On-demand production of syngas from methanol

Abstract

A reactor system and method are provided for subjecting a feedstock comprising methanol to methanol cracking and reverse water-gas shift reactions to produce syngas wherein heat for endothermic methanol cracking and reverse water-gas shift reactions is provided by resistance heating.

Description

[0001] This application is a divisional application of an application with a filing date of September 24, 2020, application number 202080070202.7, and invention name “On-demand production of synthesis gas from methanol”. Technical Field

[0002] A reactor system and method are provided for generating synthesis gas from a feedstock containing methanol in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions, wherein heat for the methanol cracking and reverse water gas shift reactions is provided by resistive heating. Background Art

[0003] Syngas production is usually carried out in large chemical plants due to the energy-intensive reactions required to facilitate its production. This makes small-scale production difficult. In addition, the toxicity of syngas, especially due to its carbon monoxide content, makes its storage difficult and poses a significant risk.

[0004] There is a need to produce syngas on demand using a relatively simple production setup in a smaller facility, requiring minimal operator input, using reactants that are easily stored to produce syngas.

[0005] Systems and methods for performing endothermic catalytic reactions are described in co-pending patent application PCT / EP2019 / 062424. An adiabatic POst converter (APOC) reactor is described in WO 2019 / 110267. Summary of the invention

[0006] Thus, in a first aspect, there is provided a reactor system for producing synthesis gas from a feedstock comprising methanol in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions, the reactor system comprising:

[0007] - a source of a feedstock comprising methanol and water;

[0008] - a structured catalyst arranged for catalyzing said methanol cracking and reverse water gas shift reactions of said feedstock, said structured catalyst comprising macrostructures of electrically conductive material, said macrostructures supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material;

[0009] - a pressure-resistant shell containing the structured catalyst, the pressure-resistant shell comprising an inlet for admitting the feedstock and an outlet for letting out the product gas, wherein the inlet is located so that the feedstock enters the structured catalyst at a first end of the structured catalyst and the product gas leaves the structured catalyst from a second end of the structured catalyst;

[0010] - a thermal insulation layer between the structured catalyst and the pressure shell;

[0011] - at least two conductors electrically connected to the structured catalyst and to a power source disposed outside the pressure vessel, wherein the power source is sized to heat at least a portion of the structured catalyst to a temperature of at least 500° C. by passing an electric current through the macrostructure, wherein the at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct an electric current from one conductor substantially toward the second end of the structured catalyst and back to a second of the at least two conductors;

[0012] - An outlet for a first product gas comprising synthesis gas.

[0013] In another aspect, there is provided a method for performing methanol cracking and reverse water gas shift reactions of a feedstock comprising methanol and water in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions in a reactor system to produce synthesis gas, the reactor system comprising a pressure shell containing a structured catalyst, the structured catalyst being arranged to catalyze the methanol cracking and reverse water gas shift reactions of the feedstock, the structured catalyst comprising a macrostructure of an electrically conductive material, the macrostructure supporting a ceramic coating, wherein the ceramic coating supports a catalytically active material; wherein the reactor system is provided with a thermal insulation layer between the structured catalyst and the pressure shell; the method comprising the following steps:

[0014] - pressurizing the raw material,

[0015] - supplying the pressurized feedstock to the pressure shell through an inlet, the inlet being located so that the feedstock enters the structured catalyst at a first end of the structured catalyst; subjecting the feedstock to methanol cracking and reverse water gas shift reactions on the structured catalyst; and discharging product gas from the pressure shell, wherein the product gas leaves the structured catalyst from a second end of the structured catalyst;

[0016] - providing electrical power via an electrical conductor connected from a power source positioned outside the pressure vessel to the structured catalyst, allowing an electric current to run through the macrostructure, thereby heating at least a portion of the structured catalyst to a temperature of at least 500° C., wherein the at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct an electric current from one conductor substantially toward the second end of the structured catalyst and back to a second of the at least two conductors, thereby heating at least a portion of the structured catalyst to a temperature sufficient to cause the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst, thereby heating at least a portion of the structured catalyst to a temperature sufficient to cause the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst,

[0017] - Discharging a first product gas comprising synthesis gas from the reactor system.

[0018] In another aspect, there is provided a method for rapidly switching metal-catalyzed methanol cracking and reverse water gas shift reactions of a feedstock comprising methanol and water from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or from a second steady-state reaction condition (B) to a first steady-state reaction condition (A) in a reactor system as described herein; the method comprising the following steps:

[0019] In the first steady-state reaction condition (A):

[0020] - supplying the feedstock to the reactor system at a first total flow rate, and

[0021] - providing a first electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, thereby allowing a first current to flow through the conductive material,

[0022] thereby heating at least a portion of the structured catalyst to a first temperature at which the feedstock is converted over the structured catalyst under the first steady-state reaction condition (A) to a first product gas mixture; and causing the first product gas to be discharged from the reactor system;

[0023] And, in the second steady-state reaction condition (B):

[0024] - supplying the feedstock to the reactor system at a second total flow rate,

[0025] - providing a second electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, thereby allowing a second current to flow through the conductive material,

[0026] thereby heating at least a portion of the structured catalyst to a second temperature; converting the feedstock at the second temperature over the structured catalyst under the second steady-state reaction condition (B) to a second product gas mixture; and exhausting the second product gas from the reactor system;

[0027] The second electric power is higher than the first electric power; and / or the second total flow is higher than the first total flow.

[0028] Further aspects of the invention are set out in the following detailed description, examples and appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1a shows a cross-section of one embodiment of a reactor system of the present invention having a structured catalyst comprising an array of macrostructures in cross-section;

[0030] Figure 1b Shows Figure 1a A reactor system wherein a portion of the pressure vessel and thermal insulation are removed;

[0031] Figure 2 is an enlarged view of a portion of a reactor system;

[0032] Figure 3a and 3b shows a schematic cross-section of one embodiment of a reactor system of the present invention comprising a structured catalyst;

[0033] Figure 4 and 5 An embodiment of a structured catalyst having an array of macrostructures is shown viewed from above and from the side, respectively;

[0034] Figure 6 An embodiment of a structured catalyst according to the present invention is shown;

[0035] Figure 7 and 8 An embodiment of a structured catalyst having a connector is shown;

[0036] Fig. 9 The equilibrium composition of methanol cracking and reverse water gas shift according to CH3OH, H2O, H2, CO2 and CO varies with temperature at 29 barg when 33% CH3OH, 33% H2O and 33% CO2 are used as feedstocks. Fig.10The temperature variations of the equilibrium compositions of methanol cracking, reverse water gas shift and methanation reactions according to CH3OH, H2O, H2, CO2 and CO at 29 barg when 33% CH3OH, 33% H2O and 33% CO2 are used as feedstocks are shown.

[0037] Fig.11 One embodiment of a process including a reactor system and feedstock setup is shown.

[0038] Fig.12 One embodiment of a process including a reactor system, an adiabatic post converter, and feedstock provisioning is shown.

[0039] Fig.13 One embodiment of a process including feedstock preparation, a reactor system, an upgrading unit including flash separation and CO2 removal, and waste gas stream recycle is shown.

[0040] Fig.14 One embodiment of a process including feedstock preparation, a reactor system, an upgrading unit including flash separation and membranes, and waste gas stream recycle is shown.

[0041] Fig.15 One embodiment of a process including feedstock preparation, a reactor system, an upgrading unit including flash separation, CO2 removal and a cold box, and waste gas stream recycle is shown. DETAILED DESCRIPTION

[0042] Electrically heated methanol cracking provides a solution for rapidly heating methanol cracking and reverse water gas shift catalyst to produce synthesis gas on demand. This allows rapid production of synthesis gas in, for example, chemical facilities to promote other chemical reactions of these molecules. Examples of such reactions include phosgene, acetic acid, and oxo alcohols. In addition, the solution allows the use of relatively simple production settings in smaller facilities, requiring minimal operator input, and using easily stored reactants for synthesis gas production to achieve on-demand production of synthesis gas. Moreover, the method also provides a solution for on-demand production of synthesis gas based on the fluctuating power availability of renewable power sources (such as wind or solar energy).

[0043] This technology describes how an electrically heated reactor can facilitate the production of syngas from methanol in an on-demand process in a compact design.

[0044] The methanol reaction can be summarized as:

[0045]

[0046] where ΔH R =41 kJ / mol, and ΔH R =91kJ / mol.

[0047] In addition, the reverse water-gas shift reaction is utilized:

[0048]

[0049] Typically, catalysts with catalytically active materials including copper (Cu) are used for methanol cracking and reverse water gas shift. However, catalysts with catalytically active materials including nickel (Ni) or precious metals may also be used, which have higher temperature stability. Other catalyst systems may include Fe or Mn as catalytically active materials. Depending on the type of catalyst, feed composition and operating conditions, methanation (and reverse steam reforming) reactions may also occur:

[0050]

[0051] Compact electroreactors using monolithic catalysts can be easily operated and produce syngas when needed using an easy start-up principle. This provides a relatively inexpensive facility where syngas can be produced only in the required amount, with little to no need for syngas storage, while also reducing or completely eliminating syngas transportation. The simple reactor equipment and simple operation of the methanol cracking process make syngas production attractive in non-stationary facilities, which reduces the risks of syngas handling.

[0052] Furthermore, using electricity as a heat source allows for rapid startup and shutdown (on the order of minutes or hours). This almost instantaneous switchover from standby to syngas production and back also reduces the need for syngas storage.

[0053] Thus, there is provided a reactor system for producing synthesis gas from a feedstock comprising methanol and water in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions, the reactor system comprising:

[0054] - a source of a feedstock comprising methanol and water;

[0055] - a structured catalyst arranged for catalyzing said methanol cracking and reverse water gas shift reactions of said feedstock, said structured catalyst comprising macrostructures of electrically conductive material, said macrostructures supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material;

[0056] - a pressure-resistant shell containing the structured catalyst, the pressure-resistant shell comprising an inlet for admitting the feedstock and an outlet for letting out the product gas, wherein the inlet is located so that the feedstock enters the structured catalyst at a first end of the structured catalyst and the product gas leaves the structured catalyst from a second end of the structured catalyst;

[0057] - a thermal insulation layer between the structured catalyst and the pressure shell;

[0058] - at least two conductors electrically connected to the structured catalyst and to a power source disposed outside the pressure vessel, wherein the power source is sized to heat at least a portion of the structured catalyst to a temperature of at least 500° C. by passing an electric current through the macrostructure, wherein the at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct an electric current from one conductor substantially toward the second end of the structured catalyst and back to a second of the at least two conductors;

[0059] - An outlet for product gas comprising synthesis gas.

[0060] The layout of the reactor system allows for feeding the pressurized feedstock to the reactor system at the inlet and directing the gas into the pressure vessel of the reactor system. Inside the pressure vessel, an arrangement of thermal insulation and inert materials is arranged to direct the feedstock through the structured catalyst where it will come into contact with the catalyst material, wherein the catalytically active material will promote the methanol cracking and reverse water gas shift reactions. In addition, the heating of the structured catalyst will supply the required heat for the endothermic reaction. The product gas from the heated structured catalyst is directed to the reactor system outlet.

[0061] The close proximity between the catalytically active material and the electrically conductive material enables efficient heating of the catalytically active material by close proximity heat conduction from the electrically conductive material of the resistive heating. Thus, an important feature of the resistive heating process is that the energy is supplied within the object itself, rather than from an external heat source via thermal conduction, convection, and radiation. In addition, the hottest portion of the reactor system will be located within the pressure vessel of the reactor system. Preferably, the power source and the size of the structured catalyst are configured so that at least a portion of the structured catalyst reaches a temperature of at least 500° C., preferably at least 900° C. The surface area of ​​the electrically conductive material, the proportion of the electrically conductive material coated with the ceramic coating, the type and structure of the ceramic coating, and the amount and composition of the catalytically active catalyst material can be tailored to the specific reaction under given operating conditions.

[0062] The conductive material is suitably a macrostructure. As used herein, the term "macrostructure" is intended to mean a structure large enough to be seen with the naked eye without the need for a magnifying device. The size of the macrostructure is typically in the range of centimeters or even meters. It is advantageous to make the size of the macrostructure correspond at least in part to the internal dimensions of the pressure shell containing the structured catalyst, leaving room for the thermal insulation layer and the conductor. Two or more macrostructures can be connected to provide a macrostructure array, at least one of whose external dimensions is in the meter range, such as 2m or 5m. Such two or more macrostructures can be represented as a "macrostructure array". In this case, it is advantageous to make the size of the macrostructure array correspond at least in part to the internal dimensions of the pressure shell containing the structured catalyst (leaving room for the thermal insulation layer). A conceivable macrostructure array can occupy 0.1 to 10m 3 Or even larger volumes. The structured catalyst may comprise a single macrostructure or an array of macrostructures, wherein (one or more) macrostructures support a ceramic coating, and the ceramic coating supports a catalytically active material. In the array of macrostructures, the macrostructures may be electrically connected to each other; however, optionally, the macrostructures are not electrically connected to each other. Thus, the structured catalyst may comprise two or more macrostructures positioned adjacent to each other. (One or more) macrostructures may be extruded and sintered structures or 3D printed structures. 3D printed macrostructures may be provided with or without subsequent sintering.

[0063] The physical dimensions of the macrostructures may be any suitable dimensions; thus, the height may be smaller than the width of the macrostructure, or vice versa.

[0064] The macrostructure supports a ceramic coating, wherein the ceramic coating supports a catalytically active material. The term "macrostructure supporting a ceramic coating" means that the macrostructure is coated with a ceramic coating on at least a portion of the surface of the macrostructure. Thus, the term does not mean that all surfaces of the macrostructure are coated with the ceramic coating; in particular, there is no coating on at least the portion of the macrostructure that is electrically connected to the conductor. The coating is a ceramic material having pores in the structure that allow the catalytically active material to be supported on and within the coating. Advantageously, the catalytically active material comprises catalytically active particles having a size ranging from about 2 nm to about 250 nm.

[0065] Preferably, the macrostructure has been manufactured by extruding a mixture of powdered metal particles and a binder into an extruded structure and subsequently sintering the extruded structure to provide a material with a high geometric surface area per volume. Preferably, the extruded structure is sintered in a reducing atmosphere to provide the macrostructure. Optionally, the macrostructure is 3D printed, a metal additive manufacturing melting process, i.e. a 3D printing process that does not require subsequent sintering, such as a powder bed fusion or direct energy deposition process. Examples of such powder bed fusion or direct energy deposition processes are laser beam, electron beam or plasma 3D printing processes. As another option, the macrostructure can be manufactured as a 3D metal structure by means of a binder-based metal additive manufacturing process and then sintered at a first temperature T1 in a non-oxidizing atmosphere, where T1>1000°C, to provide the macrostructure.

[0066] A ceramic coating, which may contain a catalytically active material, is provided to the macrostructure, followed by a second sintering in an oxidizing atmosphere to form a chemical bond between the ceramic coating and the macrostructure. Alternatively, the catalytically active material may be impregnated onto the ceramic coating after the second sintering. When a chemical bond is formed between the ceramic coating and the macrostructure, it is possible to have a particularly high thermal conductivity between the electrically heated macrostructure and the catalytically active material supported by the ceramic coating, thereby providing close and almost direct contact between the heat source and the catalytically active material of the structured catalyst. Due to the close proximity between the heat source and the catalytically active material, heat transfer is efficient, and thus the structured catalyst can be heated very efficiently. Therefore, a compact reactor system is possible in terms of gas processing per reactor system volume, and therefore the reactor system accommodating the structured catalyst can be compact.

[0067] As used herein, the terms "3D printing" and "3D printing" are intended to refer to metal additive manufacturing processes. Such metal additive manufacturing processes cover 3D printing processes in which material is joined to a structure under computer control to create a three-dimensional object, wherein the structure will be solidified, such as by sintering, to provide a macrostructure. Moreover, such metal additive manufacturing processes cover 3D printing processes that do not require subsequent sintering, such as powder bed fusion or direct energy deposition processes. Examples of such powder bed fusion or direct energy deposition processes are laser beam, electron beam or plasma 3D printing processes.

[0068] The reactor system does not require a furnace, which significantly reduces the overall size of the reactor.

[0069] The conductive material comprises Fe, Ni, Cu, Co, Cr, Al, Si or an alloy thereof. Such alloys may contain further elements, such as Mn, Y, Zr, C, Co, Mo or a combination thereof. Preferably, the conductive material comprises Fe, Cr, Al or an alloy thereof. Such alloys may contain further elements, such as Si, Mn, Y, Zr, C, Co, Mo or a combination thereof. Preferably, the catalytically active material is a particle having a size of 2 nm to 250 nm. Preferably, the conductor and the conductive material are made of a material different from the conductive material. The conductor may be, for example, iron, nickel, aluminum, copper, silver or an alloy thereof. The ceramic coating is an electrically insulating material, the thickness of which is typically in the range of about 100 μm, for example 10-500 μm.

[0070] The conductive material is advantageously a coherent or always internally connected material, so as to realize the conductivity in the whole conductive material, thereby realize the thermal conductivity in the whole structured catalyst, particularly provide the heating of the catalyst material. Through the coherent or always internally connected material, it is possible to ensure the uniform distribution of electric current in the conductive material, and therefore ensure the uniform distribution of heat in the structured catalyst. Throughout the text, the term "coherent (coherent)" means a synonym of cohesion, and therefore refers to the material that is always internally connected or always coupled. The structured catalyst is a coherent or always internally connected material that controls the connectivity in the material of the structured catalyst and therefore obtains the conductivity of the conductive material. It should be noted that even if the conductive material is further modified, such as providing a slit in multiple parts of the conductive material or implementing an insulating material in the conductive material, it is still represented that the conductive material is a coherent or always internally connected material.

[0071] The gas flow over the structured catalyst may be axial or coaxial with the current path through the structured catalyst, perpendicular to the current path, or have any other suitable direction relative to the current path.

[0072] Methanol cracking and reverse water gas shift reactions are highly endothermic. High temperatures, usually in excess of 700-1000°C, are required to achieve acceptable conversion of methanol in the feed and good selectivity to CO.

[0073] Control of the co-feed of H2O and CO2 is used to control the composition of the resulting syngas. Increasing the content of H2O will reduce the severity of the gas environment and reduce the risk of unwanted side reactions such as carbon formation. Increasing the content of CO2 will increase the selectivity to CO by displacing the reverse water gas shift reaction.

[0074] The feedstock can be a liquid or gaseous feedstock, but is preferably a gaseous feedstock. The feedstock is suitably pressurized in a liquid state before evaporation, and then the gaseous feedstock is fed into the reactor. This arrangement requires less compression energy.

[0075] In one embodiment, the raw material for methanol cracking and reverse water gas shift reaction is a substantially pure methanol stream, containing a small amount of water according to hydration from the atmosphere. In another embodiment, the raw material is a mixture of methanol and steam, and the ratio of methanol to steam is 1:0.5. In another embodiment, the ratio is 1:0.2, 1:3 or between the two. In a preferred embodiment, the raw material is a mixture of CO2, steam and methanol. The ratio between CO2 and methanol in the feed can be any value between 5:1 and 0.1:1. In one embodiment, the raw material is prepared by preparing a substantially pure H2O stream, a stream containing methanol and a gas stream rich in CO2 at a preferred temperature and pressure, respectively, and then mixing them in a preferred ratio to prepare the raw material. Substantially pure H2O stream is understood to be a stream that generally contains more than 98% H2O, such as demineralized water. A gas stream rich in CO2 is understood to contain more than 50% CO2, preferably more than 80% CO2, and even more preferably more than 99% CO2. In another embodiment, the raw material contains other alcohols other than methanol, such as ethanol, propanol and / or butanol. Typically, the concentration of such other alcohols in the feedstock will be less than 10% by volume, such as less than 5%, or less than 2%. Other oxygen-containing compounds such as aldehydes, ethers and / or ketones may also be present in the feedstock, typically at a concentration of less than 2% by volume, such as less than 0.5% by volume. The term "conductive" is intended to mean that the resistivity at 20°C is within 10 -5 Up to 10 -8 Thus, the conductive material is, for example, a metal such as copper, silver, aluminum, chromium, iron, nickel, or an alloy of the metal. Furthermore, the term "electrically insulating" is intended to mean a material with a resistivity higher than 10 Ω·m at 20°C, for example a material with a resistivity of 10 Ω·m at 20°C. 9 Up to 10 25 In the range of Ω·m.

[0076] When the reactor system includes a thermal insulation layer located between the structured catalyst and the pressure shell, appropriate thermal and electrical insulation is obtained between the structured catalyst and the pressure shell. The presence of a thermal insulation layer between the pressure shell and the structured catalyst helps to avoid excessive heating of the pressure shell and helps to reduce heat loss to the surrounding environment. The temperature of the structured catalyst can reach about 1300°C, at least in some parts thereof, but by using a thermal insulation layer between the structured catalyst and the pressure shell, the temperature of the pressure shell can be maintained at a significantly lower temperature, such as 500°C or even 100°C, which is advantageous because typical construction steel is generally not suitable for pressure applications at temperatures above 1000°C. In addition, the thermal insulation layer between the pressure shell and the structured catalyst helps to control the current within the reactor system because the thermal insulation layer is also electrically insulating. The thermal insulation layer can be one or more layers of solid material, such as ceramics, inert materials, fibrous materials, bricks or gas barriers or combinations thereof. Therefore, it is also conceivable that the purge gas or the limiting gas constitutes or forms part of the thermal insulation layer.

[0077] Furthermore, it should be noted that the term "thermal insulating material" refers to a material having a thermal conductivity of about 10 W·m -1 ·K -1 Materials with a thermal conductivity of 2000 Å or less. Examples of thermal insulating materials are ceramics, bricks, alumina-based materials, zirconia-based materials, and the like.

[0078] Advantageously, any relevant gaps between the structured catalyst, the thermal insulation layer, the pressure shell and / or any other components in the reactor system are filled with inert materials, for example in the form of inert granules. Such gaps are, for example, the gap between the bottom of the structured catalyst and the pressure shell and the gap between the side of the structured catalyst and the insulating layer covering the inner side of the pressure shell. The inert material can be, for example, a ceramic material in the form of granules or tiles. The inert material helps control the gas distribution through the reactor system and controls the gas flow through the structured catalyst. Moreover, the inert material usually has a thermal insulation effect.

[0079] The pressure shell has a design pressure of 2 bar to 30 bar appropriately. The actual operating pressure will depend on aspects such as the endothermic reaction, the size of the facility. Since the hottest part of the reactor system is a conductive material, the conductive material will be surrounded by a thermal insulation layer and located in the pressure shell of the reactor system, so the temperature of the pressure shell can be kept significantly lower than the maximum process temperature. This allows the pressure shell to have a relatively low design temperature, for example, the design temperature of the pressure shell is 500 ° C or 300 ° C or preferably 200 ° C or 100 ° C, while having a maximum process temperature of 400 ° C or preferably 700, but even 1100 ° C, or even up to 1300 ° C on the structured catalyst. At lower temperatures among these temperatures, the material strength is higher (corresponding to the design temperature of the pressure shell mentioned above). This provides an advantage when designing a chemical reactor. Suitably, the design pressure of the pressure shell is 2 bar to 30 bar or 30 to 200 bar. As a compromise between process economy and thermodynamic constraints, preferably about 30 bar.

[0080] The resistivity of the conductive material is suitably 10 -5 Ω·m to 10 -7 Ω·m. Materials with resistivity in this range provide efficient heating of the structured catalyst when powered by a power source. The resistivity of graphite at 20°C is about 10 -5 Ω·m, the resistivity of kanthal at 20℃ is about 10 -6 Ω·m, while the resistivity of stainless steel at 20°C is about 10 -7 Ω·m. The conductive material may have a resistivity of about 1.5·10 at 20°C, for example. -6 Ω·m FeCr alloy.

[0081] Typically, the pressure vessel includes an inlet for admitting process gas and an outlet for discharging product gas, wherein the inlet is located proximate to a first end of the pressure vessel and the outlet is located proximate to a second end of the pressure vessel, and wherein at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the inlet than to the outlet. Thus, the at least two conductors can be placed in a significantly cooler portion of the reactor system, because the temperature of the inlet gas will be lower than the temperature of the product gas, the conductive material will be cooler at the most upstream portion of the material due to the heat consumed by the chemical reaction process, and the feedstock fed through the inlet can cool the at least two conductors and then be heated by the heated structured catalyst further along the path of the gas on the heated structured catalyst. Advantageously, the temperature of all conductive elements other than the conductive material is kept low to protect the connection between the conductor and the structured catalyst. When the temperature of the conductor and other conductive elements other than the conductive material is relatively low, there are fewer restrictions on the materials suitable for the conductor and other conductive elements other than the conductive material. When the temperature of the conductive element increases, its resistivity increases; therefore, it is desirable to avoid unnecessary heating of all other components in the reactor system other than the conductive material. The term "conductive elements other than conductive material" is intended to encompass associated conductive elements arranged to connect a power source to the structured catalyst other than the conductive structured catalyst itself.

[0082] It should be noted that the systems of the present invention may include any suitable number of power sources and any suitable number of conductors connecting the power source(s) and the conductive material(s) of the structured catalyst.

[0083] Suitably, at least two conductors are guided through the pressure hull in a sleeve so that the at least two conductors are electrically insulated from the pressure hull. The sleeve may be made in part of a plastic and / or ceramic material. The term "sleeve" is intended to indicate a device that allows two pieces of hardware to be mechanically connected in a pressure-bearing configuration. Thus, the pressure within the pressure hull may be maintained even if the at least two conductors are guided through the pressure hull. Non-limiting examples of sleeves may be an electrically insulating sleeve, a dielectric sleeve, a dynamic compression seal, a compression sleeve or a flange. The pressure hull typically comprises side walls, end walls, flanges and possibly other parts. The term "pressure hull" is intended to cover any of these components.

[0084] The pressure shell may also include one or more inlets close to or in combination with at least one sleeve to allow cooling gas to flow on, around, near or inside at least one conductor in the pressure shell. Therefore, the conductor is cooled, so the temperature experienced by the sleeve remains very low. If cooling gas is not used, the conductor can be heated by the raw material fed to the reactor system, the resistance heating of the conductor due to the applied current, and / or the heat conduction from the structured catalyst. The cooling gas can be, for example, hydrogen, argon, water, nitrogen, carbon dioxide, methanol or a mixture thereof. The temperature of the cooling gas entering the pressure shell can be, for example, about 50°C or 200°C or 250°C. In one embodiment, (one or more) conductors are hollow so that the cooling gas can flow through the (one or more) conductors and cool it (them) from the inside. By keeping the temperature of the sleeve at a lower level, for example, at about 100-200°C, it is easier to achieve a leakproof configuration. Typically, a portion of the raw materials, such as one of the reactants, is fed into the pressure shell as a cooling gas. In another embodiment, a portion of the raw materials or a gas having the same composition as the raw materials is used as a cooling gas.

[0085] The reactor system may also include an inner tube in a heat exchange relationship with the structured catalyst, wherein the inner tube is adapted to extract product gas from the structured catalyst so that the product gas flowing through one or more inner tubes is in a heat exchange relationship with the gas flowing on the structured catalyst, but is electrically separated from the structured catalyst. This is a layout represented herein as a bayonet reactor system. In this layout, the product gas in the inner tube helps to heat the process gas flowing on the structured catalyst. The electrical insulation between the inner tube and the structured catalyst may be a gas in the form of a gap or distance between the inner tube and the structured catalyst, or an inert material loaded around the inner tube and the structured catalyst. The gas may pass through the structured catalyst in an upward flow or downward flow direction.

[0086] The connection between the structured catalyst and the at least two conductors can be a mechanical connection, a welded connection, a brazed connection, or a combination thereof. The structured catalyst can include terminals physically and electrically connected to the structured catalyst to facilitate electrical connection between the conductive material and the at least two conductors. The term "mechanical connection" is intended to mean a connection in which two components are mechanically held together, such as by threading or by clamping, so that current can flow between the components.

[0087] The conductive materials placed in the conductive material array can be electrically connected to each other. The connection between two or more conductive materials can be by mechanical connection, clamping, soldering, welding or any combination of these connection methods. Each conductive material can include a terminal to facilitate electrical connection. Two or more conductive materials can be connected to a power source in series or in 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 always connected material; therefore, uniform conductivity throughout the two or more conductive materials is promoted. Alternatively or additionally, the structured catalyst may include an array of conductive materials that are not electrically connected to each other. Instead, two or more conductive materials are placed together in a pressure-resistant shell, but are not electrically connected to each other. In this case, the structured catalyst therefore includes conductive materials connected in parallel to the power source.

[0088] Ceramic coatings with or without catalytically active materials can be added directly to the metal surface of the conductive material by wash coating. Wash coating of metal surfaces is a well-known process; descriptions are given, for example, in Cybulski, A., and Moulijn, JA, "Structured catalysts and reactors", Marcel Dekker, Inc, New York, 1998, Chapter 3 and references therein. The ceramic coating can be added to the surface of the conductive material and the catalytically active material can be added subsequently; alternatively, the ceramic coating containing the catalytically active material is added to the macrostructure or conductive material. The ceramic coating can be, for example, an oxide containing Al, Zr, Mg, Ce and / or Ca. Exemplary coatings are calcium aluminate or magnesium aluminum spinel. Such ceramic coatings can contain additional elements, such as La, Y, Ti, K or combinations thereof. The ceramic coating is an electrically insulating material whose thickness is typically in the range of about 100 μm, say 10-500 μm.

[0089] Extruded and sintered or 3D printed macrostructures result in homogeneous and coherent macrostructures, which can then be coated with a ceramic coating.

[0090] The conductive material and the ceramic coating may have been sintered in an oxidizing atmosphere to form a chemical bond between the ceramic coating and the conductive material; this provides a particularly high thermal conductivity between the conductive material and the catalytically active material supported by the ceramic coating. Thus, the structured catalyst is compact in terms of heat transfer to the active catalytic sites, and the reactor system housing the structured catalyst can be compact and limited primarily by the chemical reaction rate.

[0091] In one embodiment, the structured catalyst has at least one electrically insulating component arranged to increase the current path between the conductors to a length greater than the maximum dimension of the structured catalyst. Providing a current path between the conductors that is greater than the maximum dimension of the structured catalyst can be achieved by providing (one or more) electrically insulating components located between the conductors and preventing the current from flowing through a portion of the structured catalyst. Such electrically insulating components are arranged to increase the current path and thus increase the resistance through the structured catalyst. Therefore, the current path through the structured catalyst can be longer than the maximum dimension of the structured catalyst, for example, by 50%, 100%, 200%, 1000% or even more than 10000%.

[0092] In addition, such an electrically insulating member is arranged to direct current from a conductor closer to the first end of the structured catalyst than to the second end toward the second end of the structured catalyst and back to a second conductor closer to the first end of the structured catalyst than to the second end. Preferably, the current is arranged to flow from the first end of the structured catalyst to the second end and back to the first end. As shown in the accompanying drawings, the first end of the structured catalyst is its top end. Figure 5-7 The arrow indicated as "z" in the figure represents the z-axis along the length of the structured catalyst. The main current path running through the structured catalyst will have a positive or negative value of the z-coordinate of the accompanying current density vector along most of the length of the current path. The main current path means the path of electrons through the macrostructure of the structured catalyst with the highest current density. The main current path can also be understood as the path with the minimum length through the macrostructure of the structured catalyst. Geometrically, the main current path can be quantified as the maximum current density vector in a plane perpendicular to the gas flow direction of the coherent part of the macrostructure. As shown in the figure, at the bottom of the structured catalyst, the current will turn, and the z-coordinate of the accompanying current density vector here will be zero.

[0093] As used herein, the term coherent portion is intended to refer to a cross-sectional area of ​​a macrostructure wherein all walls of the coherent portion are geometrically connected to one or more other walls of the coherent portion in the same plane.

[0094] In one embodiment, the structured catalyst has at least one electrically insulating component arranged to conduct an electric current through the structured catalyst so as to ensure that for at least 70% of the length of the structured catalyst, the current density vector of the main current path has a non-zero component value parallel to the length of the structured catalyst. Thus, for at least 70% of the length of the structured catalyst, the current density vector will have a positive or negative component value parallel to the length of the structured catalyst. Thus, for at least 70%, for example 90% or 95% of the length of the structured catalyst, i.e. Figures 5 to 10As seen in , along the z-axis of the structured catalyst, the current density vector of the main current path will have a positive or negative value along the z-axis. This means that the current is forced to flow from the first end of the structured catalyst to the second end, and then forced to flow to the first end again. The temperature of the gas entering the first end of the structured catalyst and the endothermic methanol cracking and reverse water gas shift reactions occurring on the structured catalyst absorb heat from the structured catalyst. To this end, the first end of the structured catalyst remains colder than the second end, and by ensuring that the current density vector of the main current path has a non-zero component value parallel to the length of the structured catalyst, this occurs with a substantially continuously increasing temperature curve, which gives a controllable reaction front. In one embodiment, the current density vector has a non-zero component value parallel to the length of the structured catalyst in 70%, preferably 80%, more preferably 90%, and even more preferably 95% of the length of the structured catalyst. It should be noted that the term "length of the structured catalyst" is intended to represent the size of the structured catalyst in the direction of gas flow. In the structured catalyst shown in the accompanying drawings, the length is longitudinal, that is, its longest dimension. This is shown by arrows representing z in some drawings.

[0095] Non-limiting examples of insulating components are cutouts, slits or holes in the structure. Optionally, solid insulating materials, such as ceramics, in the cutouts or slits in the structure can be used. In the case where the solid insulating material is a porous ceramic material, the catalytically active material can be advantageously incorporated into the hole by, for example, impregnation. The solid insulating material in the cutout or slit helps to keep the parts of the structured catalyst on the sides of the cutout or slit separate from each other. As used herein, the term "maximum dimension of the structured catalyst" is intended to represent the maximum internal dimension of the geometric form occupied by the structured catalyst. If the structured catalyst is box-shaped, the maximum dimension will be the diagonal from one corner to the farthest corner, also referred to as the space diagonal.

[0096] It should be noted that even though the current through the structured catalyst may be arranged to have a tortuous or curved path through the structured catalyst due to the electrically insulating components arranged to increase the current path, the gas passing through the reactor system enters at one end of the reactor system and passes over the structured catalyst once before being discharged from the reactor system. Inert material is advantageously present in the associated gap between the structured catalyst and the rest of the reactor system to ensure that the gas within the reactor system passes over the structured catalyst and catalyst material herein.

[0097] The length of the gas channel through the structured catalyst is suitably less than the length of the current channel from one electrode through the structured catalyst and to the next electrode. The ratio of gas channel length to current channel length may be less than 0.6, or 0.3, 0.1, or even as low as 0.002.

[0098] Typically, the structured catalyst has an electrical insulating component that is arranged to make the current path through the structured catalyst a zigzag path. Here, the terms "zigzag path" and "zigzag approach" are intended to represent a path with a corner that tracks the path from one conductor to another conductor at a variable angle. A zigzag path is, for example, a path that goes up, turns, and then goes down. A zigzag path can have many turns, going up and then down through the structured catalyst multiple times, even if one turn is enough to make the path a zigzag path.

[0099] It should be noted that an insulating component arranged to increase the current path is not necessarily associated with a ceramic coating on a conductive material. Although such a ceramic coating is also considered to be electrically insulating, it does not change the length of the current path between the conductors connected to the conductive material.

[0100] The macrostructure can have multiple parallel channels, multiple non-parallel channels and / or multiple labyrinth channels, wherein the channels have walls defining the channels. Therefore, several different forms of macrostructures can be used, as long as the surface area of ​​the structured catalyst exposed to the gas is as large as possible. In a preferred embodiment, the macrostructure has parallel channels because such parallel channels give the structured catalyst a very small pressure drop. In a preferred embodiment, the parallel longitudinal channels are inclined in the longitudinal direction of the macrostructure. In this way, the gas molecules flowing through the macrostructure will mostly tend to hit the walls in the channel, rather than just flowing directly through the channel without contacting the wall. In order to provide a macrostructure with sufficient resistivity, the size of the channel should be appropriate. For example, the channel can be square (as seen in a cross section perpendicular to the channel) and the side length of the square is 1 to 3 mm; however, it is conceivable that the channel has a maximum range of up to about 4 cm in the cross section. The thickness of the wall can be, for example, 0.2 to 2 mm, for example, about 0.5 mm, and the thickness of the ceramic coating supported by the wall is 10 μm to 500 μm, for example, 50 μm to 200 μm, for example, 100 μm. In another embodiment, the macrostructure of the structured catalyst is cross-corrugated.

[0101] Typically, when macrostructures are extruded or 3D printed, the pressure drop from the inlet to the outlet of the reactor system can be significantly reduced compared to reactors where the catalyst material is in pellet form.

[0102] Suitably, the reactor system also includes a bed of second catalyst material upstream of the structured catalyst within the pressure shell. Here, the term "upstream" is viewed from the direction of flow of the feedstock. Therefore, the term "upstream" is intended here to mean that the feedstock is directed through the bed of second catalyst material before reaching the structured catalyst. This provides a situation in which the second catalyst material can be arranged to pretreat the feed stream. There is no need to provide specific heating to the bed of second catalyst material; however, if the bed of second catalyst material is in close proximity to the structured catalyst, the bed of second catalyst material can be heated indirectly. Optionally, the second catalyst material can be heated. In order to clarify the terms used herein, it should be noted that the term "structured catalyst" may also be expressed as "first catalyst material" to distinguish it from the second and / or third and / or fourth catalyst material.

[0103] In one embodiment, the first catalyst material has different active material segments. Thus, the most upstream portion of the catalyst material is predominantly reactive toward one reaction, while a second portion is predominantly reactive toward another reaction.

[0104] The reactor system may further include a third catalyst material in the form of catalyst pellets, extrudates or particles loaded into the channels of the macrostructure. In this embodiment, the reactor system will therefore have a catalytically active material in the coating of the macrostructure and a third catalyst material in the form of catalyst pellets, extrudates or particles in the channels of the macrostructure. Pellets are, for example, prepared to a size that loosely matches the channel size to form a single pellet string stacked on each other in the channels of the macrostructure. Alternatively, pellets, extrudates or particles can be prepared to a size significantly smaller than the channel size to form a packed bed in each channel. As used herein, the term "pellet" is intended to represent any well-defined structure with a maximum external dimension in the range of millimeters or centimeters, and "extrudate" and "particle" are intended to define a catalyst material with a maximum external dimension defined within a range.

[0105] A bed of a fourth catalyst material may be placed within the pressure shell and downstream of the structured catalyst. This fourth catalyst material may be in the form of catalyst pellets, extrudates or granules.

[0106] Thus, the first, second, third, and fourth catalyst materials can be catalyst materials suitable for methanol cracking, reverse water gas shift reaction, and / or methanation / steam reforming reaction. In one embodiment, such catalyst is CuZn / Al2O3. In another embodiment, such catalyst is Ni / MgAl2O3. In a configuration comprising a combination of the second, third, and fourth catalyst materials in the reactor system, the catalyst of each catalyst material can be different.

[0107] The geometric surface area of ​​the macrostructure can range from 100 to 3000 m2 / m 3 , e.g. 500 to 1100m 2 / m 3 Typically, the material of the macrostructure is chosen to provide 500W / m 2 Up to 50000W / m 2 Preferably, the resistive heating of the material provides 5 kW / m 2 Up to 12kW / m 2 , for example 8kW / m 2 Up to 10kW / m 2 The heat flux is given as heat / geometric surface area of ​​the surface exposed to the gas.

[0108] In one embodiment, the structured catalyst includes a first part arranged to generate a first heat flux and a second part arranged to generate a second heat flux, wherein the first heat flux is lower than the second heat flux, and wherein the first part is located upstream of the second part. Here, the term "the first part is located upstream of the second part" is intended to indicate that the gas fed to the reactor system arrives at the first part before the gas arrives at the second part. The first part and the second part of the structured catalyst can be two different macro structures supporting the ceramic coating (which supports the catalytically active material), wherein the two different macro structures can be arranged to generate different heat fluxes for a given current and voltage. For example, the first part of the structured catalyst can have a large surface area, while the second part of the structured catalyst has a smaller surface area. This can be achieved by providing a structured catalyst in a second part having a cross-sectional area less than the cross-sectional area of ​​the first part. Alternatively, the current path through the first part of the structured catalyst can be straighter than the current path through the second part of the structured catalyst, so that the current is more tortuous or bent through the second part than through the first part of the structured catalyst, thereby the current generates more heat in the second part of the structured catalyst than in the first part. As previously mentioned, the slits or cuts in the macrostructure can make the current path through the macrostructure zigzag. It should be noted that the first and second parts of the structured catalyst can experience different currents and voltages so that different heat fluxes can be provided. However, due to the different physical properties of the first and second parts as described above, the different heat fluxes of the first and second parts can also be achieved by providing the same current and voltage in / on the first and second parts. In a further embodiment, the structured catalyst includes a third part arranged to generate a third heat flux, wherein the third heat flux is lower than the first and / or second heat flux, and wherein the third part is downstream of the first and / or second part.

[0109] The predetermined temperature range of the gas leaving the pressure vessel / reactor system is 500 to 1300° C. The product gas outlet temperature leaving the structured catalyst is measured directly below or on the most downstream surface of the structured catalyst. The measurement technology can be a thermocouple (by voltage drop), a resistance temperature detector or infrared detection. The measurement point can be separated from the structured catalyst and embedded in the downstream inert material / catalyst, or directly on the surface with an insulating surface covering.

[0110] The structured catalyst in the reactor system suitably has a ratio of the area equivalent diameter of the horizontal cross section through the structured catalyst to the height of the structured catalyst in the range of 0.1 to 2.0. The area equivalent diameter of the cross section through the reactor system is defined as the diameter of a circle having an area equivalent to the cross-sectional area. When the ratio of the area equivalent diameter to the height of the structured catalyst is 0.1 to 2.0, the pressure shell containing the structured catalyst can be relatively small compared to other reactor systems for endothermic reactions (e.g., tubular reformers currently used for steam methane reforming).

[0111] Typically, the gas flows through the reactor system in an upward or downward flow direction so that the gas flows through the channels therein along the height of the structured catalyst. When the structured catalyst includes a plurality of macrostructures or an array of macrostructures, the individual macrostructures within the array may be placed side by side, stacked one on top of the other, or in combination thereof. It should be emphasized that when the structured catalyst includes more than one macrostructure, the size of the structured catalyst is the size of the more than one macrostructure. Thus, as an example, if the structured catalyst includes two macrostructures stacked one on top of the other, each having a height h, the height of the structured catalyst is 2h.

[0112] The volume of the structured catalyst is selected taking into account the desired feed conversion rate and / or the temperature exiting the reactor system in relation to the heat generating capacity of the conductive material.

[0113] Suitably, the height of the reactor system is from 0.5 to 7 m, more preferably from 0.5 to 3 m. Exemplary values ​​for the height of the reactor system are heights of less than 5 meters, preferably less than 2 m or even 1 m. The size of the reactor system and the size of the structured catalyst within the reactor system are related; of course, the pressure hull and thermal insulation make the reactor system slightly larger than the structured catalyst itself.

[0114] In one embodiment, the first product gas comprises methane, for example a minimum of 0.5 vol% or a minimum of 1.0 vol%. The reactor system may further comprise an upgrading unit arranged to receive the product gas and separate it into an upgraded synthesis gas stream and a waste gas stream.

[0115] A method for generating synthesis gas by subjecting a raw material containing methanol to methanol cracking and reverse water gas shift reaction in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions in a reactor system, the reactor system comprising a pressure shell accommodating a structured catalyst, the structured catalyst being arranged to catalyze the methanol cracking of the raw material, the structured catalyst comprising a macroscopic structure of a conductive material, the macroscopic structure supporting a ceramic coating, wherein the ceramic coating supports a catalytically active material; wherein the reactor system is provided with a thermal insulation layer between the structured catalyst and the pressure shell.

[0116] The method comprises the following steps:

[0117] - pressurizing the raw material,

[0118] - supplying the pressurized feedstock to the pressure shell through an inlet, the inlet being located so that the feedstock enters the structured catalyst at a first end of the structured catalyst; subjecting the feedstock to methanol cracking and reverse water gas shift reactions on the structured catalyst; and discharging product gas from the pressure shell, wherein the product gas leaves the structured catalyst from a second end of the structured catalyst;

[0119] - providing electrical power via an electrical conductor connected from a power source positioned outside the pressure vessel to the structured catalyst, allowing current to flow through the macrostructure, thereby heating at least a portion of the structured catalyst to a temperature of at least 500° C., wherein the at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct current from one conductor to flow substantially toward the second end of the structured catalyst and back to a second of the at least two conductors, thereby heating at least a portion of the structured catalyst to a temperature sufficient to cause the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst,

[0120] - Discharging a first product gas comprising synthesis gas from the reactor system.

[0121] Whenever possible, all details of the system given above relate to the method described above.

[0122] In one aspect, the feedstock is pressurized to a pressure of 2 to 30 bar. The feedstock may be pressurized to a pressure of 30 to 200 bar. Suitably, at least a portion of the structured catalyst is heated to a temperature of at least 500°C, preferably at least 700°C. The maximum temperature to which the structured catalyst is heated is about 1400°C.

[0123] One aspect of the method further comprises the step of introducing a cooling gas through the pressure vessel via the inlet so as to allow the cooling gas to flow over the at least one conductor.

[0124] The method may further comprise an adiabatic post-converter, wherein a first product gas comprising synthesis gas from the reactor system is provided to the adiabatic post-converter, the adiabatic post-converter comprising a fifth catalyst active for catalytic steam methane reforming, methanation and reverse water gas shift reactions; and in the adiabatic post-converter, at least a portion of the first product gas and the heated CO2-rich gas stream are subjected to steam methane reforming, methanation and reverse water gas shift reactions to provide a second product gas, the second product gas being a synthesis gas stream rich in CO. The use of an adiabatic post-converter enables the entire process to be operated under very harsh conditions and low steam addition, since in this way carbon limitations, which would otherwise impose process limitations on the reactor system, can be partially circumvented.

[0125] In one embodiment, the second product gas comprises at least 0.5% methane by volume, such as at least 1.0% methane.

[0126] A CO-rich synthesis gas stream is understood to be a gas stream having a relatively high amount of CO. In one embodiment, the second product gas of the CO-rich synthesis gas comprises a gas mixture having a H2 / CO ratio of less than 3, such as preferably less than 2, or even less than 1.

[0127] One embodiment of the present invention further comprises the step of heating the CO2 rich gas stream in a fired heater to form a heated CO2 rich gas stream.

[0128] One embodiment of the present invention further comprises the step of heating the CO2 rich gas stream in an electrically heated heater to form a heated CO2 rich gas stream.

[0129] One embodiment of the present invention further comprises the step of heating the CO 2 rich gas stream by heat exchange with superheated steam to form a heated CO 2 rich gas stream.

[0130] One embodiment of the present invention further comprises the step of heating the CO2 rich gas stream by heat exchange with at least a portion of the second product gas stream exiting the adiabatic post converter to form a heated CO2 rich gas stream.

[0131] The heating of the CO2-rich gas stream can be combined, so that more than one of the following is used: a fired heater, an electrically heated heater, heat exchange with superheated steam, and heat exchange with a second product gas stream. In the case of a combination, in one embodiment, the CO2-rich gas stream is first heated by superheated steam (if heating with superheated steam is used), then in a fired heater or electrically heated heater (if flame / electric heating is used), and finally by heat exchange with at least a portion of the product gas leaving the adiabatic post-converter (if such heat exchange is used). The process may also include the step of feeding the first product gas or the second product gas containing synthesis gas to an upgrading unit and separating it into an upgraded synthesis gas stream and an exhaust gas stream. The upgrading unit can be arranged so that the exhaust gas stream is compressed and recycled and mixed with the feedstock supply before passing through the structured catalyst.

[0132] The upgrading units may include flash separation units, pressure swing adsorption (PSA) units, temperature swing adsorption (TSA) units, membrane units, CO2 separation, or a combination of CO2 separation and cold boxes. A cold box is defined as a cryogenic process for separating a mixture of H2, CO, and other gases into a slightly purer CO stream, a slightly purer H2 stream, and a balancing stream remaining in the feed stream.

[0133] Flash separation refers to a phase separation unit in which a stream is separated into a liquid phase and a gas phase according to the thermodynamic phase equilibrium at a given temperature.

[0134] CO2 separation refers to units that remove CO2 from process gases using processes such as chemical absorption. In chemical absorption, the gas containing CO2 passes through a solvent that reacts with CO2 and binds it in this way. Most chemical solvents are amines, which are divided into primary amines such as monoethanolamine (MEA) and diglycolamine (DGA), secondary amines such as diethanolamine (DEA) and diisopropanolamine (DIPA), or tertiary amines such as triethanolamine (TEA) and methyldiethanolamine (MDEA), but ammonia and liquid alkali metal carbonates such as K2CO3 and NaCO3 can also be used.

[0135] Pressure swing adsorption refers to a unit that separates heavy gases (such as CO2) from lighter gases (such as H2) by adsorption. In this type of equipment, a dynamic equilibrium is established between adsorption and desorption of the heavy gas on the adsorbent material. Adsorption can be caused by steric, kinetic or equilibrium effects. The exact mechanism will be determined by the adsorbent used, and the equilibrium saturation will depend on the temperature and pressure. Typically, the adsorbent material is treated in the process gas until it is close to saturation and then needs to be regenerated. Regeneration can be accomplished by changing the pressure or temperature. In practice, this means using a dual reactor process, first saturating the adsorbent at high pressure or low temperature in one reactor, and then switching the reactor to desorb the heavy gas in the same reactor by reducing the pressure or increasing the temperature.

[0136] Membrane refers to a separation on an at least partially solid barrier (e.g. a polymer) in which the transport of individual gas species occurs at different rates defined by their permeabilities. This allows components in the membrane retentate to be concentrated or diluted.

[0137] Cryogenic separation refers to the process of separating individual components from a gas mixture by controlling the temperature, utilizing the phase change of different substances in the gas.

[0138] Therefore, a method is provided for quickly switching the metal-catalyzed methanol cracking and reverse water gas shift reaction of a feedstock containing methanol from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or from the second steady-state reaction condition (B) to the first steady-state reaction condition (A) in a reactor system as described herein.

[0139] Achieving steady-state conditions is defined as when central process parameters (eg, feed flow rates, outlet temperatures, and reactant conversions) reach values ​​within ±15% of the average process value for the given process parameter over the subsequent hour.

[0140] Condition A or B of the present invention involves a state in which a feedstock comprising methanol and any one of water, carbon dioxide, hydrogen, nitrogen or argon is heated at a total flow rate of 500 Nm3 / h to 100000 Nm3 / h at a pressure of 5 barg to 150 barg with a balanced electric heating system catalyst to heat the product gas outlet temperature leaving the structured catalyst to a temperature of 300 to 1300° C. As the feedstock passes through the monolith, it will react toward the equilibrium of the reaction.

[0141] In one embodiment of the present invention, when using selective methanol and shift catalyst, the process comprises initial reaction conditions A, wherein the feedstock consists of 33.0% CH3OH, 33% H2O, 33% CO2, 0.1% N2 and 0.9% H2, with a total flow of 384 Nm3 / h, a temperature of 200°C and a pressure of 29.2 barg. A first electrical power of 142 kW is provided to produce an almost balanced gas consisting of 0.4% CH3OH, 9.7% H2O, 52.9% H2, 33.1% CO2, 0.1% N2 and 6.5% CO, with a total flow of 632 Nm3 / h, a temperature of 300°C and a pressure of 29.1 barg. Switching to condition B in about 90 minutes, while applying a second electrical power of 382 kW, produces an almost balanced gas consisting of 0.0% CH3OH, 25.8% H2O, 34.4% H2, 14.0% CO2, 0.1% N2 and 25.8% CO, with a total flow rate of 637 Nm3 / h, a temperature of 920°C and a pressure of 29.1 barg.

[0142] In one embodiment of the present invention, when using selective methanol and shift catalysts, the process includes initial reaction conditions A, wherein the feedstock consists of 17.8% CH3OH, 28.4% H2O, 53.2% CO2, 0.2% N2 and 0.5% H2, with a total flow rate of 2074 Nm3 / h, a temperature of 260°C and a pressure of 48.8 barg. A first electrical power of 1538 kW is provided to produce an almost balanced gas consisting of 0.0% CH3OH, 30.6% H2O, 17.0% H2, 30.0% CO2, 0.12% N2 and 22.7% CO, with a total flow rate of 2810 Nm3 / h, a temperature of 920°C and a pressure of 48.7 barg. In about 25 minutes, the process is switched to condition B, while applying a second electrical power of 2902 kW and increasing the total feed flow rate to 3792 Nm 3 / h, producing an almost balanced gas composed of 0.0% CH3OH, 31.0% H2O, 16.5% H2, 29.2% CO2, 0.1% N2 and 23.2% CO, with a total flow of 5137Nm3 / h, a temperature of 950°C and a pressure of 48.7barg.

[0143] In one embodiment of the present invention, when using non-selective methanol and shift catalysts, and catalytic methanation reaction, the method includes initial reaction conditions A, wherein the feedstock consists of 32.9% CH3OH, 32.9% H2O, 32.9% CO2, 0.3% N2 and 1.0% H2, with a total flow rate of 1043 Nm3 / h, a temperature of 260°C, and a pressure of 34.1 barg. A first electrical power of 28.2 kW is provided to produce an almost balanced gas consisting of 0.0% CH3OH, 37.6% H2O, 8.7% H2, 33.2% CO2, 0.3% N2, 2.9% CO and 17.4% CH4, with a total flow rate of 1284 Nm3 / h. 3 / h, temperature of 590 ° C, pressure of 34.0 barg. In about 70 minutes, it switches to condition B, while applying a second electric power of 1063 kW, producing an almost balanced gas composed of 0.0% CH3OH, 27.4% H2O, 32.5% H2, 13.0% CO2, 0.2% N2, 26.6% CO and 0.4% CH4, with a total flow of 1718 Nm3 / h, a temperature of 1010 ° C, and a pressure of 34.0 barg.

[0144] The term "vice versa" is used to indicate that the method is equally applicable when switching from the first reaction condition (A) to the second reaction condition (B) as when switching from the second reaction condition (B) to the first reaction condition (A). It is worth noting that the switch from condition A to condition B is considered complete when the process value of the system reaches within 85% of the steady-state condition.

[0145] The reactor system is as described above; that is, it comprises a pressure shell containing a structured catalyst arranged to catalyze a reaction of a feedstock comprising methanol, the structured catalyst comprising a macrostructure of an electrically conductive material, the macrostructure supporting a ceramic coating, wherein the ceramic coating supports a catalytically active material, and wherein the reactor system is provided with a thermal insulation layer between the structured catalyst and the pressure shell. All details described above with respect to the reactor system are relevant to the present technology.

[0146] The method of this aspect of the invention comprises the following steps:

[0147] In the first steady-state reaction condition (A):

[0148] - supplying the feedstock to the reactor system at a first total flow rate, and

[0149] - providing a first electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, thereby allowing a first current to flow through the conductive material,

[0150] thereby heating at least a portion of the structured catalyst to a first temperature at which the feedstock is converted over the structured catalyst under the first steady-state reaction condition (A) to a first product gas mixture; and causing the first product gas to be discharged from the reactor system;

[0151] And, in the second steady-state reaction condition (B):

[0152] - supplying the feedstock to the reactor system at a second total flow rate,

[0153] - providing a second electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, thereby allowing a second current to flow through the conductive material,

[0154] thereby heating at least a portion of the structured catalyst to a second temperature; converting the feedstock at the second temperature over the structured catalyst under the second steady-state reaction condition (B) to a second product gas mixture; and exhausting the second product gas from the reactor system;

[0155] To achieve the first and second steady-state reaction conditions (A) and (B), the second electrical power is higher than the first electrical power; and / or the second total flow rate is higher than the first total flow rate.

[0156] It is noteworthy that an increase in the total flow rate will increase the input of cold feedstock, thereby cooling the structured catalyst and reducing reactivity, thereby achieving the second steady-state reaction condition (B). Significant changes in flow rate will change the energy required for the process.

[0157] Changes in total flow may include changes in total flow without compositional changes or changes in composition, such as increasing recycle flow or changing a portion of the feedstock.

[0158] In one embodiment, the ratio (A:B) of the total gas feed flow rate in the first reaction condition A and the second reaction condition B is at least 1:10. Therefore, switching between conditions A and B allows a significant increase / reduction in the output of product gas. When the present invention is used for energy storage, for example, this is advantageous, wherein excess electrical energy from an energy grid is available, and in this way can be stored as chemical energy, and vice versa, to increase the availability of electrical energy in the grid when electrical energy is needed elsewhere. In addition, this embodiment allows the use of the present invention to supply a large amount of product gas during the period when the downstream process needs it, and in other cases the present invention is operated under standby conditions. If there is no continuous demand for product gas, this is advantageous.

[0159] In another embodiment, the product gas outlet temperature from the structured catalyst in reaction conditions B is 50°C to 800°C higher than the product gas outlet temperature from the structured catalyst in reaction conditions A, for example 100°C to 500°C higher, preferably 150°C to 400°C higher. This allows for rapid startup of the reactor system from a cold state to operating conditions. This is advantageous in the case of system startup, where the startup procedure comprises the following steps:

[0160] Heating process equipment in non-condensing gases to a temperature above the condensation point of the facility under steady-state conditions at full load,

[0161] Pressurize the raw materials,

[0162] · feeding the raw material components into the reactor system while applying a first electrical power,

[0163] • Switching to a higher operating temperature by applying a second electrical power.

[0164] In this way, all steps of the startup procedure are relatively quick.

[0165] The product gas outlet temperature from the structured catalyst in reaction condition B is typically no more than 50°C higher than the product gas outlet temperature from the structured catalyst in reaction condition A. This allows for rapid changes between conditions A and B without significantly changing the composition of the product gas from the system. In this way, product gas requirements for downstream processes of the reactor system can be easily supplied in different amounts without significantly disturbing the chemical environment of these.

[0166] In one embodiment, the switching between reaction conditions A and B comprises a gradual change in the total gas feed flow rate from the first total flow rate to the second total flow rate, and a simultaneous gradual change in the potential applied to the conductive material from the first electrical power to the second electrical power. In this way, the product gas composition can also remain almost constant during the transition phase. In one embodiment, the gradual change is performed in such a way that the flow rate is increased in small steps while the electrical power is increased to maintain an almost constant product gas outlet temperature from the structured catalyst.

[0167] In one embodiment, the reactor system also includes a control system, which is arranged to control the power supply to ensure that the temperature of the gas leaving the pressure shell is within a predetermined range and / or to ensure that the conversion rate of the raw material is within a predetermined range. The control of the power supply is the control of the electrical output from the power supply. The control of the power supply can be performed, for example, as a control of the voltage and / or current from the power supply, as a control of whether the power supply is turned on or off, or as a combination thereof. The power provided to the structured catalyst can be in the form of alternating current or direct current.

[0168] According to one embodiment, a proportional-integral-derivative (PID) controller controls the potential based on feedback readings from a process value of the product gas outlet temperature of the structured catalyst.

[0169] The methods described herein allow for rapid switching between conditions A and B. Thus, suitably, switching between reaction conditions A and B occurs within a time period of less than 3 hours, such as less than 2 hours, such as less than 60 min, preferably less than 30 min, even more preferably less than 15 min.

[0170] In one embodiment, switching between reaction conditions A and B comprises supplying a second electrical power to the structured catalyst. This suitably occurs whilst maintaining the total flow rate substantially constant.

[0171] In one aspect, the switching between reaction conditions A and B comprises a transition state between said reaction conditions A and B; said transition state comprises a first period of time, in which the power is cut off; followed by a second period of time, in which the structured catalyst is supplied with said second electrical power of condition B. This allows a more rapid establishment of a stable state.

[0172] In one aspect, the transition between reaction conditions A and B comprises a transition state between the reaction conditions A and B; the transition state comprises a first period of time in which the third electrical power is supplied to the structured catalyst; followed by a second period of time in which the second electrical power of condition B is supplied to the structured catalyst, the third electrical power being higher than the second electrical power. This allows a more rapid establishment of a stable state.

[0173] The method may include subjecting the hydrogen-containing product gas to other steps such as purification, pressurization, heating, cooling, etc. to provide a final product gas for use downstream of the reactor system of the present invention.

[0174] Furthermore, it should be noted that the order in which the method steps are written is not necessarily the order in which the method steps occur, as two or more steps may occur simultaneously or in a different order than that shown above.

[0175] In one embodiment, the method includes the step of pressurizing the raw material upstream of the pressure shell to a pressure of up to at least 2 bar. The selected operating pressure is determined by the integration of the endothermic reaction and the reactor in the surrounding process steps. In a preferred embodiment, the raw material is pressurized by using a pump for the liquid components of the raw material, such as methanol and water, and a compressor for the gaseous components, such as carbon dioxide. A mixer and / or preheater can be included downstream of the pressurizing device to provide the required reaction mixture and inlet temperature of the reactor system.

[0176] In one embodiment of the process according to the invention, the temperature of the feed entering the reactor system is from 100° C. to 400° C. However, in a preferred embodiment, the temperature and pressure of the feed are adjusted to ensure that the feed is above the dew point.

[0177] In one embodiment of the process of the invention, the structured catalyst is heated so that the maximum temperature of the structured catalyst is between 500°C and 1300°C. The temperature used will depend on the endothermic reaction. The maximum temperature of the structured catalyst depends on the material of the conductive material; thus, if the conductive material is a FeCr alloy, which melts at a temperature between 1380°C and 1490°C (depending on the actual alloy), if the melting point of the conductive material is about 1400°C, then the maximum temperature should be slightly below the melting point, for example about 1300°C, because the material will become soft and ductile when approaching the melting point. The maximum temperature may be further limited by the durability of the catalyst material, the coating and the catalytically active material.

[0178] In one embodiment, the method according to the invention further comprises the step of introducing a cooling gas through the pressure vessel via the inlet to allow the cooling gas to flow through the at least one conductor and / or the sleeve. The cooling gas may advantageously be hydrogen, nitrogen, methanol or any other gas suitable for cooling the area or zone around the at least one conductor. A portion of the feedstock may be fed into the pressure vessel as cooling gas.

[0179] In one embodiment according to the invention, the method further comprises the step of introducing a cooling gas through the pressure hull via the inlet to allow the cooling gas to flow through at least one conductor and / or the sleeve. The cooling gas may be any suitable gas; examples of such gases are hydrogen, nitrogen, methanol, methane or mixtures thereof. The cooling gas may flow through the conductor(s) and cool it(them) from the inside; in this case, the conductor(s) need to be hollow to accommodate the cooling gas flowing therein.

[0180] The catalyst material used for the reaction can be CuZnO / Al2O3, Fe / Al2O4NiGa / MgAl2O4, Mn / ZrO2, CuZn / ZrO2, CoSn / Al2O3, Ni / Al2O3, Ni / ZrO2, Ni / MgAl2O3, Ni / CaAl2O3, Ru / MgAl2O3 or Rh / MgAl2O3. The catalytically active material can be Cu, Zn, ZnO, Fe, Mn, Ga, Ni, Ru, Rh, Ir or a combination thereof, while the ceramic coating can be Al2O3, ZrO2, MgAl2O3, CaAl2O3 or a combination thereof and may be mixed with oxides of Y, Ti, La or Ce. The maximum temperature of the reactor can be between 500-1300°C. The pressure of the feedstock can be between 2-180 bar, preferably about 25 bar. In one embodiment, the macrostructure is made of an alloy of FeCrAl, supporting a ceramic coating of a mixture of ZrO2 and Al2O3, and CuZn as a catalytically active material. In another embodiment, the macrostructure is made of an FeCrAl alloy, supporting a ceramic coating of a mixture of ZrO2 and MgAl2O4, and Ni as a catalytically active material. In another embodiment, the macrostructure is made of an FeCrAl alloy, supporting a ceramic coating of ZrO2, and Mn as a catalytically active material.

[0181] In one embodiment, the reactor can be configured to have catalytic activity for methanol cracking in the low temperature region (inlet portion) of the reactor, while using a more heat-resistant catalyst system in the high temperature portion of the reactor that is more active for the reverse water gas shift catalyst. In a preferred embodiment, the reactor has a second catalyst material of CuZnO / Al2O3, wherein the macrostructure is a second catalyst material made of Fe CrAl alloy, supporting a ZrO2 ceramic coating, Mn as a catalytically active material, and a third catalyst material is CuZnO / Al2O3. In another embodiment, the reactor has a second catalyst material of CuZnO / Al2O3, wherein the macrostructure is a second catalyst material made of Fe Cr Al alloy, supporting a ZrO2 ceramic coating, Mn as a catalytically active material, the third catalyst material is CuZnO / Al2O3, located in the most upstream portion of the macro support channel, and the fourth catalyst system is Ni / CaAl2O4.

[0182] Detailed description with drawings

[0183] The same reference numerals refer to the same elements throughout the drawings.

[0184] Figure 1aA cross section through one embodiment of a reactor system 100 according to the present invention is shown. The reactor system 100 includes a structured catalyst 10, which is arranged as an array of macrostructures 5. Each macrostructure 5 in the array is coated with a ceramic coating impregnated with a catalytically active material. Moreover, the reactor system 100 includes conductors 40, 40' connected to a power source (not shown in the figure) and the structured catalyst 10 (i.e., the array of macrostructures). The conductors 40, 40' are guided through the wall of the pressure vessel 20 containing the structured catalyst via a sleeve 50 and through the insulating material 30 on the inside of the pressure vessel. The conductor 40' is connected to the array of macrostructures 5 by a conductor contact rail 41.

[0185] In one embodiment, the power supply supplies a voltage of 26 V and a current of 1200 A. In another embodiment, the power supply supplies a voltage of 5 V and a current of 240 A. The current is conducted through the electrical conductors 40, 40' to the conductor contact rails 41, and the current flows from a conductor contact rail 41, for example from Figure 1a The conductor rail, seen on the left in the middle, flows through the structured catalyst 10 to another conductor rail 41, for example Figure 1a The conductor rail is seen on the right in the figure. The current can be either alternating current, i.e. running in both directions alternately, or direct current and running in either direction.

[0186] The macrostructure 5 is made of an electrically conductive material. Particularly preferred is kanthal, an alloy consisting of aluminum, iron and chromium. A ceramic coating, such as an oxide, applied to the structure catalyst 5 is impregnated with a catalytically active material. The conductors 40, 40' are made of materials such as iron, aluminum, nickel, copper or alloys thereof.

[0187] During operation, a feedstock comprising methanol enters the reactor system 100 from above as indicated by arrow 11. A product gas comprising synthesis gas leaves the reactor system from its bottom as indicated by arrow 12.

[0188] Figure 1b Shows Figure 1a The reactor system 100, wherein a portion of the pressure vessel 20 and the thermal insulation layer 30 are removed, Figure 2 is an enlarged view of a portion of the reactor system 100. Figure 1b and 2 The connection ratio between the conductor 40' and the conductor contact rail 41 is Figure 1a It is shown more clearly. Furthermore, it can be seen that the conductor 40 is guided through the wall of the pressure hull in the sleeve 50 and that one conductor 40 is divided into three conductors 40' inside the pressure hull. It should be noted that the number of conductors 40' can be any suitable number, for example less than three or even more than three.

[0189] exist Figure 1a , 1b 2, the conductors 40, 40' are guided through the wall of the pressure vessel 20 containing the structured catalyst and through the insulating material 30 on the inner side of the pressure vessel via the sleeve 50. The raw materials for methanol cracking and reverse water gas shift reaction enter the reactor system 100 via the inlet on the upper side of the reactor system 100 as shown by arrow 11, and the converted product gas leaves the reactor system 100 via the outlet at the bottom of the reactor system 100 as shown by arrow 12. In addition, one or more additional inlets ( Figures 1a to 2 The cooling gas may be hydrogen, nitrogen, methane or a mixture thereof. The temperature of the cooling gas when entering the pressure vessel may be, for example, about 100° C.

[0190] exist Figures 1a to 2 In the reactor system 100 shown, the inert material ( Figure 1a-2 The inert material (not shown) is advantageously present between the lower side of the structured catalyst 10 and the bottom of the pressure-resistant shell. Moreover, the inert material is advantageously present between the outer side of the structured catalyst 10 of the macrostructure 5 and the insulating material 30. Therefore, one side of the insulating material 30 faces the inner side of the pressure-resistant shell 20, while the other side of the insulating material 30 faces the inert material. The inert material is, for example, a ceramic material and can be in the form of a granular material. The inert material helps to control the pressure drop across the reactor system 100 and control the flow of the gas through the reactor system 100 so that the gas flows on the surface of the structured catalyst 10.

[0191] Figure 3a and 3b A schematic cross-section of one embodiment of a reactor system 100', 100" of the present invention including a structured catalyst 10' is shown. The structured catalyst 10' may be composed of a single macrostructure having a ceramic coating supporting a catalytically active material, or it may include two or more macrostructures. Each of the reactor systems 100', 100" includes a pressure shell 20 and a thermal insulation layer 80 between the structured catalyst 10' and the pressure shell 20. An inert material 90 may be used to fill the gap between the structured catalyst 10' and the thermal insulation layer or the pressure shell 20. Figure 3a and 3b In the figure, inert material 90 is represented by the dashed area; inert material 90 can be in any suitable form, such as in the form of inert granules, and it is, for example, a ceramic material. Inert material 90 helps control the pressure drop through the reactor system and control the gas flow through the reactor system. Moreover, the inert material generally has a thermal insulation effect.

[0192] from Figure 3a and 3b As can be seen, the reactor system 100', 100" also includes inner tubes 15 in heat exchange relationship with the structured catalyst 10'. The inner tubes 15 are adapted to draw product gas from the structured catalyst 10' such that the product gas flowing through the one or more inner tubes is in heat exchange relationship with the gas flowing over the structured catalyst; however, the inner tubes 15 are electrically insulated from the structured catalyst 10' by thermal insulation layers 80, inert materials 90, gaps, or a combination. This is an arrangement that is denoted as a bayonet reactor system. In this arrangement, the product gas within the inner tubes assists in heating the process gas flowing over the macrostructure. Figure 3a and 3b In the illustrated arrangement, feedstock enters the reactor system 100', 100" as indicated by arrow 11 and continues into the structured catalyst 10' as indicated by arrow 13. As the feedstock passes over the structured catalyst 10', it undergoes methanol cracking and reverse water gas shift reactions. The gas leaving the structured catalyst 10' is at least partially converted to synthesis gas. The at least partially converted gas flows from the structured catalyst 10' into the inner tube 15 as indicated by arrow 14 and leaves the inner tube as indicated by arrow 12. Even though there is a thermal insulation layer 80 between the inner tube 15 and the structured catalyst 10', some heat transfer will occur from the gas within the inner tube 15 and the gas within or upstream of the structured catalyst 10'. Figure 3a and 3b In the embodiment shown, the feedstock flows downward through the structured catalyst 10 ′ and upward through the inner tube 15 ; however, it is contemplated that the configuration could be reversed so that the feedstock flows upward through the structured catalyst 10 ′ and downward through the inner tube 15 .

[0193] Figure 4 and 5 One embodiment of a structured catalyst comprising an array of macrostructures is shown viewed from above and from the side, respectively. Figure 4 A structured catalyst 10 comprising an array of macrostructures 5 is shown as seen from above, i.e. as seen from Figure 1a and 1b As seen by arrow 11 in FIG. 1 . The array has 6 rows (i.e. Figure 1a , 1b , 1c, 1d, 1e and 1f). The macrostructures 5 in each row are connected to the adjacent macrostructures (one or more) 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 means of connecting pieces 3.

[0194] Figure 5 Shown from the side Figure 4A structured catalyst 10 having an array of macrostructures 5. Figure 5 It can be seen that each macrostructure 5 is perpendicular to Figure 4 The cross section shown extends longitudinally. Each macrostructure 5 has a slit 60 cut into it along its longitudinal direction (see Figure 5 ). Thus, when powered by a power source, current enters the array of macrostructures 5 via the conductor contact rail 41, is directed downward through the first macrostructure 5 to the lower limit of the slit 60, and is then directed upward toward the connector 3. Current is directed downward and upward through each macrostructure 5 in each row 1a-1f of macrostructures 5 in the array 10 via a corresponding zigzag path. This configuration advantageously increases the electrical resistance on the structured catalyst 10.

[0195] Figure 6 The structured catalyst 10 according to the present invention is shown in a perspective view. The structured catalyst 10 comprises a macrostructure coated with a ceramic coating impregnated with a catalytically active material. Within the structured catalyst are channels 70 extending in the longitudinal direction of the macrostructure 5 (by Figure 6 The passage is defined by a wall 75. Figure 6 In the embodiment shown, the walls 75 define a plurality of parallel square channels 70 when viewed in the direction of flow indicated by arrow 12. When viewed from above, the structured catalyst 10 has a substantially square perimeter defined by side lengths e1 and e2. However, the perimeter may also be circular or other shapes.

[0196] The walls 75 of the structured catalyst 10 are made of an extruded or 3D printed material coated with a ceramic coating, such as an oxide, which has been applied to 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 are present on each wall within the structured catalyst 10 over which the gas flow flows during operation and interacts with the heated surface and catalytically active material of the structured catalyst.

[0197] Thus, during use in the reactor system to perform methanol cracking and reverse water gas shift reactions, the feedstock flows through the channels 70 and interacts with the heated surface of the structured catalyst and the catalytically active material supported by the ceramic coating.

[0198] exist Figure 6In the structured catalyst 10 shown, a slit 60 has been cut into the structured catalyst 10. In this case, the slit 60 forces the current to take a zigzag route downwards and then upwards within the macrostructure, thereby increasing the current path and therefore increasing the resistance and therefore the heat dissipated within the macrostructure. The slits 60 within the macrostructure may be provided with an embedded insulating material to ensure that no current flows in the lateral direction of the slits 60.

[0199] The channels 70 in the structured catalyst 10 are open at both ends. When the structured catalyst is used in a reactor system, the feedstock is moved along the Figure 1a and 1b The flow of the liquid through the unit is in the direction indicated by the arrows 11 and 12 and is heated by contact with the wall 75 of the channel 70 and by heat radiation. The heat induces the desired methanol cracking and reverse water gas shift reactions. The wall 75 of the channel 70 may have a thickness of, for example, 0.5 mm, and the ceramic coating applied to the wall 75 may have a thickness of, for example, 0.1 mm. Although the arrows 11 and 12 (see Figure 1a and 1b ) shows that the flow of the raw material is downward, but the opposite flow direction, i.e., upward, is also conceivable.

[0200] Figure 7 The perspective view shows the connector 7 attached. Figure 1a and 1b The structured catalyst 10 is provided with a plurality of connectors 7. The connectors 7 each connect a portion of the structured catalyst 10 to the conductors 40. The conductors 40 are all connected to a power source (not shown). Each connector 7 is connected to the upper portion of the structured catalyst. When the conductors 40 are connected to the power source, the current is guided to the corresponding connector 7 via the conductors and flows through the structured catalyst 10. The slits 60 block the current from flowing in the lateral direction ( Figure 7 Therefore, the current flows in the partially structured catalyst along the slits 60 in a manner as follows: Figure 7 Run in the downward direction as shown, then Figure 7 It is shown running transversely from below the slit 60 to the longitudinal direction and finally the current runs upward in the longitudinal direction of the structured catalyst to another connector 7 . Figure 7 The connector 7 in the structured catalyst is mechanically fastened to the structured catalyst by means of mechanical fastening means such as screws and bolts. However, additional or alternative fastening means are conceivable. In one embodiment, the power supply generates a voltage of 3 V and a current of 400 A. The connector 7 is made of a material such as iron, aluminum, nickel, copper or an alloy thereof, for example.

[0201] As described above, the structured catalyst 10 is coated with a ceramic coating, such as an oxide, that supports a catalytically active material. However, the portion of the structured catalyst 10 that is connected to the connector 7 should not be coated with an oxide. Instead, the macrostructure of the structured catalyst should be exposed to or directly connected to the connector 7 in order to obtain a good electrical connection between the macrostructure and the connector.

[0202] When the connector 7 and thus the conductor 40 are connected to the same end of the structured catalyst 10, i.e. to the Figure 7 At the upper end shown, feedstock entering a reactor system containing structured catalyst 10 will be able to cool connector 7 and conductor 40. For example, feedstock entering such a reactor system may have a temperature of 200°C or 400°C, thus preventing connector 7 and conductor 40 from reaching temperatures much above that temperature.

[0203] Figure 8 Another embodiment of a structured catalyst 10'' with a connector 7'' is shown. The structured catalyst 10'' is, for example, Figure 6 Each connector 7'' has three holes on its upper side for connecting conductors (not shown). A piece of electrically insulating material 61 is located in the slit 60 (see Figure 6 )Inside.

[0204] Fig. 9 The thermodynamic equilibrium of the methanol cracking reaction and the reverse water gas shift reaction is shown as a function of temperature when a mixture of 33.3% CH3OH, 33.3H2O and 33.3CO2 is used as feedstock at a pressure of 29 barg when using a selective cracking and shift catalyst. The figure illustrates that the selectivity to CO increases by increasing the outlet temperature of the reactor system. When operating at an outlet temperature of 500°C, a gas with a H2 / CO ratio of 3.0 is produced, which decreases to 1.2 by increasing the temperature to 1000°C. Shifting the reverse water gas shift reaction toward the CO side using a higher operating temperature enables the selective production of a CO-rich syngas.

[0205] Fig.10The thermodynamic equilibrium of methanol cracking, methanation and reverse water gas shift reactions is shown as a function of temperature when a mixture of 33.3% CH3OH, 33.3H2O and 33.3CO2 is used as feedstock at 29 barg pressure when using non-selective cracking and shift catalysts. The figure illustrates that by increasing the outlet temperature of the reactor system, the selectivity for CO increases and the by-product of CH4 decreases. When operating at an outlet temperature of 500°C, a gas with a H2 / CO ratio of 5.6 is produced, which is reduced to 1.2 by increasing the temperature to 1000°C. In addition, the methane concentration decreases from 19.5% at 500°C to 0.3% at 1000°C. Shifting the reverse water gas shift reaction towards the CO side using higher operating temperatures enables the selective production of CO-rich syngas.

[0206] Fig.11 An embodiment of the method is shown, in which a raw material is provided by mixing CH3OH and H2O and pressurizing them by a pump 130 and then evaporating them in a preheater 140 to prepare a gas-phase raw material. At the same time, a CO2 raw material is compressed in a compressor 120 and sent to a reactor system 100 together with the CH3OH and H2O raw materials. In the reactor system 100, the temperature is increased while promoting at least methane cracking and reverse water gas shift reactions to provide hot synthesis gas as a first product gas.

[0207] Fig.12 Shows something like Fig.11 The present invention relates to an embodiment of the process of claim 1, but without feeding CO2 to the reactor system. Instead, the CO2 feedstock is compressed in compressor 120 and heated in parallel heater 121 and sent to adiabatic post-converter 150. The heated CO2 is mixed with the first product gas from the reactor system 100 before or in the adiabatic post-converter. This produces a second product gas that is richer in CO than the first product gas.

[0208] Fig.13 Shows something like Fig.11 An embodiment of the method includes an upgrading unit, which includes a flash separation unit 152 and a CO2 removal unit 151. The first product gas from the reactor system 100 is cooled in the heat exchange unit 141 to below the dew point of water in the stream. Liquid water is separated in the flash separation unit 152 to produce a condensate and a dry product gas. The dry product gas is sent to the CO2 removal unit 151, where the CO2 is separated into an exhaust gas stream containing a substantially pure CO2 stream and leaving an upgraded synthesis gas stream. The exhaust gas stream of substantially pure CO2 is recycled back to the CO2 compressor 120 and used as a feedstock for the reactor system 100.

[0209] Fig.14 Shows something like Fig.11 The embodiment of the method of the present invention comprises an upgrading unit, which includes a flash separation unit 152 and a membrane 153. The first product gas from the reactor system 100 is cooled in the heat exchange unit 141 to below the dew point of the water in the stream. The liquid water is separated in the flash separation unit 152 to produce a condensate and a dry product gas. The dry product gas is sent to the membrane unit 153, where mainly CO2 and H2 permeate through the membrane to produce an exhaust gas stream and leave a retentate of an upgraded synthesis gas stream. The exhaust gas stream is partially recycled back to the reactor system by using a dedicated compressor 155.

[0210] Fig.15 Shows something like Fig.13 The embodiment of the method includes a cold box 159 unit. The stream from the CO2 removal unit 151 is sent to the cold box unit 159, which produces a waste gas stream consisting mainly of CH4 and H2, and two upgraded synthesis gas streams, one rich in H2 and the other rich in CO.

[0211] It should be noted that even though the structured catalyst shown in the figures is shown as having channels with square cross-sections, as seen perpendicular to the z-axis, any suitable shape of the channel cross-section is conceivable. Thus, the channels of the structured catalyst may alternatively be, for example, triangular, hexagonal, octagonal or circular, with triangular, square and hexagonal shapes being preferred.

[0212] Although the present invention has been illustrated by the description of various embodiments and examples and these embodiments and examples have been described in considerable detail, it is not the intention of the applicant to limit or in any way restrict the scope of the appended claims to such details. Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the present invention in its broader aspects is not limited to the specific details, representative methods and illustrative examples shown and described. Therefore, these details may be deviated from without departing from the spirit or scope of the applicant's overall inventive concept.

[0213] Invention Project

[0214] 1. A reactor system for producing synthesis gas from a feedstock comprising methanol under methanol cracking and reverse water gas shift reaction conditions in the presence of a catalyst, the reactor system comprising:

[0215] - a source of a feedstock comprising methanol and water;

[0216] - a structured catalyst arranged to catalyze methanol cracking and reverse water gas shift reactions of said feedstock, said structured catalyst comprising macrostructures of electrically conductive material, said macrostructures supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material;

[0217] - a pressure-resistant shell containing the structured catalyst, the pressure-resistant shell comprising an inlet for admitting the feedstock and an outlet for letting out the product gas, wherein the inlet is located so that the feedstock enters the structured catalyst at a first end of the structured catalyst and the product gas leaves the structured catalyst from a second end of the structured catalyst;

[0218] - a thermal insulation layer between the structured catalyst and the pressure shell;

[0219] - at least two conductors electrically connected to the structured catalyst and to a power source disposed outside the pressure vessel, wherein the power source is sized to heat at least a portion of the structured catalyst to a temperature of at least 500° C. by passing an electric current through the macrostructure, wherein the at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct an electric current from one conductor substantially toward the second end of the structured catalyst and back to a second of the at least two conductors;

[0220] - An outlet for a first product gas comprising synthesis gas.

[0221] 2. The reactor system according to item 1, wherein the structured catalyst is arranged to catalyze methanation and steam reforming reactions.

[0222] 3. The reactor system according to item 1 or 2, wherein the power supply is sized to heat at least a portion of the structured catalyst to a temperature of at least 500°C, preferably at least 700°C.

[0223] 4. A reactor system according to any of the preceding items, wherein the feedstock additionally comprises CO2.

[0224] 5. A reactor system according to any of the preceding items, wherein the feedstock additionally comprises H2, N2, CH4 and / or Ar.

[0225] 6. The reactor system according to any of the preceding items, wherein the design pressure of the pressure vessel is 2 to 30 bar.

[0226] 7. The reactor system according to any one of items 1 to 5, wherein the design pressure of the pressure shell is 30 to 200 bar.

[0227] 8. A reactor system according to any one of the preceding items, wherein the resistivity of the conductive material is 10 -5 Ω·m to 10 -7 Ω·m.

[0228] 9. The reactor system according to any of the preceding clauses, wherein the at least two conductors are guided through the pressure vessel in a sleeve such that the at least two conductors are electrically insulated from the pressure vessel.

[0229] 10. The reactor system of item 9, wherein the pressure vessel further comprises one or more inlets proximate to or in combination with at least one sleeve to allow cooling gas to flow on, around, near or within at least one conductor within the pressure vessel.

[0230] 11. A reactor system according to any of the preceding items, wherein the reactor system further comprises an inner tube in heat exchange relationship with the structured catalyst but electrically insulated, the inner tube being adapted to draw product gas from the structured catalyst such that the product gas flowing through the inner tube is in heat exchange relationship with the gas flowing over the structured catalyst.

[0231] 12. The reactor system according to any of the preceding items, wherein the connection between the structured catalyst and the at least two conductors is a mechanical connection, a welded connection, a brazed connection or a combination thereof.

[0232] 13. A reactor system according to any of the preceding items, wherein the conductive material comprises a 3D printed or extruded and sintered macrostructure, the macrostructure supporting a ceramic coating, wherein the ceramic coating supports a catalytically active material.

[0233] 14. The reactor system according to any of the preceding clauses, wherein the structured catalyst comprises an array of macrostructures electrically connected to each other.

[0234] 15. The reactor system according to any of the preceding clauses, wherein the structured catalyst has an electrically insulating component arranged to increase the length of the main current path between the at least two conductors to a length greater than the largest dimension of the structured catalyst.

[0235] 16. A reactor system according to any of the preceding claims, wherein the structured catalyst has at least one electrically insulating component, the at least one electrically insulating component being arranged to direct current through the structured catalyst so as to ensure that for at least 70% of the length of the structured catalyst, the current density vector of the main current path has a non-zero component value parallel to the length of the structured catalyst.

[0236] 17. The reactor system according to any of the preceding items, wherein the macrostructure has a plurality of parallel channels, a plurality of non-parallel channels and / or a plurality of labyrinthine channels.

[0237] 18. The reactor system according to any of the preceding clauses, wherein the reactor system further comprises a bed of a second catalyst material upstream of the structured catalyst within the pressure shell.

[0238] 19. A reactor system according to any of the preceding items, wherein the reactor system further comprises a third catalyst material loaded into the channels of the macrostructure, the third catalyst material being in the form of catalyst pellets, extrudates or granules.

[0239] 20. The reactor system according to any of the preceding clauses, wherein the reactor system further comprises a fourth catalyst material bed within the pressure shell downstream of the structured catalyst.

[0240] 21. A reactor system according to any of the preceding clauses, wherein the material of the macrostructure is selected to be arranged to generate 500 to 50,000 W / m 2 The heat flux of the material.

[0241] 22. A reactor system according to any of the preceding items, wherein the structured 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 wherein the first portion is located upstream of the second portion.

[0242] 23. A reactor system according to any of the preceding items, wherein the structured catalyst comprises 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 wherein the third portion is downstream of the first portion and / or the second portion.

[0243] 24. A reactor system according to any one of the preceding items, wherein the reactor system further comprises a control system, which is arranged to control the power supply to ensure that the temperature of the gas leaving the pressure vessel is within a predetermined range and / or to ensure that the conversion rate of the feedstock is within a predetermined range.

[0244] 25. The reactor system according to any of the preceding items, wherein the structured catalyst within the reactor system has a ratio of the area equivalent diameter of a horizontal cross-section through the structured catalyst to the height of the structured catalyst in the range of 0.1 to 2.0.

[0245] 26. The reactor system according to any of the preceding items, wherein the height of the reactor system is from 0.5 to 7 m, more preferably from 0.5 to 3 m.

[0246] 27. A reactor system according to any of the preceding clauses, wherein the length of gas passing through the structured catalyst is less than the length of electric current passing through the structured catalyst from one electrode to the next electrode.

[0247] 28. A reactor system according to any of the preceding clauses, wherein the catalytically active material comprises different segments, each segment comprising catalytically active material reactive towards a different chemical reaction.

[0248] 29. A reactor system according to any preceding clause, arranged such that the outlet temperature of the product stream from the reactor system is between 500-1300°C, such as between 800-1100°C, or between 850-1050°C.

[0249] 30. A method for subjecting a feedstock comprising methanol and water to methanol cracking and reverse water gas shift reaction in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions to produce synthesis gas in a reactor system, the reactor system comprising a pressure shell containing a structured catalyst, the structured catalyst being arranged to catalyze the methanol cracking and reverse water gas shift reactions of the feedstock, the structured catalyst comprising macrostructures of conductive material, the macrostructures supporting a ceramic coating, wherein the ceramic coating supports a catalytically active material; wherein the reactor system is provided with a thermal insulation layer between the structured catalyst and the pressure shell; the method comprising the following steps:

[0250] - pressurizing the raw material,

[0251] - supplying the pressurized feedstock to the pressure shell through an inlet, wherein the inlet is located so that the feedstock enters the structured catalyst at a first end of the structured catalyst; allowing the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst and exhausting product gas from the pressure shell, wherein the product gas leaves the structured catalyst from a second end of the structured catalyst;

[0252] - providing electrical power via an electrical conductor connected from a power source positioned outside the pressure vessel to the structured catalyst, allowing electrical current to flow through the macrostructure, thereby heating at least a portion of the structured catalyst to a temperature of at least 500° C., wherein the at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct electrical current from one conductor substantially toward the second end of the structured catalyst and back to a second of the at least two conductors, thereby heating at least a portion of the structured catalyst to a temperature sufficient to cause the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst, thereby heating at least a portion of the structured catalyst to a temperature sufficient to cause the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst,

[0253] - Discharging a first product gas comprising synthesis gas from the reactor system.

[0254] 31. The method according to item 30, wherein the structured catalyst is arranged to catalyze the methanation / steam reforming reaction.

[0255] 32. The method according to any one of items 30 to 31, wherein the feedstock is pressurized to a pressure of 2 to 30 bar.

[0256] 33. The method according to any one of items 30 to 31, wherein the feedstock is pressurized to a pressure of 30 to 200 bar.

[0257] 34. A method according to any one of items 30 to 33, wherein the feedstock additionally comprises CO2.

[0258] 35. A method according to any one of items 30 to 34, wherein the feedstock additionally comprises H2, N2, CH4 and / or Ar.

[0259] 36. The process according to any one of items 30 to 35, wherein at least a portion of the structured catalyst is heated to a temperature of at least 500°C, preferably at least 700°C.

[0260] 37. The method according to any one of items 30 to 36, further comprising the step of introducing a cooling gas through the pressure hull via an inlet so as to allow the cooling gas to flow over at least one conductor.

[0261] 38. A method according to any one of items 30 to 37, wherein a first product gas containing synthesis gas from a reactor system is provided to an adiabatic post-converter, the adiabatic post-converter containing a fifth catalyst for catalyzing steam methane reforming, methanation and reverse water gas shift reactions; and in the adiabatic post-converter, at least a portion of the product gas stream and a heated CO2-rich gas stream are subjected to steam methane reforming, methanation and reverse water gas shift reactions to provide a second product gas, which is a CO-rich synthesis gas stream.

[0262] 39. The method according to item 38 further includes the step of heating the CO2-rich gas stream in a fired heater to form the heated CO2-rich gas stream.

[0263] 40. The method according to item 38, further comprising the step of heating the CO2-rich gas stream in an electrically heated heater to form the heated CO2-rich gas stream.

[0264] 41. The method according to item 38, further comprising the step of heating the CO2-rich gas stream by heat exchange with superheated steam to form the heated CO2-rich gas stream.

[0265] 42. The method according to item 38 also includes the step of heating the CO2-rich gas stream by heat exchange with at least part of the product gas stream leaving the adiabatic post-converter to form the heated CO2-rich gas stream.

[0266] 43. The method according to any one of items 30 to 42, wherein the method further comprises the step of feeding the first product gas or the second product gas comprising synthesis gas to an upgrading unit and separating it into an upgraded synthesis gas stream and one or more waste gas streams.

[0267] 44. A method according to any one of items 30 to 43, wherein the H2 / CO ratio of the first product gas or the second product gas is lower than 3, such as lower than 2, or such as lower than 1.

[0268] 45. The method according to any one of items 30 to 44, wherein the method further comprises the step of recycling one or more waste gas streams to an upstream unit of the upgrading unit.

[0269] 46. ​​A method for rapidly switching metal-catalyzed methanol cracking and reverse water gas shift reaction of a feedstock containing methanol from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or from a second steady-state reaction condition (B) to a first steady-state reaction condition (A) in a reactor system according to any one of claims 1 to 29; the method comprising the following steps:

[0270] In the first steady-state reaction condition (A):

[0271] - supplying the feedstock to the reactor system at a first total flow rate, and

[0272] - providing a first electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, thereby allowing a first current to flow through the conductive material,

[0273] thereby heating at least a portion of the structured catalyst to a first temperature at which the feedstock is converted over the structured catalyst under the first steady-state reaction condition (A) to a first product gas mixture; and causing the first product gas to be discharged from the reactor system;

[0274] And, in the second steady-state reaction condition (B):

[0275] - supplying the feedstock to the reactor system at a second total flow rate,

[0276] - providing a second electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, thereby allowing a second current to flow through the conductive material,

[0277] thereby heating at least a portion of the structured catalyst to a second temperature; converting the feedstock at the second temperature over the structured catalyst under the second steady-state reaction condition (B) to a second product gas mixture; and exhausting the second product gas from the reactor system;

[0278] The second electric power is higher than the first electric power; and / or the second total flow is higher than the first total flow.

[0279] 47. A method according to item 46, wherein 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 to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct current from one conductor to flow substantially toward the second end of the structured catalyst and back to the second of the at least two conductors.

[0280] 48. The method according to any one of items 46 to 47, wherein the ratio of the total gas feed flow in the first reaction condition A to the second reaction condition B (A:B) is at least 1:10.

[0281] 49. A process according to any one of items 46 to 48, wherein the product gas outlet temperature from the structured catalyst in reaction conditions B is 50°C to 600°C higher than the product gas outlet temperature from the structured catalyst in reaction conditions A, for example 100°C to 500°C higher, preferably 150°C to 400°C higher.

[0282] 50. A method according to any one of items 46 to 49, wherein the switching between reaction conditions A and B includes gradually changing the total gas feed flow rate from the first total flow rate to the second total flow rate and simultaneously gradually changing the potential applied to the conductive material from the first electric power to the second electric power.

[0283] 51. The process according to any one of items 46 to 50, wherein the product gas outlet temperature from the structured catalyst in reaction conditions B is no more than 50°C higher than the product gas outlet temperature from the structured catalyst in reaction conditions A.

[0284] 52. The method according to any one of items 46 to 51, wherein a proportional-integral-derivative (PID) controller controls the potential based on feedback readings from a process value of the product gas outlet temperature of the structured catalyst.

[0285] 53. The process according to any one of items 46 to 52, wherein the product gas outlet temperature leaving the structured catalyst is measured directly below or on the most downstream surface of the structured catalyst.

[0286] 54. A method according to any one of items 46 to 53, wherein the switching between reaction conditions A and B occurs within a time period of less than 3 hours, such as less than 2 hours, such as less than 60 min, preferably less than 30 min, even more preferably less than 15 min.

[0287] 55. The method according to any one of items 46 to 54, wherein switching between reaction conditions A and B comprises providing a second electrical power to the structured catalyst.

[0288] 56. A method according to any one of items 46 to 55, 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 time period in which power is cut off; followed by a second time period in which the second electrical power of condition B is supplied to the structured catalyst.

[0289] 57. A method according to any one of items 46 to 56, 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 time period, wherein a third electrical power is supplied to the structured catalyst; followed by a second time period, wherein the second electrical power of condition B is supplied to the structured catalyst, and the third electrical power is higher than the second electrical power.

Claims

1. A reactor system for producing synthesis gas from a feedstock comprising methanol under methanol cracking and reverse water gas shift reaction conditions in the presence of a catalyst, the reactor system comprising: - a source of a feedstock comprising methanol and water; - a structured catalyst arranged for catalyzing said methanol cracking and reverse water gas shift reactions of said feedstock, said structured catalyst comprising macrostructures of electrically conductive material, said macrostructures supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material; - a pressure-resistant shell containing the structured catalyst, the pressure-resistant shell comprising an inlet for admitting the feedstock and an outlet for letting out the product gas, wherein the inlet is located so that the feedstock enters the structured catalyst at a first end of the structured catalyst and the product gas leaves the structured catalyst from a second end of the structured catalyst; - a thermal insulation layer between the structured catalyst and the pressure shell; - at least two conductors electrically connected to the structured catalyst and to a power source disposed outside the pressure vessel, wherein the power source is sized to heat at least a portion of the structured catalyst to a temperature of at least 500° C. by passing an electric current through the macrostructure, wherein the at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct an electric current from one conductor substantially toward the second end of the structured catalyst and back to a second of the at least two conductors; - an outlet for a first product gas comprising synthesis gas; wherein the reactor system is configured such that the temperature of the feedstock entering the reactor system is in the range of 100°C to 400°C, and the temperature of the gas leaving the reactor system is in the range of 500°C to 1300°C; and The raw material entering the structured catalyst from the first end and the methanol cracking and reverse water gas shift reactions occurring on the structured catalyst absorb heat from the structured catalyst; and there is a substantially continuously increasing temperature curve in a length direction parallel to the structured catalyst.

2. The reactor system of claim 1, wherein the structured catalyst is arranged to catalyze methanation and steam reforming reactions.

3. A reactor system according to claim 1 or 2, wherein the power supply is dimensioned to heat at least a portion of the structured catalyst to a temperature of at least 500°C, preferably at least 700°C.

4. The reactor system according to claim 1 or 2, wherein the feedstock additionally comprises CO2.

5. The reactor system according to claim 1 or 2, wherein the feedstock additionally comprises H2, N2, CH4 and / or Ar.

6. A method for subjecting a feedstock comprising methanol and water to methanol cracking and reverse water gas shift reactions in the presence of a catalyst under methanol cracking and reverse water gas shift reaction conditions to produce synthesis gas in a reactor system, the reactor system comprising a pressure resistant shell containing a structured catalyst, the structured catalyst being arranged to catalyze the methanol cracking and reverse water gas shift reactions of the feedstock, the structured catalyst comprising macrostructures of an electrically conductive material, the macrostructures supporting a ceramic coating, wherein the ceramic coating supports a catalytically active material; The reactor system is provided with a thermal insulation layer between the structured catalyst and the pressure shell; the method comprises the following steps: - pressurizing the raw material, - supplying the pressurized feedstock to the pressure shell through an inlet, wherein the inlet is located so that the feedstock enters the structured catalyst at a first end of the structured catalyst; allowing the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst and exhausting product gas from the pressure shell, wherein the product gas leaves the structured catalyst from a second end of the structured catalyst; - providing electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, allowing current to flow through the macrostructure, thereby heating at least a portion of the structured catalyst to a temperature of at least 500° C., wherein the at least two conductors are connected to the structured catalyst at a location on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct an electric current from one conductor substantially toward the second end of the structured catalyst and back to a second of the at least two conductors, thereby heating at least a portion of the structured catalyst to a temperature sufficient to cause the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst, thereby heating at least a portion of the structured catalyst to a temperature sufficient to cause the feedstock to undergo methanol cracking and reverse water gas shift reactions on the structured catalyst, - allowing a first product gas comprising synthesis gas to be discharged from the reactor system; wherein the reactor system is configured such that the temperature of the feedstock entering the reactor system is in the range of 100°C to 400°C, and the temperature of the gas leaving the reactor system is in the range of 500°C to 1300°C; and The raw material entering the structured catalyst from the first end and the methanol cracking and reverse water gas shift reactions occurring on the structured catalyst absorb heat from the structured catalyst; and there is a substantially continuously increasing temperature curve in a length direction parallel to the structured catalyst.

7. A method according to claim 6, wherein a first product gas containing synthesis gas from a reactor system is provided to an adiabatic post-converter, the adiabatic post-converter containing a fifth catalyst for catalyzing steam methane reforming, methanation and reverse water gas shift reactions; and in the adiabatic post-converter, at least a portion of the product gas stream and a heated CO2-rich gas stream are subjected to steam methane reforming, methanation and reverse water gas shift reactions to provide a second product gas, which is a CO-rich synthesis gas stream.

8. The method according to claim 6 or 7, wherein the method further comprises the step of feeding the first product gas or the second product gas comprising synthesis gas to an upgrading unit and separating it into an upgraded synthesis gas stream and one or more waste gas streams.

9. The method according to claim 8, wherein the method further comprises the step of recycling one or more waste gas streams to a unit upstream of the upgrading unit.

10. A method for rapidly switching metal-catalyzed methanol cracking and reverse water gas shift reaction of a feedstock containing methanol from a first steady-state reaction condition (A) to a second steady-state reaction condition (B) or from a second steady-state reaction condition (B) to a first steady-state reaction condition (A) in a reactor system according to any one of claims 1 to 5; the method comprising the following steps: In the first steady-state reaction condition (A): - supplying the feedstock to the reactor system at a first total flow rate, and - providing a first electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, thereby allowing a first current to flow through the conductive material, thereby heating at least a portion of the structured catalyst to a first temperature at which the feedstock is converted over the structured catalyst under the first steady-state reaction condition (A) to a first product gas mixture; and causing the first product gas to be discharged from the reactor system; And, in the second steady-state reaction condition (B): - supplying the feedstock to the reactor system at a second total flow rate, - providing a second electrical power via an electrical conductor connecting a power source placed outside the pressure vessel to the structured catalyst, thereby allowing a second current to flow through the conductive material, thereby heating at least a portion of the structured catalyst to a second temperature; converting the feedstock to a second product gas mixture over the structured catalyst at the second steady-state reaction conditions (B) at the second temperature; and exhausting the second product gas from the reactor system; The second electric power is higher than the first electric power; and / or the second total flow is higher than the first total flow.

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