell may further include one or more inlets near or in combination with at least one of the fittings to allow a cooling gas to flow over, around, near, or inside at least one conductor within the pressure shell. This cools the conductor, and as a result, keeps the temperature of the fittings low. If a cooling gas is not used, the conductors can be heated by the feedstock supplied to the reactor system, resistance heating of the conductors by the applied current, and / or heat conduction from the structural catalyst. The cooling gas may be, for example, hydrogen, argon, water, nitrogen, methanol, or a mixture thereof. The temperature of the cooling gas upon entry into the pressure shell may be, for example, about 50°C or 100°C. In embodiments, the conductors are hollow so that the cooling gas can flow through the conductor(s) and cool them from the inside. Keeping the temperature of the fittings low, for example around 50-100°C, facilitates a leak-resistant configuration. Typically, a portion of the feedstock, such as one of the reactants, is supplied to the pressure shell as a cooling gas. In another embodiment, a portion of the raw material or a gas having the same composition as the raw material is used as a cooling gas.

[0052] The reactor system may further include an inner tube in a heat exchange relationship with the structural catalyst, where the product gas flowing through the inner tube or the tube is in a heat exchange relationship with the gas flowing over the structural catalyst, but the inner tube is adapted to draw the product gas away from the structural catalyst so that it is electrically isolated from the structural catalyst. This layout is called a bayonet reactor system. In this layout, the product gas in the inner tube assists in heating the process gas flowing over the structural catalyst. Electrical insulation between the inner tube and the structural catalyst can be in the form of a gap or distance between the inner tube and the structural catalyst, or in the form of an inert material packed around the inner tube and the structural catalyst. The gas can pass through the structural catalyst in an upflow or downflow direction.

[0053] The connection between the structural catalyst and at least two conductors may be a mechanical connection, a welded connection, a brazed connection, or a combination thereof. The structural catalyst may include end portions that are physically and electrically connected to the structural catalyst in order to facilitate the electrical connection between the conductive material and at least two conductors. The term "mechanical connection" means a connection in which two components are mechanically held together by a screw connection or clamp so that current can flow between the components.

[0054] Conductive materials arranged in an array of conductive materials may be electrically connected to one another. Connections between two or more conductive materials may be by mechanical connection, clamping, soldering, welding, or any combination of these connection methods. Each conductive material may include end portions to facilitate electrical connection. Two or more conductive materials may be connected to a power source in series or parallel. The electrical connection between two or more conductive materials is advantageously coherent and uniform along the connection surface between the two or more conductive materials, so that the two or more conductive materials act as a single coherent or coherent internally connected material; here, uniform electrical conductivity of the entire conductive material is promoted. Alternatively, or additionally, the structural catalyst may include an array of conductive materials that are not electrically connected to one another. Instead, two or more electrically conductive materials are arranged together within a pressure shell but are not electrically connected to one another. In this case, the structural catalyst therefore includes conductive materials connected in parallel to the power source.

[0055] Ceramic coatings containing or not containing catalytically active materials can be directly added to the metal surface of a conductive material by wash coating. Wash coating of metal surfaces is a well-known process, and its description is found, for example, in Cybulski, A., and Moulijn, J.A., “Structured catalytics and reactors”, Marcel Dekker, Inc., New York, 1998, Chapter 3, and in the references herein. The ceramic coating may be added to the surface of the conductive material, after which the catalytically active material may be added, or alternatively, a ceramic coating containing the catalytically active material may be added to the macrostructure or the conductive material. The ceramic coating may be an oxide containing, for example, Al, Zr, Mg, Ce, and / or Ca. Exemplary coatings are calcium aluminate (calcium aluminate) or magnesium aluminum spinel. Such ceramic coatings may contain further elements such as La, Y, Ti, K, or combinations thereof. Ceramic coatings are electrical insulating materials and typically have a thickness of about 100 μm, for example, in the range of 10 to 500 μm.

[0056] By extruding and sintering the macrostructure or 3D printing it, a uniform and coherent macrostructure can be obtained, which can then be coated with a ceramic coating.

[0057] The conductive material and the ceramic coating may be sintered in an oxidizing atmosphere to form a chemical bond between the ceramic coating and the conductive material. This results in particularly high thermal conductivity between the conductive material and the catalytically active material supported by the ceramic coating. As a result, the structural catalyst is compact in terms of heat transfer to the catalytically active site, and the reactor system housing the structural catalyst can be compact and limited mainly by the rate of the chemical reaction.

[0058] In the embodiment, the conductor is positioned at the opposite end of the structural catalyst, so that the entire current path within the monolith runs from one side of the structural catalyst to the opposite end. This could be, for example, from top to bottom.

[0059] In one embodiment, the structural catalyst has at least one electrically insulating component arranged to increase the length of the current path between conductors to a length greater than the maximum dimension of the structural catalyst. Providing a current path between conductors greater than the maximum dimension of the structural catalyst may also be achieved by providing an electrically insulating component (or a plurality of electrically insulating components) arranged between the conductors to prevent current from flowing through a portion of the structural catalyst. Such electrically insulating components are arranged to increase the current path and therefore increase the resistance through the structural catalyst. Thereafter, the current path through the structural catalyst can be made, for example, 50%, 100%, 200%, 1000%, or 10000% longer than the maximum dimension of the structural catalyst.

[0060] Furthermore, such electrically insulating components are arranged to guide current from one conductor closer to the first end of the structural catalyst than to the second end, toward the second end of the structural catalyst, and back to a second conductor closer to the first end of the structural catalyst than to the second end. Preferably, the current is arranged to flow from the first end of the structural catalyst to the second end and back to the first end. As seen in the figures, the first end of the structural catalyst is its upper end. The arrow labeled "z" in Figures 5-7 indicates the z-axis along the length of the structural catalyst. The main current path throughout the structural catalyst will have a positive or negative z-coordinate of the current density vector that accompanies most of the length of the current path. The main current path refers to the path with the highest current density among the electron paths through the macrostructure of the structural catalyst. Alternatively, the main current path can be understood as the path with the shortest length through the macrostructure of the structural catalyst. Geometrically, the main current path can be quantified as the maximum current density vector in the plane perpendicular to the gas flow direction of the coherent portion of the macrostructure. At the bottom of the structural catalyst, the current swirls as shown in the figure, and the z-coordinate of the accompanying current density vector becomes zero.

[0061] In this specification, the term "coherent portion" refers to a cross-sectional area of ​​a macrostructure in which all walls of the coherent portion are geometrically connected to one or more other walls of the coherent portion within the same plane.

[0062] In the embodiment, the structural catalyst comprises at least one electrically insulating component arranged to conduct current through the structural catalyst such that, for at least 70% of the length of the structural catalyst, the current density vector of the main current path has a non-zero component value parallel to the length of the structural catalyst. Thus, for at least 70% of the length of the structural catalyst, the current density vector will have a positive or negative component value parallel to the length of the structural catalyst. Thus, for at least 70%, e.g., 90% or 95%, of the length of the structural catalyst, i.e., along the z-axis of the structural catalyst as seen in Figures 5-10, the current density vector of the main current path will have a positive or negative value along the z-axis. This means that current flows from the first end to the second end of the structural catalyst, and then again towards the first end. Heat is absorbed from the structural catalyst by the temperature of the gas entering the first end of the structural catalyst and by the endothermic methanol decomposition reaction occurring on the structural catalyst. Therefore, the first end of the structural catalyst remains cooler than the second end, and this is achieved with a substantially continuously increasing temperature profile, by causing the current density vector of the main current path to have a non-zero component value parallel to the length of the structural catalyst, thereby providing a controllable reaction front. In embodiments, the current density vector has a non-zero component value parallel to the length of the structural catalyst at 70%, preferably 80%, more preferably 90%, and even more preferably 95% of the length of the structural catalyst. Note that the term “length of the structural catalyst” refers to the dimension of the structural catalyst in the direction of the gas flow. In a structural catalyst as shown in the figures, the length is in the longitudinal direction, i.e., its longest dimension. This is indicated by the arrow pointing to z in some figures.

[0063] Non-limiting examples of insulating portions are cuts, slits, or holes in a structure. Optionally, a solid insulating material, such as ceramic, can be used in the cuts or slits of the structure. If the solid insulating material is a porous ceramic material, the catalytically active material can be advantageously incorporated into the pores, for example, by impregnation. The solid insulating material in the cuts or slits helps to separate the portions of the structural catalyst on the sides of the cuts or slits from each other. As used herein, the term “maximum dimensions of the structural catalyst” means the maximum internal dimensions of the geometric form that the structural catalyst takes up. If the structural catalyst is box-shaped, the maximum dimension is the diagonal from one corner to the furthest corner, and may also be denoted as the spatial diagonal.

[0064] The current flowing through the structural catalyst may be arranged to twist or coil its path through the structural catalyst by electrically insulating components positioned to increase the current path, but it should be noted that the gas flowing through the reactor system has an inlet at one end of the reactor system and passes over the structural catalyst once before exiting the reactor system. An inert material is advantageously present in the relevant gap between the structural catalyst and the rest of the reactor system to ensure that the gas in the reactor system passes through the structural catalyst and the catalyst material.

[0065] The length of the gas passage through the structural catalyst is preferably shorter (smaller) than the length of the current passage from one electrode through the structural catalyst to the next electrode. The ratio of the gas passage length to the current passage length may be less than 0.6, or less than 0.3, less than 0.1, or less than 0.002.

[0066] Typically, a structural catalyst has electrically insulating components arranged such that the current path through the structural catalyst forms a zigzag path. Here, the terms “zigzag path” and “zigzag route” refer to a path with variable-angle corners that follows a path from one conductor to another. A zigzag path is, for example, a path that proceeds upward, makes a turn, and then proceeds downward. A zigzag path may have multiple turns within the structural catalyst, proceeding upward and then downward, or it may have multiple turns.

[0067] It should be noted that insulating components placed to increase the current path are not necessarily related to ceramic coatings on conductive materials. While these ceramic coatings are also considered electrically insulating, they do not change the length of the current path between conductors connected to the conductive material.

[0068] The macrostructure can have multiple parallel channels, multiple non-parallel channels, and / or multiple labyrinthine channels, where the channels have defining walls. This allows for the use of several different forms of the macrostructure, as long as the surface area of ​​the structural catalyst exposed to the gas is as large as possible. In a preferred embodiment, the macrostructure has parallel channels, as such parallel channels provide a structural catalyst with very low pressure loss. In a preferred embodiment, the parallel longitudinal channels are distorted in the longitudinal direction of the macrostructure. In this way, gas molecules flowing through the macrostructure tend to collide with the walls within the channels rather than simply flowing linearly through the channels without contacting the walls. The dimensions of the channels need to be appropriate to provide a macrostructure with sufficient resistivity. For example, the channels may be quadratic (viewed in a cross-section perpendicular to the channel) and have side lengths of a square between 1 and 3 mm, but channels with a maximum range in cross-section up to about 4 cm are conceivable. The walls may have a thickness of, for example, 0.2 to 2 mm, or about 0.5 mm, and the ceramic coating supported by the walls may have a thickness of 10 μm to 500 μm, for example, 50 μm to 200 μm, or 100 μm. In another embodiment, the macrostructure of the structural catalyst is cross-waveform.

[0069] Generally, when macrostructures are extruded or 3D printed, the pressure loss from the inlet to the outlet of the reactor system can be significantly reduced compared to reactors where the catalyst material is in the form of pellets.

[0070] Preferably, the reactor system further comprises a bed of second catalyst material upstream of the structural catalyst in the pressure shell. Here, the term “upstream” is viewed from the direction of the feed material flow. Therefore, “upstream” here means that the feed material is guided through the bed of second catalyst material before reaching the structural catalyst. This provides a situation in which the second catalyst material may be positioned to pre-adjust the feed flow. The bed of second catalyst material does not necessarily need to be heated; however, if the bed of second catalyst material is in close proximity to the structural catalyst, it may be heated indirectly. Alternatively, the second catalyst material may be heated. To clarify the terminology used herein, it should be noted that the term “structural catalyst” may also be written as “first catalyst material” to distinguish it from second and / or third and / or fourth catalyst materials.

[0071] The reactor system may further include a third catalytic material in the form of catalyst pellets, extruded or granules loaded into channels of a macrostructure. In this embodiment, the reactor system thus has a catalytically active material in the coating of the macrostructure, as well as a third catalytic material in the form of catalyst pellets, extruded or granules within channels of the macrostructure. The pellets are prepared, for example, to dimensions that loosely match the size of the channels in order to form a single row of pellets stacked on top of each other within the channels of the macrostructure. Alternatively, the pellets, extruded or granules may be prepared to dimensions considerably smaller than the size of the channels in order to form a filling bed within each channel. As used herein, the term “pellet” refers to any distinct structure having a maximum external dimension within the range of millimeters or centimeters, and “extruded” and “granules” refer to catalytic material having a maximum external dimension defined within a certain range.

[0072] A fourth catalyst material bed may be located within the pressure shell and downstream of the structural catalyst. Such a fourth catalyst material may be in the form of catalyst pellets, extruded materials, or granules.

[0073] Therefore, the first, second, third, and fourth catalyst materials can be catalyst materials suitable for methanol decomposition reactions. In one embodiment, this catalyst is CuZn / Al2O3. In a configuration in which the reactor system includes a combination of the second, third, and fourth catalyst materials, the catalysts of each catalyst material may be different.

[0074] The geometric surface area of ​​the macrostructure is 100-3000 m². 2 / m 3 For example, 500-1100m 2 / m 3 This may be the case. Typically, macrostructured materials are heated by resistance heating of the material at 500 W / m². 2 ~50000W / m 2 A material is selected to be arranged to supply a heat flux of 5 kW / m². Preferably, the material is heated by resistance heating, 2 More than 12kW / m 2 For example, 8kW / m 2 More than 10kW / m 2 The following heat flux is supplied. The heat flux is given as heat per unit geometric surface area of ​​the surface exposed to the gas.

[0075] In one embodiment, the structural catalyst comprises a first portion arranged to generate a first heat flux and a second portion arranged to generate a second heat flux, wherein the first heat flux is lower than the second heat flux and the first portion is upstream of the second portion. Here, the term “the first portion is upstream of the second portion” means that the gas supplied to the reactor system reaches the first portion before it reaches the second portion. The first and second portions of the structural catalyst may be two different macrostructures supporting a ceramic coating supporting a catalytically active material, and the two different macrostructures may be arranged to generate different heat fluxes for a given current and voltage. For example, the first portion of the structural catalyst may have a large surface area, and the second portion of the structural catalyst may have a smaller surface area. This can be achieved by providing the second portion of the structural catalyst with a structural catalyst having a smaller cross-sectional area than the first portion. Alternatively, the current path through the first part of the structural catalyst may be more linear than the current path through the second part of the structural catalyst, and therefore the current will twist and wind more through the second part than through the first part of the structural catalyst, thereby generating more heat in the second part of the structural catalyst than in the first part. As mentioned above, if slits or cuts are made in the macrostructure, the current path may flow in a zigzag pattern within the macrostructure. It should be noted that the first and second parts of the structural catalyst may receive different currents and voltages to supply different heat fluxes. However, different heat fluxes in the first and second parts can also be achieved by supplying the same current and voltage through / on the first and second parts, due to the different physical properties of the first and second parts as shown above. In a further embodiment, the structural catalyst comprises a third portion arranged to generate a third heat flux, the third heat flux being lower than the first and / or second heat fluxes, and the third portion being downstream of the first and / or second portions.

[0076] The specified temperature range for the gas exiting the pressure shell / reactor system is 200–1300°C. The product gas outlet temperature from the structural catalyst is measured at the surface directly below or furthest downstream of the structural catalyst. Measurement techniques that can be used include thermocouples (by voltage drop), resistance temperature detectors, or infrared detection. The measurement point can be separated from the structural catalyst and embedded in the downstream inert gas / catalyst, or it can be directly located on a surface with an insulating surface coating.

[0077] Preferably, the structural catalyst in the reactor system has a ratio of the area-equivalent diameter of the horizontal cross-section passing through the structural catalyst to the height of the structural catalyst in the range of 0.1 to 2.0. The area-equivalent diameter of the cross-section passing through the reactor system is defined as the diameter of a circle having an area equivalent to the area of ​​the cross-section. When the ratio of the area-equivalent diameter to the height of the structural catalyst is 0.1 to 2.0, the pressure shell housing the structural catalyst can be made relatively smaller compared to other endothermic reactor systems such as the current tubular reformers for steam methane reforming.

[0078] Typically, since the gas flows in an upflow or downflow direction within the reactor system, the gas flows through channels in the structural catalyst along their height. If the structural catalyst includes multiple arrays or arrays of macrostructures, the individual macrostructures in the array may be arranged side by side, on top of each other, or in combination thereof. If the structural catalyst includes two or more macrostructures, it is emphasized that the dimensions of the structural catalyst are the dimensions of the two or more macrostructures. For example, if the structural catalyst is composed of two macrostructures, each having a height h, placed on top of each other, then the height of the structural catalyst is 2h.

[0079] The volume of the structural catalyst is selected considering the desired supply conversion rate, which correlates with the heat generated by the conductive material, and / or the temperature from the reactor system.

[0080] Preferably, the height of the reactor system is 0.5 to 7 m, more preferably 0.5 to 3 m. Exemplary values ​​for the reactor system height are less than 5 m, preferably less than 2 m, and even less than 1 m. The dimensions of the reactor system correlate with the dimensions of the structural catalyst within the reactor system. Of course, the pressure shell and insulating layer make the reactor system somewhat larger than the structural catalyst itself.

[0081] The reactor system may further include an upgrade unit positioned to receive the hydrogen-containing product stream and separate it into an upgraded hydrogen stream and an off-gas stream.

[0082] A reactor system is provided, comprising a pressure shell housing a structural catalyst arranged to catalyze the methanol decomposition reaction of a feedstock, wherein, under methanol decomposition reaction conditions, a method is provided for carrying out the reaction of a feedstock containing methanol to hydrogen in the presence of the catalyst, wherein the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supports a ceramic coating, the ceramic coating supports a catalytically active material; and the reactor system is provided with thermal insulation between the structural catalyst and the pressure shell.

[0083] The above method includes the following steps: - Step of pressurizing the supply raw material. - The steps of supplying the pressurized feed material to the pressure shell through an inlet positioned such that the feed material enters the structural catalyst at a first end of the structural catalyst, causing the feed material to undergo methanol decomposition on the structural catalyst, discharging the product gas from the pressure shell, and allowing the product gas to exit the structural catalyst at a second end of the structural catalyst; - Power is supplied from a power source located outside the pressure shell via (multiple) electrical conductors connected to the structural catalyst, allowing current to flow through the macrostructure, thereby heating at least a portion of the structural catalyst to a temperature of at least 150°C, preferably, the at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and the structural catalyst is configured such that current flows from one conductor substantially to the second end of the structural catalyst and back to the second of the at least two conductors, thereby heating at least a portion of the structural catalyst to a temperature sufficient for the feed material to carry out a methanol decomposition reaction on the structural catalyst; - A step of discharging hydrogen-containing product gas from the reactor system.

[0084] All details of the above system are, to the extent possible, related to the method described above.

[0085] In one embodiment, the feed material is pressurized to a pressure between 2 and 30 bar. The feed material may also be pressurized to a pressure between 30 and 200 bar. Preferably, at least a portion of the structural catalyst is heated to a temperature of at least 150°C, preferably at least 300°C. The maximum temperature to which the structural catalyst is heated is about 1400°C.

[0086] In one embodiment of the method, the step of introducing a cooling gas through an inlet via a pressure shell is further included so that the cooling gas flows over at least one conductor.

[0087] This method may further include the step of supplying a hydrogen-containing product stream to an upgrade unit and separating it into an upgraded hydrogen stream and an off-gas stream. The upgrade unit may be positioned so that some or all of the off-gas stream is recycled and mixed with the feedstock before passing over the structural catalyst.

[0088] The upgraded unit may consist of a flash separation unit, a pressure swing adsorption (PSA) unit, a temperature swing adsorption (TSA) unit, a membrane unit, a CO2 separation unit, or a combination of CO2 separation and a cold box. The cold box is defined as a cryogenic process for separating a mixture of H2, CO, and other gases into a partially pure CO stream, a partially pure H2 stream, and a balance stream remaining from the feed stream.

[0089] Flash separation refers to a phase separation device that separates a flow into a liquid phase and a gas phase according to thermodynamic phase equilibrium at a certain temperature.

[0090] CO2 separation refers to equipment that utilizes processes such as chemical absorption to retransfer CO2 from process gases. In chemical absorption, a gas containing CO2 is passed over a solvent that reacts with CO2, causing the CO2 to bind to the solvent. Most chemical solvents are amines, classified into primary amines such as monoethanolamine (MEA) and digylcholamine (DGA), secondary amines such as diethanolamine (DEA) and diisopropanolamine (DIPA), and tertiary amines such as triethanolamine (TEA) and methyldiethanolamine (MDEA). Liquid alkali carbonates such as ammonia, K2CO3, and NaCO3 can also be used.

[0091] Swing adsorption refers to a device that separates heavy gases (such as CO2) from light gases (such as H2) through adsorption. In this type of device, a dynamic equilibrium is established between the adsorption and desorption of heavy gases on the adsorbent material. Adsorption can occur through steric, kinetic, or equilibrium effects. The exact mechanism depends on the adsorbent used, and the equilibrium saturation depends on temperature and pressure. Typically, the adsorbent is treated in the process gas until near saturation, after which regeneration is necessary. Regeneration can be achieved by changing the pressure or temperature. In practice, a two-reactor process is used, meaning that the adsorbent is first saturated in one reactor at high pressure or low temperature, and then the reactor is switched, and the heavy gas is desorbed from the same reactor by lowering the pressure or raising the temperature.

[0092] A membrane, in this context, refers to separation over a barrier that is at least partially solid, such as a polymer, where individual gas species are transported at different rates determined by their permeability. This allows for increasing or diluting the concentration of components contained within the membrane.

[0093] Low-temperature separation refers to the process of separating individual components from a gas mixture by controlling the temperature and utilizing the phase changes of different types of gases.

[0094] In a preferred embodiment, the upgrading unit is configured to produce an upgraded, substantially pure H2 stream and an equilibrium off-gas as a balance.

[0095] In one embodiment, the off-gas is used for power generation in a gas engine.

[0096] In one embodiment, the method further includes the step of supplying the upgraded hydrogen stream from the upgrade unit to a downstream plant for power generation. In one embodiment, the power plant may be a solid oxide fuel cell, a gas engine, or a gas turbine. This allows the use of energy storage technology when methanol is used as the energy vector.

[0097] In one embodiment, the electricity required for the reaction system according to the present invention is produced, at least in part, from renewable resources such as wind or solar power.

[0098] Accordingly, the reactor system described herein provides a method for quickly switching the metal-catalyzed methanol decomposition reaction of a feedstock containing methanol from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or vice versa.

[0099] A steady state is defined as the point at which the central process parameters (such as supply flow rate, outlet temperature, and reactant conversion rate) reach a value within ±15% of the average process value of a given process parameter over a given period of time.

[0100] Condition A or B of the present invention is a feedstock containing methanol and one of water, hydrogen, nitrogen, or argon, supplied at 300 Nm³. 3 / h~100000Nm 3 This includes a state in which the catalyst is heated by a system that, at a total flow rate of / h, heats the product gas outlet temperature from the structural catalyst to a temperature of 150-1300°C in a balanced manner using electricity (by electric force equilibrium) at a pressure of 5 barg-150 barg. The feed material reacts toward the equilibrium of the reaction as it passes through the monolith.

[0101] In embodiments of the present invention, the method involves supplying raw materials that have a temperature of 200°C at a pressure of 29.2 barg and 100 Nm 3 With a total flow rate of / h, initial reaction conditions A consist of 54.6% CH3OH, 43.7% H2O, 0.6% N2, and 1.1% H2. When a first power supply of 36kW is applied, a gas in near equilibrium consisting of 7.1% CH3OH, 3.7% H2O, 66.2% H2, 20.2% CO2, 0.3% N2, and 2.5% CO is produced at 183Nm³. 3 At a total flow rate of / h, the gas is produced at a temperature of 220°C and a pressure of 29.1 barg. Switching to condition B over approximately 90 minutes while applying a second power of 57 kW results in a nearly equilibrium gas consisting of 0.9% CH3OH, 3.8% H2O, 69.4% H2, 17.5% CO2, 0.3% N2, and 8.2% CO, at a pressure of 29.1 bar and a temperature of 300°C, with a total flow rate of 206 Nm³. 3 It is generated by the total flow rate per hour.

[0102] In embodiments of the present invention, the method involves supplying a raw material that has a temperature of 200°C at a pressure of 29.2 barg and a torque of 547 Nm 3Initial reaction conditions A, consisting of 70.7% CH3OH, 28.3% H2O, 0.4% N2, and 0.7% H2, are included at a total flow rate of / h. When a first power supply of 43kW is applied, a gas in near equilibrium consisting of 1.8% CH3OH, 1.1% H2O, 68.4% H2, 11.0% CO2, 0.2% N2, and 17.5% CO is produced at 1275Nm³. 3 The total flow rate per hour is generated at a temperature of 300°C and a pressure of 29.1 barg. A second power of 791 kW is applied, and the total supply flow rate is 938 Nm³. 3 When switching to condition B over approximately 25 minutes while increasing the rate by / h, a pressure of 29.1 barg and a temperature of 32°C are obtained, resulting in 2224 Nm 3 At a total flow rate of / h, a gas is produced that is in near equilibrium, consisting of 0.9% CH3OH, 1.3% H2O, 68.7% H2, 10.6% CO2, 0.2% N2, and 18.3% CO.

[0103] The term "reverse" is used in this invention to mean switching from the first reaction condition (A) to the second reaction condition (B), as in switching from the second reaction condition (B) to the first reaction condition (A). It should be noted that the switch from condition A to B is considered complete when the system's process value reaches within 85% of the steady-state condition.

[0104] The reactor system is as described above; namely, it comprises a pressure shell housing a structural catalyst arranged to catalyze the reaction of a feedstock containing methanol, the structural catalyst comprising a macrostructure of a conductive material, the macrostructure supporting a ceramic coating, the ceramic coating supporting a catalytically active material, and the reactor system being provided with thermal insulation between the structural catalyst and the pressure shell. All the details described above relating to the reactor system are relevant to this technology.

[0105] The method according to this embodiment of the present invention includes the following steps: Under the first steady-state reaction condition (A) described above, - A step of supplying the raw material to the reactor system at a first total flow rate, and -A power source located outside the pressure shell is supplied with a first power via an electrical conductor connected to the structural catalyst, thereby causing a first current to flow through the conductive material. The steps include: heating at least a portion of the structural catalyst to a first temperature, at which point the feed material is converted on the structural catalyst into a first product gas mixture under the first steady-state reaction conditions (A); and discharging the first product gas from the reactor system. Then, under the second steady-state reaction condition (B) - A step of supplying the raw material to the reactor system at a second total flow rate, and -A power source located outside the pressure shell is supplied with a second power via an electrical conductor connected to the structural catalyst, thereby causing a second current to flow through the conductive material. The steps include: heating at least a portion of the structural catalyst to a second temperature; at this temperature, converting the feed material into a second product gas mixture on the structural catalyst under the second steady-state reaction conditions (B); and discharging the second product gas from the reactor system.

[0106] To achieve the first and second steady-state reaction conditions (A) and (B), the second power is greater than the first power; and / or the second total flow rate is greater than the first total flow rate.

[0107] It is noteworthy that as the total flow rate increases, the input of cooling feedstock increases, which cools the structural catalyst and reduces its reactivity so that the second steady-state reaction condition (B) is achieved. Large changes in flow rate alter the energy required for this method.

[0108] Changes in total flow rate may include changes in total flow rate without any change in composition, or changes in composition such as an increase in the recycling flow rate or a change in some of the supplied raw materials.

[0109] In one embodiment, the ratio of the total gas supply flow rates under the first reaction condition A to the second reaction condition B (A:B) is at least 1:10. Switching between conditions A and B allows for a significant increase / decrease in the amount of product gas produced. This is advantageous when the invention is used for energy storage, for example, when excess electrical energy from the energy grid is available and can thus be stored as chemical energy, or conversely, when it increases the availability of electrical energy in the grid when electrical energy is needed elsewhere. Furthermore, this embodiment allows the invention to be used to supply large quantities of product gas for periods required by downstream processes, or to operate in a standby state otherwise. This is advantageous when there is no continuous demand for product gas.

[0110] In another embodiment, the product gas outlet temperature from the structural catalyst under reaction condition B is 20°C to 400°C higher, for example, 100°C to 200°C higher, preferably 50°C to 100°C higher, than the product gas outlet temperature from the structural catalyst under reaction condition A. This allows the reactor system to be quickly brought up from a low temperature state to operating conditions. This is advantageous in the system startup situation, and the startup procedure includes the following steps: - A step of heating process equipment in a non-condensable gas to a temperature above the condensation point under steady-state conditions of a fully operational plant. • A step of pressurizing the supplied raw material components, • A step of supplying raw material components to the reactor system while applying a first power supply, • The second power-on step switches to a higher operating temperature. Thus, all steps of the startup procedure are performed relatively quickly.

[0111] The product gas outlet temperature from the structural catalyst under reaction condition B typically does not exceed 50°C higher than the product gas outlet temperature under reaction condition A (it typically only exceeds 50°C higher). Therefore, it is possible to quickly switch between conditions A and B without significantly altering the product gas composition from the system. In this way, the demand for product gas for downstream processes of the reactor system can be easily supplied in different quantities without significantly interfering with these chemical environments.

[0112] In one embodiment, switching between reaction conditions A and B includes gradually changing the total gas supply flow rate from the first total flow rate to the second total flow rate and simultaneously gradually changing the applied potential on the conductive material from the first power to the second power. In this way, the product gas composition can be kept substantially constant even during the transition phase. In one embodiment, the stepwise change is performed by increasing the flow rate in small increments while increasing the power in order to keep the product gas outlet temperature from the structural catalyst substantially constant.

[0113] In embodiments, the reactor system further comprises a control system configured to control the power supply to ensure that the temperature of the gas exiting the pressure shell is within a predetermined range and / or that the conversion of the feedstock is within a predetermined range. Power supply control is control of the electrical output from the power supply. Power supply control can be carried out, for example, as control of the voltage and / or current from the power supply, as control of whether the power supply is turned on or off, or a combination thereof. The power supplied to the structural catalyst can be in the form of alternating current or direct current.

[0114] According to one embodiment, a proportional-integral-derivative (PID) controller controls the potential based on a feedback reading of the process value of the product gas outlet temperature from the structural catalyst.

[0115] The method described herein allows for a rapid switch between conditions A and B. Preferably, the switch between reaction conditions A and B is made over a period of less than 3 hours, for example less than 2 hours, for example less than 60 minutes, preferably less than 30 minutes, and more preferably less than 15 minutes.

[0116] In one embodiment, switching between reaction conditions A and B involves supplying a second power to the structural catalyst. This is preferably done while keeping the total flow rate essentially constant.

[0117] In one embodiment, the switching between reaction conditions A and B includes a transition state between the reaction conditions A and B; the transition state includes a first period during which the power is turned off, followed by a second period during which the structural catalyst is supplied with the second power of condition B. This allows for the establishment of a steady state more quickly.

[0118] In one embodiment, the switching between reaction conditions A and B includes a transition state between reaction conditions A and B; the transition state includes a first period during which a third power is supplied to the structural catalyst, followed by a second period during which the structural catalyst is supplied with the second power of condition B, wherein the third power is greater than the second power. This allows for the establishment of a steady state more quickly.

[0119] This method includes further steps performed on the hydrogen-containing product gas, such as purification, pressurization, heating, and cooling, to provide a final product gas for application downstream of the reactor system of this invention.

[0120] Furthermore, it should be noted that the order in which the steps of this method are written is not necessarily the order in which the steps of this method are performed, or the order may differ from that shown above, as two or more steps may be performed simultaneously.

[0121] In embodiments, the method includes the step of pressurizing the gas upstream of the pressure shell to a pressure of at least 2 bar. The selected operating pressure is defined by the integration of the reactor in the endothermic reaction and surrounding method steps.

[0122] In embodiments of the method according to the present invention, the temperature of the feedstock introduced into the reactor system is between 100°C and 400°C. However, in preferred embodiments, the temperature and pressure of the feedstock are adjusted to ensure that the feedstock is above its dew point.

[0123] In embodiments of the method of the present invention, the structural catalyst is heated such that its maximum temperature is between 150°C and 1300°C. The temperature used will depend on the endothermic reaction. The maximum temperature of the structural catalyst depends on the material of the conductive material; therefore, in the case of an FeCr alloy where the conductive material melts at a temperature of 1380°C to 1490°C (depending on the actual alloy), the maximum temperature should be slightly lower than the melting point, such as about 1300°C if the melting point of the conductive material is about 1400°C, because the material becomes soft and ductile as it approaches the melting point. The maximum temperature may also be limited by the durability of the catalyst material, coating, and catalytically active material.

[0124] In embodiments, the method according to the present invention further includes the step of injecting a cooling gas from an inlet through a pressure shell to enable the cooling gas to flow over at least one conductor and / or fitting. The cooling gas may be, advantageously, hydrogen, nitrogen, methanol, or any other gas suitable for cooling an area or zone around at least one conductor. A portion of the feed material can be supplied to the pressure shell as the cooling gas.

[0125] In embodiments of the present invention, the method further includes the step of injecting a cooling gas from an inlet through a pressure shell so that the cooling gas flows over at least one conductor and / or fitting. The cooling gas may be any suitable gas; examples of such gases are hydrogen, nitrogen, methanol, methane, or mixtures thereof. The cooling gas can flow through a conductor (or multiple conductors) and cool it (or them) from within; in this case, the conductor (or multiple conductors) must be hollow to accommodate the cooling gas flowing through it.

[0126] The catalyst material for the reaction may be CuZnO / Al2O3, Fe / Al2O4NiGa / MgAl2O4, or CuZn / ZrO2. The catalytically active material may be Cu, Zn, ZnO, Fe, Ga, Ni, or a combination thereof, and the ceramic coating may be mixed with Al2O3, ZrO2, MgAl2O3, CaAl2O3, or a combination thereof, and potentially with oxides of Y, Ti, La, or Ce. The maximum temperature of the reactor may be between 150 and 1300°C. The pressure of the feedstock may be between 2 and 200 bar, preferably about 25 bar. In an embodiment, the macrostructure is made from an alloy of FeCrAl supporting a ceramic coating of a ZrO2 and Al2O3 mixture, and has CuZn as the catalytically active material.

[0127] Detailed description of the drawing In the diagram, similar reference numbers indicate similar elements.

[0128] Figure 1a is a cross-sectional view through one embodiment of a reactor system 100 according to the present invention. The reactor system 100 comprises a structural catalyst 10 arranged as an array of macrostructures 5. Each macrostructure 5 in the array is coated with a ceramic coating impregnated with a catalytically active substance. The reactor system 100 further includes a power source (not shown) and conductors 40, 40' connected to the structural catalyst 10, i.e., the array of macrostructures. The conductors 40, 40' are led through the walls of a pressure shell 20 housing the structural catalyst, through insulating material 30 inside the pressure shell, and via fittings 50. The conductors 40' are connected to the array of macrostructures 5 by conductor contact rails 41.

[0129] In one embodiment, the power supply provides a voltage of 26V and a current of 1200A. In another embodiment, the power supply provides a voltage of 5V and a current of 240A. The current is guided through the electrical conductors 40, 40' to the conductor contact rails 41, and flows through the structural catalyst 10 from one conductor contact rail 41, for example, the conductor contact rail shown on the left in Figure 1a, to the other conductor contact rail 41, for example, the conductor contact rail shown on the right in Figure 1a. The current can be an alternating current, which may flow alternately in both directions, for example, or it may be a direct current, which may flow in either of two directions.

[0130] The macrostructure 5 is made of a conductive material. Particularly preferred is Kanthal, an alloy composed of aluminum, iron, and chromium. The ceramic coating, such as an oxide, applied to the structural catalyst 5 is impregnated with a catalytically active substance. The conductors 40, 40' are made of materials such as iron, aluminum, nickel, copper, or alloys thereof.

[0131] During operation, the feedstock containing methanol enters the reactor system 100 from above, as indicated by arrow 11. The product stream containing hydrogen exits the reactor system from below, as indicated by arrow 12.

[0132] Figure 1b shows the reactor system 100 of Figure 1a with some layers of the pressure shell 20 and insulation material 30 removed, and Figure 2 is a magnified view of a portion of the reactor system 100. In Figures 1b and 2, the connection between the conductor 40' and the conductor contact rail 41 is shown more clearly than in Figure 1a. Furthermore, it can be seen that the conductor 40 is guided through the wall of the pressure shell by the fitting 50, and that one conductor 40 is divided into three conductors 40' within the pressure shell. Note that the number of conductors 40' may be any appropriate number, such as less than three or more than three.

[0133] In the reactor system shown in Figures 1a, 1b, and 2, conductors 40, 40' are guided through the wall of the pressure shell 20 housing the structural catalyst, through insulating material 30 inside the pressure shell, and via fitting 50. The feedstock for the methanol decomposition reaction flows into the reactor system 100 through an inlet on the upper side of the reactor system 100, as indicated by arrow 11, and the converted product stream exits the reactor system 100 through an outlet on the lower side of the reactor system 100, as indicated by arrow 12. Furthermore, one or more additional inlets (not shown in Figures 1a-2) are advantageously present near or in combination with fitting 50. Such additional inlets allow a cooling gas to flow over, around, near, or inside at least one conductor in the pressure shell to reduce heating of the fitting. The cooling gas may be, for example, hydrogen, nitrogen, methane, or a mixture thereof. The temperature of the cooling gas upon entry into the pressure shell may be, for example, about 100°C.

[0134] In the reactor system 100 shown in Figures 1a and 2, an inert material (not shown in Figures 1a and 2) is advantageously present between the underside of the structural catalyst 10 and the bottom of the pressure shell. Furthermore, the inert material is advantageously present between the outer side of the structural catalyst 10 of the macrostructure 5 and the insulating material 30. Thus, one side of the insulating material 30 faces the inside of the pressure shell 20, and the other side of the insulating material 30 faces the inert material. The inert material is, for example, a ceramic material and may be in the form of pellets. The inert material helps to control the pressure loss across the reactor system 100 and control the gas flow through the reactor system 100, thereby ensuring that the gas flows over the surface of the structural catalyst 10.

[0135] Figures 3a and 3b are schematic cross-sectional views according to one embodiment of a reactor system 100', 100'' of the present invention, which includes a structural catalyst 10'. The structural catalyst 10' may consist of a single macrostructure having a ceramic coating supporting the catalytically active material, or it may include two or more macrostructures. Each of the reactor systems 100', 100'' includes a pressure shell 20 and an insulating layer 80 between the structural catalyst 10' and the pressure shell 20. An inert material 90 can be used to fill the gap between the structural catalyst 10' and the insulating layer or the pressure shell 20. In Figures 3a and 3b, the inert material 90 is shown as a dotted line region, and the inert material 90 may be in any suitable form, for example, in the form of inert pellets, which are made of, for example, ceramic material. The inert material 90 helps to control the pressure drop through the reactor system and to control the gas flow through the reactor system. Furthermore, the inert material typically has a thermal insulation effect.

[0136] From Figures 3a and 3b, it can be seen that the reactor systems 100', 100'' further include an inner tube 15 in a heat exchange relationship with the structural catalyst 10'. The inner tube 15 is adapted to draw the product gas from the structural catalyst 10' such that the product gas flowing through the inner tube or the tube is in a heat exchange relationship with the gas flowing over the structural catalyst, but the inner tube 15 is electrically insulated from the structural catalyst 10' by either an insulating layer 80, an inert material 90, a gap, or a combination thereof. This is a layout referred to as a bayonet reactor system. In this layout, the product gas in the inner tube assists in heating the process gas flowing over the macrostructure. In the layouts shown in Figures 3a and 3b, the feed material enters the reactor systems 100', 100'' as indicated by arrow 11, and then enters the structural catalyst 10' as indicated by arrow 13. While the feed material passes over the structural catalyst 10', it undergoes methanol decomposition. The gas exiting the structural catalyst 10' is converted to hydrogen, at least partially. The gas, at least partially converted, flows from the structural catalyst 10' into the inner tube 15 as indicated by arrow 14 and out of the inner tube as indicated by arrow 12. Even with the presence of an insulating layer 80 between the inner tube 15 and the structural catalyst 10', some heat transfer will occur between the gas in the inner tube 15 and the gas in or upstream of the structural catalyst 10'. In the embodiments shown in Figures 3a and 3b, the feed material flows downward through the structural catalyst 10' and upward through the inner tube 15; however, the configuration can also be reversed so that the feed material flows upward through the structural catalyst 10' and downward through the inner tube 15.

[0137] Figures 4 and 5 show embodiments of a structural catalyst including an array of macrostructures viewed from above and a side view, respectively. Figure 4 shows a structural catalyst 10 including an array of macrostructures 5 viewed from above, i.e., from arrow 11 in Figures 1a and 1b. This array has six rows of five macrostructures 5, namely 1a, 1b, 1c, 1d, 1e, and 1f. Each macrostructure 5 in each row is connected to its adjacent macrostructures (multiple macrostructures) in the same row, and the two outermost macrostructures in each row are connected to the conductor contact rail 41. Adjacent macrostructures 5 in a row of macrostructures are connected to each other by connecting pieces 3.

[0138] Figure 5 is a side view of the structural catalyst 10 having the rows of macrostructures 5 shown in Figure 4. From Figure 5, it can be seen that each macrostructure 5 extends longitudinally perpendicular to the cross-section seen in Figure 4. Each macrostructure 5 has a slit 60 cut along its longitudinal direction (see Figure 5). Therefore, when energized by a power supply, the current enters the array of macrostructures 5 via the conductive contact rail 41, is guided downward through the first macrostructure 5 to the lower limit of the slit 60, and then guided upward toward the connecting piece 3. The current is guided downward and upward through each macrostructure 5 in each row 1a to 1f of the macrostructures 5 in the array 10, via the corresponding zigzag path. This configuration advantageously increases the resistance (tolerance) on the structural catalyst 10.

[0139] Figure 6 is a perspective view of the structural catalyst 10 according to the present invention. The structural catalyst 10 includes a macrostructure coated with a ceramic coating impregnated with a catalytically active substance. Within the structural catalyst are channels 70 extending along the longitudinal direction of the macrostructure 5 (indicated by the arrow "h" in Figure 6), and the channels are defined by walls 75. In the embodiment shown in Figure 6, the walls 75 define a number of parallel square channels 70 when viewed from the direction of flow, as indicated by the arrow 12. When viewed from above, the structural catalyst 10 has a substantially square perimeter defined by edge lengths e1 and e2. However, the perimeter can be circular or of another shape.

[0140] The walls 75 of the structural catalyst 10 are extruded or 3D printed materials coated with a ceramic coating, such as an oxide, which is coated onto the macrostructure. In the figure, the ceramic coating is not shown. The ceramic coating is impregnated with a catalytically active material. The ceramic coating, and therefore the catalytically active material, is present on all walls of the structural catalyst 10 as a gas flow flows through it during operation, interacting with the heated surface of the structural catalyst and the catalytically active material internally.

[0141] Therefore, during use in the reactor system for methanol decomposition, the feed material flows through channel 70 and interacts internally with the heated surface of the structural catalyst and the catalytically active material supported by the ceramic coating.

[0142] In the structural catalyst 10 shown in Figure 6, a slit 60 is cut into the structural catalyst 10. This slit 60 forces the current within the macrostructure to take a zigzag path, in this example, downward and then upward, thereby increasing the current path, and consequently the resistance and the heat dissipated within the macrostructure. The slit 60 within the macrostructure may be provided with an embedded insulating material to prevent current from flowing in the direction transverse of the slit 60.

[0143] The channels 70 within the structural catalyst 10 are open at both ends. When the structural catalyst is used in a reactor system, the feed material flows through the unit in the direction indicated by arrows 11 and 12 in Figures 1a and 1b, and is heated by contact with the walls 75 of the channels 70 and by thermal radiation. This heat initiates the desired methanol decomposition reaction. The walls 75 of the channels 70 may have a thickness of, for example, 0.5 mm, and the ceramic coating applied to the walls 75 may have a thickness of, for example, 0.1 mm. Although arrows 11 and 12 (see Figures 1a and 1b) indicate that the feed material flow is downflow, the opposite flow direction, i.e., upflow, is also possible.

[0144] Figure 7 shows a perspective view of the structural catalyst 10 of Figures 1a and 1b with the connectors 7 attached. Each connector 7 connects a portion of the structural catalyst 10 to a conductor 40. Each conductor 40 is connected to a power source (not shown). Each connector 7 is connected to the top of the structural catalyst. When the conductor 40 is connected to the power source, current is guided through the conductor to the corresponding connector 7 and flows through the structural catalyst 10. The slit 60 obstructs the lateral (horizontal in Figure 7) flow of current along its entire length along the height h of the structural catalyst 10. Therefore, the current flows downward in the portion of the structural catalyst along the slit 60 as seen in Figure 7, then laterally in the longitudinal direction below the slit 60 as seen in Figure 7, and finally the current flows upward in the longitudinal direction of the structural catalyst to reach the other connector 7. The connectors 7 in Figure 7 are mechanically fastened to the structural catalyst by mechanical fastening means, in particular, such as screws and bolts. However, additional or alternative fastening means are also possible. In one embodiment, the power supply generates a voltage of 3V and a current of 400A. The connector 7 is made of a material such as iron, aluminum, nickel, copper, or an alloy thereof.

[0145] As described above, the structural catalyst 10 is coated with a ceramic coating such as an oxide to support the catalytically active substance. However, the portion of the structural catalyst 10 that is connected to the connector 7 must not be coated with an oxide. Instead, the macrostructure of the structural catalyst needs to be directly exposed to or connected to the connector 7 in order to obtain a good electrical connection between the macrostructure and the connector.

[0146] When the connector 7 and, consequently the conductor 40, are connected to the same end of the structural catalyst 10, i.e., the upper end as shown in Figure 7, the feed material entering the reactor system housing the structural catalyst 10 will be able to cool the connector 7 and the conductor 40. For example, the feed material entering such a reactor system may have a temperature of 200°C or 400°C, and thus the connector 7 and the conductor 40 will not reach temperatures much higher than this.

[0147] Figure 8 shows another embodiment of the structural catalyst 10'' having connectors 7''. The structural catalyst 10''' is, for example, a structural catalyst as shown in Figure 6. Each of the connectors 7''' (not shown) has three holes on its upper side for connecting to a conductor. Inside the slit 60 (see Figure 6) of the structural catalyst 10''' is a piece of electrical insulating material 61.

[0148] Figure 9 shows the thermodynamic equilibrium of the methanol decomposition reaction as a function of temperature when using a mixture of 56% CH3OH in H2O as the feedstock at a pressure of 29 barg. This figure shows that increasing the outlet temperature of the reaction system increases the conversion rate of methanol, as indicated by the decrease in the methanol content of the product gas. This is selectively converted to a mixture of hydrogen and CO / CO2. When operating at an outlet temperature of 200°C, 64% H2 is produced, but this increases to 69% H2 when the temperature is raised to 300°C. Since the conversion rate of methanol also increases with temperature, the utilization rate of the feedstock increases. Heat input to the reaction is essential to promote the endothermic reaction, which is addressed by embodiments of the present invention.

[0149] In the figure, the structural catalyst is shown as a channel with a square cross-section when viewed from a direction perpendicular to the z-axis, but the channel's cross-section can have any suitable shape. Therefore, the channel of the structural catalyst can alternatively be, for example, triangular, hexagonal, octagonal, or circular, but triangular, square, and hexagonal shapes are preferred.

[0150] While the present invention has been illustrated by descriptions of various embodiments and examples, and these embodiments and examples are described in considerable detail, it is not the applicant's intention to limit the scope of the appended claims to such detail or in any way. Additional advantages and modifications are readily apparent to those skilled in the art. Therefore, the present invention in its broader context is not limited to the specific details, representative methods, and exemplary embodiments shown and described. Accordingly, deviations from such details can be made without departing from the spirit or scope of the applicant's general inventive concept.

[0151] Items of the present invention 1. A reactor system for producing hydrogen from a feedstock containing methanol in the presence of a catalyst under methanol decomposition reaction conditions, wherein the reactor system comprises the following: - Supply of feedstock containing methanol and water; - A structural catalyst arranged to catalyze the methanol decomposition reaction of the supply material; wherein the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supporting a ceramic coating, and the ceramic coating supporting a catalytically active material. - A pressure shell housing the structural catalyst; wherein the pressure shell comprises an inlet for introducing the feed material and an outlet for discharging the product gas, the inlet being positioned such that the feed material enters the structural catalyst from a first end of the structural catalyst and the product gas exits the structural catalyst from a second end of the structural catalyst. - An insulating layer between the structural catalyst and the pressure shell; - At least two conductors electrically connected to the structural catalyst and a power supply located outside the pressure shell; wherein the power supply is sized to heat at least a portion of the structural catalyst to a temperature of at least 150°C by passing an electric current through the macrostructure. - Outlet for hydrogen-containing product flow.

[0152] 2. The reactor system according to item 1, wherein the at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and the structural catalyst is configured to carry current substantially from one conductor to the second end of the structural catalyst and back to the second of the at least two conductors.

[0153] 3. The reactor system according to item 1 or 2, wherein the power supply is sized to heat at least a portion of the structural catalyst to a temperature of at least 150°C, preferably at least 300°C.

[0154] 4. The reactor system according to any one of the above items, wherein the supply material further comprises H2, N2, or Ar.

[0155] 5. A reactor system according to any one of the above items, wherein the pressure shell has a design pressure between 2 and 30 bar.

[0156] 6. A reactor system described in any one of items 1 to 4, wherein the pressure shell has a design pressure between 30 and 200 bar.

[0157] 7. The resistivity of the conductive material is 10 -5 Ω·m~10 -7 A reactor system according to any one of the above items, wherein the value is between Ω·m.

[0158] 8. The reactor system according to any one of the above items, wherein the at least two conductors are led through a pressure shell in a fitting such that the at least two conductors are electrically insulated from the pressure shell.

[0159] 9. The reactor system according to item 8, wherein the pressure shell further includes one or more inlets near or in combination with at least one fitting to allow a cooling gas to flow over, around, near or inside at least one conductor within the pressure shell.

[0160] 10. The reactor system according to any one of the preceding items, further comprising an inner tube which is in a heat exchange relationship with the structural catalyst but is electrically insulated from the structural catalyst, wherein the inner tube is adapted to extract the product gas from the structural catalyst such that the product gas flowing through the inner tube is in a heat exchange relationship with the gas flowing over the structural catalyst.

[0161] 11. The reactor system according to any one of the preceding items, wherein the connection between the structural catalyst and the at least two conductors is a mechanical connection, a welded connection, a brazed connection, or a combination thereof.

[0162] 12. The reactor system according to any one of the above items, wherein the conductive material comprises a 3D printed or extruded and sintered macrostructure, the macrostructure supporting a ceramic coating, and the ceramic coating supporting a catalytically active material.

[0163] 13. The reactor system according to any one of the above items, comprising an array of macrostructures electrically connected to one another, wherein the structural catalyst is a structure.

[0164] 14. The reactor system according to any one of the items, wherein the structural catalyst has an electrically insulating component arranged such that the length of the main current path between the at least two conductors is longer than the maximum dimensions of the structural catalyst.

[0165] 15. The reactor system according to any one of the preceding items, wherein the structural catalyst has at least one electrically insulating component arranged to conduct current through the structural catalyst such that the current density vector of the main current path has a non-zero component value parallel to the length of the structural catalyst in at least 70% of the length of the structural catalyst.

[0166] 16. The reactor system according to any one of the above items, wherein the macrostructure has a plurality of parallel channels, a plurality of non-parallel channels, and / or a plurality of labyrinthine channels.

[0167] 17. The reactor system according to any one of the above items, further comprising a third catalyst material in the form of catalyst pellets, extruded or granules loaded into the channels of the macrostructure.

[0168] 18. The reactor system according to any one of the above items, wherein the reactor system further comprises a bed of a fourth catalyst material downstream of the structural catalyst in the pressure shell.

[0169] 19. The material of the macrostructure described above can be subjected to resistance heating of 500 to 50000 W / m². 2 A reactor system according to any one of the above items, wherein the material is selected as the material arranged to generate the heat flux.

[0170] 20. The reactor system according to any one of the preceding items, comprising a structural catalyst having a first portion arranged to generate a first heat flux and a second portion arranged to generate a second heat flux, wherein the first heat flux is lower than the second heat flux and the first portion is upstream of the second portion.

[0171] 21. A reactor system according to any one of the preceding items, comprising a structural catalyst, a third portion arranged to generate a third heat flux, wherein the third heat flux is lower than the first heat flux and / or the second heat flux, and the third portion is downstream of the first portion and / or the second portion.

[0172] 22. The reactor system according to any one of the preceding items, further comprising a control system arranged to control the power supply to ensure that the temperature of the gas exiting the pressure shell is within a predetermined range and / or that the conversion of the feedstock is within a predetermined range.

[0173] 23. The reactor system according to any one of the above items, wherein the structural catalyst in the reactor system has a ratio of the area-equivalent diameter of the horizontal cross-section passing through the structural catalyst to the height of the structural catalyst in the range of 0.1 to 2.0.

[0174] 24. The reactor system according to any one of the above items, wherein the height of the reactor system is 0.5 to 7 m, more preferably 0.5 to 3 m.

[0175] 25. The reactor system according to any one of the preceding items, wherein the length of the gas passage through the structural catalyst is shorter than the length of the current passage from one electrode through the structural catalyst to the next electrode.

[0176] 26. A method for carrying out a methanol decomposition reaction in a reactor system including a pressure shell housing a structural catalyst arranged to catalyze the methanol decomposition reaction of a feedstock, wherein, under methanol decomposition reaction conditions, a methanol decomposition reaction is performed in the presence of a catalyst, wherein the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supports a ceramic coating, the ceramic coating supports a catalytically active substance; and the reactor system is provided with thermal insulation between the structural catalyst and the pressure shell; The aforementioned method includes the following steps: - Step of pressurizing the supply raw material. - The steps of supplying the pressurized feed material to the pressure shell through an inlet positioned such that the feed material enters the structural catalyst at the first end of the structural catalyst, causing the feed material to undergo methanol decomposition on the structural catalyst, discharging the product gas from the pressure shell, and allowing the product gas to exit the structural catalyst from the second end; - A power supply located outside the pressure shell is connected to the structural catalyst via (multiple) electrical conductors, thereby allowing current to flow through the macrostructure, and thereby heating at least a portion of the structural catalyst to a temperature of at least 150°C; - A step of discharging hydrogen-containing product gas from the reactor system.

[0177] 27. The method of item 25, wherein the at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and the structural catalyst is configured such that a current flows from one conductor substantially to the second end of the structural catalyst and back to the second of the at least two conductors, thereby heating at least a portion of the structural catalyst to a temperature sufficient for the feed material to carry out a methanol decomposition reaction on the structural catalyst.

[0178] 28. The method according to item 25 or 26, wherein the supply material is pressurized to a pressure between 2 and 30 bar.

[0179] 29. The method of item 25, wherein the supply material is pressurized to a pressure between 30 and 200 bar.

[0180] 30. The method according to any one of items 26 to 29, wherein at least a portion of the structural catalyst is heated to a temperature of at least 150°C, preferably at least 300°C.

[0181] 31. The method according to any one of items 26-30, further comprising the step of introducing a cooling gas through an inlet through the pressure shell so that the cooling gas flows over at least one conductor.

[0182] 32. The item further includes the step of supplying the hydrogen-containing product stream to an upgraded unit and separating it into an upgraded hydrogen stream and an off-gas stream. The method described in any one of 26-31.

[0183] 33. The method according to item 32, wherein the product flow or the upgraded hydrogen flow from the upgrade unit is supplied to a downstream plant for power generation.

[0184] 34. A method for rapidly switching a metal-catalyzed methanol decomposition reaction of a feedstock containing methanol in a reactor system according to any one of items 1 to 25 above from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or vice versa; the method comprising the following steps: Under the first steady-state reaction condition (A) described above, - A step of supplying the raw material to the reactor system at a first total flow rate, and -A power source located outside the pressure shell is supplied with a first power via an electrical conductor connected to the structural catalyst, thereby causing a first current to flow through the conductive material. The steps include: heating at least a portion of the structural catalyst to a first temperature, at which point the feed material is converted on the structural catalyst into a first product gas mixture under the first steady-state reaction conditions (A); and discharging the first product gas from the reactor system. Then, under the second steady-state reaction condition (B) - A step of supplying the raw material to the reactor system at a second total flow rate, and -A power source located outside the pressure shell is connected to the structural catalyst via (multiple) electrical conductors to supply a second power, thereby causing a second current to flow through the conductive material. This involves heating at least a portion of the structural catalyst to a second temperature; at this temperature, under the second steady-state reaction conditions (B), the feed material is converted on the structural catalyst into a second product gas mixture; and the second product gas is discharged from the reactor system. Here, the second power is greater than the first power, and / or the second total flow rate is greater than the first total flow rate.

[0185] 35. The method of item 34, wherein the structural catalyst is constructed such that the at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and current flows from one conductor substantially to the second end of the structural catalyst and back to the second of the at least two conductors.

[0186] 36. The method according to any one of items 34 to 35, wherein the ratio (A:B) of the total gas supply flow rates under the first reaction condition A to the second reaction condition B is at least 1:10.

[0187] 37. The method according to any one of items 34 to 36, wherein the product gas outlet temperature from the structural catalyst under reaction condition B is 20°C to 400°C higher, for example, 100°C to 200°C higher, preferably 50°C to 100°C higher, than the product gas outlet temperature from the structural catalyst under reaction condition A.

[0188] 38. The method according to any one of items 34 to 37, wherein the switching between reaction conditions A and B includes gradually changing the total gas supply flow rate from the first total flow rate to the second total flow rate and simultaneously gradually changing the applied potential on the conductive material from the first power to the second power.

[0189] 39. The method according to any one of items 34 to 38, wherein the product gas outlet temperature from the structural catalyst under reaction condition B is no higher than 50°C higher than the product gas outlet temperature from the structural catalyst under reaction condition A.

[0190] 40. The method according to any one of items 34-39, wherein a proportional-integral-derivative (PID) controller controls the potential based on a feedback reading of the process value of the product gas outlet temperature from the structural catalyst.

[0191] 41. The method according to any one of items 34-40, wherein the product gas outlet temperature from the structural catalyst is measured at the surface directly below or at the downstream end of the structural catalyst.

[0192] 42. The method according to any one of items 34 to 41, wherein the switching between reaction conditions A and B is carried out over a period of less than 3 hours, e.g., less than 2 hours, e.g., less than 60 minutes, preferably less than 30 minutes, and more preferably less than 15 minutes.

[0193] 43. The method according to any one of items 34-42, wherein switching between reaction conditions A and B provides a second power supply to the structural catalyst.

[0194] 44. The method according to any one of items 34 to 43, wherein the switching between reaction conditions A and B includes a transition state between the reaction conditions A and B; the transition state includes a first period during which the power is turned off, followed by a second period during which the structural catalyst is supplied with the second power of condition B.

[0195] 45. The method according to any one of items 34 to 44, wherein the switching between reaction conditions A and B includes a transition state between reaction conditions A and B; the transition state includes a first period during which a third power is supplied to the structural catalyst, followed by a second period during which the structural catalyst is supplied with a second power of condition B, wherein the third power is greater than the second power. The present invention includes the following items. [Item 1] A reactor system for producing hydrogen from a feedstock containing methanol in the presence of a catalyst under methanol decomposition reaction conditions, the reactor system comprising the following: - Supply of feedstock containing methanol and water; - A structural catalyst arranged to catalyze the methanol decomposition reaction of the feed material; wherein the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supporting a ceramic coating, and the ceramic coating supporting a catalytically active material; - A pressure shell housing the structural catalyst; wherein the pressure shell comprises an inlet for introducing the feed material and an outlet for discharging product gases, the inlet being positioned such that the feed material enters the structural catalyst from a first end of the structural catalyst and the product gases exit the structural catalyst from a second end of the structural catalyst. - An insulating layer between the structural catalyst and the pressure shell; - At least two conductors electrically connected to the structural catalyst and a power supply located outside the pressure shell; wherein the power supply is sized to heat at least a portion of the structural catalyst to a temperature of at least 150°C by passing an electric current through the macrostructure. - Outlet for hydrogen-containing product flow. [Item 2] The reactor system according to item 1, wherein the at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and the structural catalyst is configured to substantially carry current from one conductor to the second end of the structural catalyst and back to the second of the at least two conductors. [Item 3] The reactor system according to item 1 or 2, wherein the power supply is sized to heat at least a portion of the structural catalyst to a temperature of at least 150°C, preferably at least 300°C. [Item 4] The aforementioned raw material is further H 2 、N 2 A reactor system as described in any one of items 1-3, containing , or Ar. [Item 5] A reactor system according to any one of items 1 to 4, wherein the pressure shell has a design pressure between 2 and 30 bar. [Item 6] A reactor system according to any one of items 1 to 4, wherein the pressure shell has a design pressure between 30 and 200 bar. [Item 7] A method for carrying out a methanol decomposition reaction to convert feedstocks, including methanol and water, into hydrogen in the presence of a catalyst, in a reactor system including a pressure shell housing a structural catalyst arranged to catalyze the methanol decomposition reaction of feedstocks, wherein the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supports a ceramic coating, the ceramic coating supports a catalytically active substance; and the reactor system is provided with thermal insulation between the structural catalyst and the pressure shell; The aforementioned method includes the following steps: - Step of pressurizing the supply raw material. - The pressurized feed material is supplied to the pressure shell through an inlet positioned such that the feed material enters the structural catalyst at the first end of the structural catalyst; the feed material undergoes a methanol decomposition reaction on the structural catalyst; and the product gas is discharged from the pressure shell, during which the product gas exits the structural catalyst from the second end of the structural catalyst; - A power supply located outside the pressure shell is connected to the structural catalyst via an electrical conductor, thereby allowing current to flow through the macrostructure, and thereby heating at least a portion of the structural catalyst to a temperature of at least 150°C; - A step of discharging hydrogen-containing product gas from the reactor system. [Item 8] The method according to item 7, further comprising the step of supplying a hydrogen-containing product stream to an upgraded unit and separating it into an upgraded hydrogen stream and an off-gas stream. [Item 9] The method described in item 8, further comprising the step of supplying the product gas or the upgraded hydrogen stream from the upgraded unit to a downstream plant for power generation. [Item 10] A method for rapidly switching a metal-catalyzed methanol decomposition reaction of a feedstock containing methanol in a reactor system described in any one of items 1 to 25 from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or vice versa; the method comprising the following steps: Under the first steady-state reaction condition (A) described above, - A step of supplying the raw material to the reactor system at a first total flow rate, and -A power source located outside the pressure shell is supplied with a first power via an electrical conductor connected to the structural catalyst, thereby causing a first current to flow through the conductive material. The steps include: heating at least a portion of the structural catalyst to a first temperature, at which point the feed material is converted on the structural catalyst into a first product gas mixture under the first steady-state reaction conditions (A); and discharging the first product gas from the reactor system. Then, under the second steady-state reaction condition (B) - A step of supplying the raw material to the reactor system at a second total flow rate, and -A power source located outside the pressure shell is supplied with a second power via an electrical conductor connected to the structural catalyst, thereby causing a second current to flow through the conductive material. This involves heating at least a portion of the structural catalyst to a second temperature; at this temperature, under the second steady-state reaction conditions (B), the feed material is converted on the structural catalyst into a second product gas mixture; and the second product gas is discharged from the reactor system. Here, the second power is greater than the first power, and / or the second total flow rate is greater than the first total flow rate.

Claims

1. A reactor system for producing hydrogen from a feedstock containing methanol in the presence of a catalyst under methanol decomposition reaction conditions, wherein the reactor system is - Supply of feedstock containing methanol and water; - A structural catalyst arranged to catalyze the methanol decomposition reaction of the feed material; wherein the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supporting a ceramic coating, and the ceramic coating supporting a catalytically active material; - A pressure shell housing the structural catalyst; wherein the pressure shell comprises an inlet for introducing the feed material and an outlet for discharging product gases, the inlet being positioned such that the feed material enters the structural catalyst from a first end of the structural catalyst and the product gases exit the structural catalyst from a second end of the structural catalyst. - The insulating layer between the structural catalyst and the pressure shell; - At least two conductors electrically connected to the structural catalyst and a power supply located outside the pressure shell; wherein the power supply is sized to heat at least a portion of the structural catalyst to a temperature of at least 150°C by passing an electric current through the macrostructure. - Outlet for hydrogen-containing product flow Equipped with, The reactor system wherein the at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and the structural catalyst is configured to substantially carry current from one conductor to the second end of the structural catalyst and back to the second of the at least two conductors.

2. The reactor system according to claim 1, wherein the power supply is sized to heat at least a portion of the structural catalyst to a temperature of at least 150°C.

3. The aforementioned raw materials are further H ２ , N ２ The reactor system according to claim 1 or 2, comprising , or Ar.

4. The reactor system according to any one of claims 1 to 3, wherein the pressure shell has a design pressure between 2 and 30 bar.

5. The reactor system according to any one of claims 1 to 3, wherein the pressure shell has a design pressure between 30 and 200 bar.

6. A method for carrying out a methanol decomposition reaction to convert feedstocks, including methanol and water, into hydrogen in the presence of a catalyst, in a reactor system including a pressure shell housing a structural catalyst arranged to catalyze the methanol decomposition reaction of feedstocks, wherein, in methanol decomposition reaction conditions, the structural catalyst comprises a macrostructure of a conductive material, the macrostructure supports a ceramic coating, the ceramic coating supports a catalytically active substance; and the reactor system is provided with thermal insulation between the structural catalyst and the pressure shell; - The reactor system comprises at least two conductors electrically connected to the structural catalyst and a power supply located outside the pressure shell, The at least two conductors are connected to the structural catalyst at a position on the structural catalyst closer to the first end of the structural catalyst than to the second end of the structural catalyst, and the structural catalyst is configured to substantially carry current from one conductor to the second end of the structural catalyst and back to the second conductor of the at least two conductors, The aforementioned method includes the following steps: - Step of pressurizing the supply raw material. - A step of supplying the pressurized feed material to the pressure shell through an inlet positioned such that the feed material enters the structural catalyst at the first end of the structural catalyst, causing the feed material to undergo methanol decomposition on the structural catalyst, and discharging the product gas from the pressure shell, during which the product gas exits the structural catalyst from the second end of the structural catalyst; - A power supply located outside the pressure shell is connected to the structural catalyst via an electrical conductor, thereby allowing current to flow through the macrostructure, and thereby heating at least a portion of the structural catalyst to a temperature of at least 150°C; - A step to discharge hydrogen-containing product gas from the reactor system.

7. The method according to claim 6, further comprising the step of supplying a hydrogen-containing product stream to an upgraded unit and separating it into an upgraded hydrogen stream and an off-gas stream.

8. The method according to claim 7, further comprising the step of supplying the product gas or the upgraded hydrogen stream from the upgrade unit to a downstream plant for power generation.

9. A method for rapidly switching a metal-catalyzed methanol decomposition reaction of a feedstock containing methanol from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or vice versa, in a reactor system according to any one of claims 1 to 5; the method comprising the following steps: Under the first steady-state reaction condition (A) - A step of supplying the raw material to the reactor system at a first total flow rate, and - A power supply located outside the pressure shell is connected to the structural catalyst via an electrical conductor to supply a first power, thereby causing a first current to flow through the conductive material. The steps include: heating at least a portion of the structural catalyst to a first temperature, at this temperature, under the first steady-state reaction conditions (A), the feed material being converted on the structural catalyst into a first product gas mixture; and discharging the first product gas mixture from the reactor system. Then, under the second steady-state reaction condition (B) - A step of supplying the raw material to the reactor system at a second total flow rate, and - A power source located outside the pressure shell is supplied with a second power supply via an electrical conductor connected to the structural catalyst, thereby causing a second current to flow through the conductive material. The steps include: heating at least a portion of the structural catalyst to a second temperature; at this temperature, under the second steady-state reaction conditions (B), the feed material is converted on the structural catalyst into a second product gas mixture; and discharging the second product gas mixture from the reactor system. Here, the second power is greater than the first power, and / or the second total flow rate is greater than the first total flow rate.

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