EA041440B1 - ENDOTHERMIC REACTIONS WITH RESISTANCE HEATING - Google Patents

Description

Field of invention

Embodiments of the invention relate to a reactor system and process for steam reforming of a feed gas containing hydrocarbons in which heat for the endothermic reaction is provided by resistance heating.

State of the art

In endothermic reactions, there is often a problem with the efficiency of heat transfer to the reaction zone of the catalyst bed within the reactor unit. Conventional heat transfer by convective or conductive heat transfer and/or radiative heating may not be fast enough, and often, in many configurations, the application of such heat transfer methods will be associated with significant difficulties. This problem can be illustrated by the example of a tubular reformer in a steam reformer, which can practically be considered as a large heat exchanger, with heat transfer limiting the speed of the reformer. The temperature in the most central part of the pipes of the tubular reformer is somewhat lower than the temperature outside the pipes due to the rate of heat transfer through the walls of the pipe and the catalyst inside the pipes, and also because of the endothermic nature of the steam reforming reaction.

One method of supplying heat inside the catalyst rather than outside the reactor containing the catalyst is resistance heating. DE102013226126 describes an allothermic methane reforming process with physical energy recovery, in which methane is reformed using carbon dioxide to produce a synthesis gas consisting of carbon monoxide and hydrogen. The feed gases CH ₄ and CO ₂ are fed into a fixed bed reactor consisting of electrically conductive and catalytic particles, which is electrically heated to a temperature of about 1000 K. In the fixed bed reactor, the reaction gases are converted and heat is released from the generated synthesis gas.

The aim of the invention is to provide an alternative configuration of the electrically heated steam reforming reactor system.

It is also an object of the invention to provide a reactor system with a built-in heat source and catalysts.

Furthermore, it is an object of the invention to provide a method for carrying out an endothermic reaction in which the temperature of the endothermic reaction is precisely controlled to limit an undesired side reaction, such as cracking of hydrocarbons in dehydrogenation reactions.

The advantage of the invention is that the overall emission of carbon dioxide and other climate-damaging substances can be significantly reduced, in particular if the energy used in the reactor system comes from renewable energy sources.

Brief summary of the invention

Embodiments of the invention generally relate to a reactor system for carrying out an endothermic feed gas reaction, wherein the reactor system includes:

a structured catalyst for an endothermic feed gas reaction, the structured catalyst comprising a macroscopic structure of an electrically conductive material, said macroscopic structure having a ceramic coating, the ceramic coating acting as a substrate of the catalytically active material;

a structured catalyst for catalyzing said endothermic feed gas reaction, said structured catalyst comprising an electrically conductive material and a catalytic material;

a high pressure housing in which said structured catalyst is located;

a heat-insulating layer between said structured catalyst and said pressure vessel;

at least two conductors electrically connected to said structured catalyst and to a power source located outside the pressure vessel, wherein the power source is configured to heat at least a portion of said structured catalyst to a temperature of at least 200°C by passing electric current through an electrically conductive material;

wherein said pressure vessel includes an inlet for introducing a process gas and an outlet for removing a gaseous product, wherein said inlet is located adjacent to the front of the pressure vessel and the outlet is located adjacent to the rear of the pressure vessel, wherein at least at least two conductors are connected to the structured catalyst at a point on the structured catalyst closer to the inlet than to the outlet; and moreover, the structured catalyst has electrically insulating parts located between the conductors, preventing the passage of the specified current through some part of the structured catalyst.

In accordance with the topology of the reactor system, the compressed source gas is fed into it through the inlet and directed to the pressure vessel of the reactor system. High pressure housing

- 1 041440 has such an internal configuration of heat-insulating layers and inert material that the source gas is directed through the structured catalyst, where it will be in contact with the catalytic material, while the catalytically active material will promote the steam reforming reaction. In addition, heating the structured catalyst provides the necessary heat for the endothermic reaction. The gaseous product from the heated structured catalyst is directed to the outlet from the reactor system.

Due to the close proximity between the catalytically active material and the electrically conductive material, efficient heating of the catalytically active material by conduction from the electrically conductive material heated by the resistance is possible. An important feature of the resistance heating method is that the heat is generated within the object itself, and is not heated by an external heat source through convective or conductive heat transfer and/or radiative heating. In addition, the hottest part of the reactor system will be inside the reactor pressure vessel. Preferably, the feed source and the structured catalyst are sized such that the temperature of at least a portion of the structured catalyst reaches 850-1100°C if the endothermic reaction is a steam reforming reaction, or 7001200°C if the endothermic reaction is hydrogen cyanide synthesis, or 500-700°C if the endothermic reaction is dehydrogenation, or 200-300°C if the endothermic reaction is methanol cracking, and about 500°C if the endothermic reaction is ammonia cracking. The surface area of the electrically conductive material, the portion 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 catalytic material can be adapted to the specific operating conditions of a particular endothermic reaction.

In one embodiment, the electrically conductive material is a macroscopic structure. As used throughout this document, the term macroscopic structure means that the structure is large enough to be visible to the naked eye without magnifying devices. Typically, the macroscopic structure has dimensions ranging from a few centimeters to several meters. The macroscopic structure is preferably sized to match, at least in part, the internal dimensions of the pressure vessel housing the structured catalyst, thereby saving space for the thermal insulation layer and conductors. Two or more macroscopic structures can be connected, resulting in a set of macroscopic structures, at least one of the external dimensions of which is in the meter range, for example, at least one dimension of such a set of macroscopic structures can be 2 or 5 m. Such two or more macroscopic structures may be referred to as a set of macroscopic structures. In this case, the dimensions of the set of macroscopic structures are preferably made to correspond, at least in part, to the internal dimension of the pressure vessel in which the structured catalyst is placed (saving space for the heat-insulating layer). It is assumed that such a set of macroscopic structures can occupy a volume from 0.1 to 10 m ³ or even more volume. The structured catalyst may include one macroscopic structure or a set of macroscopic structures, wherein a ceramic coating is located on the macroscopic structures, while the specified ceramic coating acts as a substrate of the catalytically active material. In a set of macroscopic structures, such macroscopic structures can be electrically connected to each other. However, as an alternative, the macroscopic structures may not be electrically connected to each other. Thus, a structured catalyst may include two or more macroscopic structures located next to each other. Macroscopic structures can be made by extrusion and sintering, or made by 3D printing technology. The macroscopic structure produced by 3D printing technology may or may not be further sintered.

The macroscopic structures may have any suitable physical dimensions, thus the height may be less than the width of the macroscopic structure, or vice versa.

A ceramic coating is disposed on said macroscopic structure, said ceramic coating acting as a support for the catalytically active material. The term macroscopic structure having a ceramic coating means that at least part of the surface of the macroscopic structure is coated with a ceramic material. Thus, this term does not mean that the entire surface of the macroscopic structure is covered with a ceramic material; in particular, at least those parts of the macroscopic structure that are electrically connected to the conductors do not have a ceramic coating. The coating is a ceramic material with pores in the structure, which allows the application of the catalytically active material on and within the coating. Advantageously, the catalytically active material comprises catalytically active particles having a size in the range of approximately 5-250 nm.

The macroscopic structure is preferably made by extruding a mixture of powdered metal particles and a binder to an extruded structure and then

- 2 041440 sintering the extruded structure, resulting in a material with a high ratio of geometric surface area to volume. Preferably, the structure obtained by extrusion is subjected to sintering in a reducing atmosphere to obtain a macroscopic structure. Alternatively, the macroscopic structure is fabricated by 3D printing and melting with a metal additive, namely using 3D printing processes that do not require subsequent sintering, such as melting a material in a preformed layer or layered electron beam technology. melting material. Examples of such preformed layer melting or layered electron beam melting technologies are 3D printing processes using a laser beam, electron beam, or plasma printing. As another alternative, the macroscopic structure can be made as a three-dimensional metal structure by a binder-based manufacturing technique using a metal additive, and then can be sintered in a non-oxidizing atmosphere at a first temperature T1, where T1>1000°C to obtain a macroscopic structure.

A ceramic coating, which may contain a catalytically active material, is applied to the macroscopic structure prior to the second sintering in an oxidizing atmosphere to form chemical bonds between the ceramic coating and the macroscopic structure. Alternatively, the catalytically active material may be impregnated onto the ceramic coating after the second sintering. When chemical bonds are formed between the ceramic coating and the macroscopic structure, a particularly high thermal conductivity is possible between the electrically heated macroscopic structure and the catalytically active material which is located on the ceramic coating, which ensures 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, so that heating of the structured catalyst can be carried out with high efficiency. Thus, an optimum gas treatment per unit volume of the reactor system can be achieved, so the reactor system containing the structured catalyst can be compact.

When used in the text of this document, the terms 3D printing technology and 3D printing mean production technology using a metal additive. Such metal-additive manufacturing techniques include 3D printing processes, in which, under automated control, a material is combined into a specific structure to obtain a three-dimensional object, in which the structure is cured, for example, by sintering, to obtain a macroscopic structure. In addition, such metal additive manufacturing technologies include 3D printing processes that do not require subsequent sintering, such as preformed layer melting technology or layered electron beam melting technology. Examples of such preformed layer melting or layered electron beam melting technologies are 3D printing processes using a laser beam, electron beam, or plasma printing.

The reactor system according to the invention does not require an oven and this greatly reduces the overall size of the reactor.

In one embodiment, the electrically conductive material is a resistance device embedded in the catalytic material of the structured catalyst. Such an embedded resistance device may be in any suitable shape, such as plates, spirals, rods, or the like, where the catalyst material may surround the embedded resistance device or may be otherwise positioned to closely contact the device.

In one embodiment, a ceramic coating is disposed on the embedded resistance device, said ceramic coating acting as a support for the catalytically active material. Thus, an embedded resistance device, similar to a macroscopic substrate, can be coated with a ceramic coating so that the catalytically active phase is directly on it, while the resistance device remains embedded in the catalytic material. In this embodiment, the catalytic material is located around the built-in resistance device, and the structured catalyst contains the catalytic material in the form of grains, extrudates or granules of the catalyst. The catalytic material may contain a suitable combination of catalyst support and catalytically active phase to catalyze an endothermic reaction.

Preferably, the electrically conductive material contains Fe, Cr, Al or an alloy thereof. Such an alloy may contain additional elements such as Si, Mn, Y, Zr, C, Co, or combinations thereof. Preferably the catalytically active material is a particle having a size of 5-250 nm. Preferably, the conductors and the electrically conductive material are made from different materials. The conductors may be made, for example, of iron, nickel, aluminium, copper, silver, or an alloy thereof.

The ceramic coating is an electrically insulating material and typically has a thickness in the range of about 100 microns, such as 10-500 microns.

The electrically conductive material is preferably a cohesive or internally integral material in order to provide electrical conductivity throughout the electrically conductive material and therefore to provide thermal conductivity throughout the structured catalyst, in particular for heating the catalytically active material. By means of a cohesive or internally solid material, it is possible to ensure a uniform distribution of current in the electrically conductive material and thus a uniform distribution of heat within the structured catalyst. Throughout this document, the term cohesive is synonymous with the term bonded, thus cohesive refers to a material that is intrinsically solid or cohesive. Because the structured catalyst is a cohesive or intrinsically solid material, control is provided over the electrical connectivity within the structured catalyst material and thus conduction of the electrically conductive material is ensured. It should be noted that even if further modifications are made to the electrically conductive material, such as slitting within portions of the electrically conductive material or embedding an insulating material into the electrically conductive material, the electrically conductive material is still a coherent or internally integral material.

The gas flow through the structured catalyst may be in the same direction as the direction of the current path through the structured catalyst, or the gas flow may be coaxial with the direction of the current path through the structured catalyst, it may be perpendicular to the current path, or have any other suitable direction with respect to the direction of the current path.

In the context of the invention, the term source gas means a gas with a composition suitable for carrying out a particular endothermic reaction. If the endothermic reaction is a steam reforming of methane, the composition of the gas may typically include hydrocarbons, methane, hydrogen, carbon monoxide, carbon dioxide, steam, and inert gases such as nitrogen and argon. If the endothermic reaction is a dehydrogenation, the feed gas may be a hydrocarbon in the form of propane or styrene, together with inert components and possibly hydrogen. If the endothermic reaction is a hydrogen cyanide synthesis or an organic nitrile synthesis process, the gas composition may include higher hydrocarbons, ammonia, methane, nitrogen, hydrogen, oxygen, and/or inert components. If the endothermic reaction is methanol cracking, the gas composition may include methanol, steam, carbon monoxide, carbon dioxide, hydrogen, and inert components. If the endothermic reaction is ammonia cracking, the gas composition may include ammonia, hydrogen, nitrogen, and inert components.

In addition, the term steam reforming means a reforming reaction according to one or more of the following equations:

CH ₄ + H ₂ O θ CO + ZN ₂ (i)

CH ₄ + 2H ₂ O θ CO ₂ + 4H ₂ (ii)

CH ₄ + CO ₂ θ 2CO + 2H ₂ (iii)

Reactions (i) and (ii) are steam methane reforming reactions, while reaction (iii) is a dry methane reforming reaction.

For higher hydrocarbons, i.e. for C _n Hm, where n>2, m>4, equation (i) has the following general form:

CnHm + η H ₂ O θ nCO + (η + m/2)H ₂ (iv) where n>2, m>4.

Steam reforming is usually accompanied by a water gas shift reaction (v):

CO + H ₂ O θ CO ₂ + H ₂ (v)

The term methane steam reforming includes reactions (i) and (ii), the term steam reforming includes reactions (i), (ii) and (iv), while the term methanation includes the reverse reaction of reaction (i). In most cases, at the outlet of the reactor system, all these reactions (i)-(v) have reached equilibrium or are close to it.

The term pre-reforming is often used to refer to the catalytic conversion of higher hydrocarbons according to reaction (iv). Pre-reforming is typically accompanied by steam reforming and/or methanation (depending on gas composition and operating conditions) and a water gas shift reaction. Pre-reforming is often carried out in adiabatic reactors, but may also take place in heated reactors.

The term hydrogen cyanide synthesis means the following reactions:

CH ₄ + 2 NH ₃ + 3 O ₂ θ 2 HCN + 6 H ₂ O (vi)

CH ₄ + ΝΗ ₃ θ HCN + ZN ₂ (vii)

- 4 041440

The term dehydrogenation means the following reactions:

R1-CH2-CH2-R2 θ Ri-CH=CH-R ₂ (viii) where R1 and R2 may be any suitable group on the hydrocarbon molecule such as -H, -CH3, -CH2 or -CH.

The term methanol cracking means the following reactions:

CH3OH θ CO + 2H ₂ (ix)

CH3OH + H ₂ O θ CO ₂ + ZH ₂ (x)

The methanol cracking reaction is usually accompanied by a water gas shift reaction (v). The term ammonia cracking means the following reactions:

2ΝΗ ₃ θ N ₂ + ZN ₂ (xi)

For example, the steam reforming reaction proceeds with the absorption of a large amount of heat. To achieve a satisfactory degree of conversion of methane in the source gas requires high temperatures, typically temperatures in excess of 800-850°C. The SMR consists of several tubes filled with catalyst grains inside a furnace. The length of the pipes, as a rule, is 10-13 m, the inner diameter is 80-160 mm. The burners placed in the furnace provide the necessary heat for the reactions by burning the fuel gas. The maximum average heat flow is often 8000090000 kcal/h/m ² of the inner surface of the pipe. The overall limitation of the heat flow is due to mechanical factors, so the power is increased by increasing the number of pipes and the size of the furnace. Detailed information about the reactor system type SMR known from the literature, for example, from the work Production of synthesis gas for Fischer-Tropsch synthesis (Synthesis gas production for FT synthesis); section 4, p. 258-352, 2004.

The term electrically conductive means materials with electrical resistivity in the range of 10 ^-5 to 10 ^-8 Ω-m at 20°C. Thus, electrically conductive materials are, for example, metals such as copper, silver, aluminium, chromium, iron, nickel or metal alloys. In addition, the term electrically insulating means materials with electrical resistivity above 10 Ω-m at 20°C, for example in the range of 109-10 ²⁵ Ω-m at 20°C.

If the reactor system includes a thermal insulation layer between the structured catalyst and the pressure vessel, the necessary thermal or electrical insulation is provided between the structured catalyst and the pressure vessel. The presence of a heat-insulating layer between the structured catalyst and the pressure vessel helps to avoid excessive heating of the pressure vessel and helps to reduce thermal loss to the environment. Temperatures in the structured catalyst, at least in some of its parts, can reach approximately 1300°C, however, using a thermal insulation layer between the structured catalyst and the pressure vessel, it is possible to maintain a lower temperature of the pressure vessel, for example, 500°C or even 100 °C, which is an advantage because typical structural steel materials cannot normally be used under load at temperatures above 1000°C. In addition, the heat insulating layer between the pressure vessel and the structured catalyst helps control the electrical current in the reactor system, since the heat insulating layer is also electrically insulating. The thermal barrier layer may be one or more layers of hard material such as ceramic, inert material, brick, or gas barrier, or a combination thereof. Thus, it is also possible for a part of the heat-insulating layer to constitute or form a purge gas or a gas inside the catalyst.

In addition, it should be noted that the term thermal insulation material means materials with a thermal conductivity of approximately 10 W(m' ¹ -K' ¹ ) or lower. Examples of thermal insulation materials are ceramics, bricks, alumina materials, zirconia materials, and the like.

Any appropriate gaps between the structured catalyst, thermal insulation layer, pressure vessel, and/or any other components within the reactor system are preferably filled with an inert material, such as grains of inert material. Such gaps may be, for example, the gap between the underside of the structured catalyst and the bottom of the pressure vessel and the gap between the sides of the structured catalyst and the insulating layer covering the inner sides of the pressure vessel. The inert material may be, for example, a ceramic material in the form of grains or tiles. The inert material helps control the distribution of gas in the reactor system and control the flow of gas through the structured catalyst. In addition, the inert material generally has a heat-insulating effect.

In one of the embodiments of the invention, the design pressure of the pressure vessel is in the range of 2-30 bar. The actual operating pressure will be determined, among other things, by the endothermic reaction and the size of the units. Since the hottest part of the reactor system is the electrically conductive material around which there will be an insulating layer inside the pressure vessel of the reactor system, the temperature of the pressure vessel will be maintained at a level significantly lower than the maximum operating temperature. This allows

- 5 041440 have a relatively low pressure vessel design temperature, e.g. 700 or

500°C, or preferably 300 or 100°C, at a maximum operating temperature on the structured catalyst of 400 or even 900 or 1100 or even up to 1300°C. The strength of the material is higher at the lower of these temperatures (corresponding to the pressure vessel design temperature as above). This provides advantages in the design of a chemical reactor.

In one embodiment of the invention, the design pressure of the pressure vessel is in the range of 30-200 bar, preferably in the range of 80-180 bar.

In one embodiment, the resistivity of the electrically conductive material is in the range of 10-5-10 ^-7 Ω-m. A material with a resistivity in this range provides efficient heating of the structured catalyst when energy is supplied from a power source. The resistivity of graphite is approximately 10 ^-5 Ω-m at 20°C, the resistivity of kanthal is approximately 10 ^-6 Ω-m at 20°C, the resistivity of stainless steel is approximately 10 ^-7 Ω-m at 20°C. The electrically conductive material may be made of, for example, FeCrAlloy with a resistivity of approximately 1.5-10 ^-6 Ω-m at 20°C.

In one embodiment, the pressure vessel includes a process gas inlet and a product gas outlet, with the inlet located closer to the front of the pressure vessel and the outlet toward the rear of the pressure vessel, with at least At least two conductors are connected to the structured catalyst at a point on the structured catalyst closer to the inlet than to the outlet. Because of this, at least two conductors can be placed in a substantially colder part of the reactor system, since the feed gas will have a lower temperature than the product gas, and the upstream part of the electrically conductive material will be colder due to absorb heat during the chemical reaction, and the feed gas fed through the inlet can cool at least two conductors before being heated by the structured catalyst downstream of the gas through the structured catalyst. The advantage is that the temperature of all electrically conductive elements, with the exception of the electrically conductive material, is maintained at a low level in order to protect the connections between the conductors and the structured catalyst. If the conductors and other electrically conductive members other than the electrically conductive material are kept at a relatively low temperature, this allows a wider range of materials to be used for the conductors and other electrically conductive members other than the electrically conductive material. As the temperature of the electrically conductive elements increases, their resistivity also increases, hence it is desirable to avoid unnecessary heating of all other parts except the electrically conductive materials within the reactor system. The term electrically conductive elements other than electrically conductive material includes corresponding electrically conductive elements that are intended to connect a power source to the structured catalyst.

In yet another embodiment, the two conductors of the reactor system may be located at opposite ends of the structured catalyst.

It should be noted that the system of the invention may include any suitable number of power supplies and any suitable number of conductors connecting the power supplies and the electrically conductive materials of the structured catalyst.

According to one embodiment of the reactor system, at least two conductors are passed through the pressure vessel by means of a fitting such that the at least two conductors are electrically isolated from the pressure vessel. The fitting may be partly made of plastic and/or ceramic material. The term fitting means a device that allows the mechanical connection of two pieces of equipment that are in such a configuration under load. With its use, the pressure inside the pressure vessel can be maintained, even if at least two conductors pass through it. Non-limiting examples of fittings include electrical insulating fittings, dielectric fittings, power compression seals, compression fittings, or flanges. The pressure vessel typically includes side walls, end walls, flanges, and possibly other elements. The term pressure vessel can refer to any of these components.

In one embodiment, the pressure housing further includes one or more inlets adjacent to or in combination with at least one fitting to allow refrigerant gas to pass through, around, adjacent to, or within at least one conductor within said housing. high pressure. In this way, cooling of the conductors is ensured and the heating temperature of the fitting is kept low. If no cooling gas is used, the conductors may be heated by the feed gas supplied to the reactor system, resistive heating of the conductor due to current injection and/or heat transfer from the structured catalyst. The cooling gas may, for example, be hydrogen, nitrogen, steam, carbon dioxide, or mixtures thereof. The temperature of the cooling gas at the supply to the pressure vessel may be, for example, approximately 100 or 200 or 250°C. In one embodiment, the conductors are hollow to allow cooling gas to pass through the conductors and cool them from the inside. By maintaining a low fitting temperature, for example around 100-200°C, it is easier to achieve a tight configuration. In one embodiment, a portion of the feed gas, such as one of the reactants, is fed into the pressure vessel as cooling gas. In yet another embodiment, a portion of the feed gas or a gas of the same composition as the feed gas is used as the cooling gas.

In one of the embodiments, the reactor system further includes an inner tube, wherein heat exchange is carried out between it and the structured catalyst, and the inner tube is configured to remove the gaseous product from the structured catalyst in such a way that between the gaseous product entering through the inner tube or pipes, there is heat exchange with the gas flowing over the structured catalyst, however, the inner tube is electrically isolated from the structured catalyst. This configuration is referred to herein as a bayonet reactor system. In this configuration, the product gas in the inner tube contributes to the heating of the process gas entering through the structured catalyst. Electrical isolation between the inner tube and the structured catalyst can be provided by gas in the gap between the inner tube and the structured catalyst, or by an inert material located around the inner tube and the structured catalyst. The gas may flow through the structured catalyst in an upward or downward direction.

In one of the embodiments of the invention, the connection between the structured catalyst and these at least two conductors is a mechanical connection, a welded joint, a solder joint, or a combination thereof. The structured catalyst may include terminals physically and electrically connected to the structured catalyst to provide a more efficient electrical connection between the electrically conductive material and the at least two conductors. The term mechanical connection means a connection in which two components are held together mechanically, such as by a threaded connection or clamp, so that current can flow between the components.

In one of the embodiments of the invention, the electrically conductive materials placed in the set of electrically conductive materials may be electrically connected to each other. The connection between two or more electrically conductive materials may be by mechanical connection, clamping, soldering, welding, or any combination of these connection methods. Each electrically conductive material may include contact leads to provide a more efficient electrical connection. Two or more electrically conductive materials can be connected to the power supply in series or in parallel. The electrical connection between two or more electrically conductive materials is preferably cohesive and uniform along the surface of the connection between the two or more electrically conductive materials, so that the two or more electrically conductive materials act as a single cohesive or internally integral material, thereby ensuring uniform electrical conductivity of the two or more electrically conductive materials. Alternatively, or additionally, the structured catalyst may include a set of electrically conductive materials that are not electrically connected to each other. Instead, two or more electrically conductive materials are placed together within the pressure vessel, but are not electrically connected to each other. Thus, in this case, the structured catalyst includes electrically conductive materials connected in parallel to a power source.

A ceramic coating, with or without a catalytically active material, can be applied directly to the metal surface of the electrically conductive material by a pickle primer. Pickling primer is a known technology and is described in e.g. Cybulski, A., and Moulijn, J. A., Structured catalysts and reactors, Marcel Dekker, Inc, New York, 1998, chapter 3, referenced herein. A ceramic coating may be applied to the surface of the electrically conductive material and then the catalytically active material may be added. Alternatively, the macroscopic structure or the electrically conductive material is coated with a ceramic coating containing the catalytically active material. The ceramic coating may be, for example, an oxide containing Al, Zr, Mg, Ce and/or Ca. The coating may be, for example, calcium aluminate or magnesium aluminum spinel. Such a ceramic coating may contain additional elements such as La, Y, Ti, K, or combinations thereof.

The ceramic coating is an electrically insulating material and typically has a thickness in the range of about 100 microns, such as 10-500 microns.

As a result of extrusion and sintering or 3D printing, a homogeneous macroscopic structure of a cohesive shape is obtained, which can subsequently be applied with a ceramic coating.

The sintering of the electrically conductive material and ceramic coating can be carried out in the oxide

- 7 041440 casting atmosphere for the formation of chemical bonds between the ceramic coating and the electrically conductive material. This provides a particularly high thermal conductivity between the electrically conductive material and the catalytically active material, which is located on the ceramic coating substrate. Thus, the structured catalyst is optimized in terms of heat transfer to the active catalytic site, and also the reactor system in which the structured catalyst is located can be optimized and limited mainly by the chemical reaction rate. Heat transfer from outside the pressure vessel to the structured catalyst is not carried out, as is the case with known SMRs, where heat transfer occurs through the walls of the pipes to the catalyst inside the pipes.

In one embodiment, the structured catalyst has electrically insulating portions by which the length of the current path between the conductors is increased to be greater than the longest dimension of the structured catalyst. A current path between conductors greater than the largest dimension of the structured catalyst can be provided by placing electrically insulating portions between the conductors when no current passes through some portion of the structured catalyst. Such electrically insulating parts are intended to increase the current path and thus increase the resistance in the structured catalyst. As non-limiting examples of insulating parts, slots, slots, bends or holes in the electrically conductive material can be given. If necessary, a solid insulating material such as ceramic can be used in the slots in the structure. In the case where the solid insulating material is a porous ceramic material, the catalytically active material may advantageously be introduced into the pores, for example by impregnation. A solid insulating material within the slot helps isolate the portions of the structured catalyst on the sides of the slot from each other. When used in the text of the present invention, the term the largest dimension of the structured catalyst means the largest internal dimension of the geometric shape occupied by the structured catalyst. If the structured catalyst is box-shaped, the largest dimension will be the diagonal from one corner to the farthest corner, also referred to as the spatial diagonal.

It should be noted that even though due to the electrically insulating parts provided to increase the current path, the current can pass through the structured catalyst with a change of direction, the gas passing through the reactor system enters one part of the reactor system and passes once over the structured catalyst before leaving the reactor system. In appropriate gaps between the structured catalyst and the rest of the reactor system, inert material is preferably present so that, within the reactor system, the gas passes over the structured catalyst and the catalytically active material.

In one embodiment, the length of the gas passage through the structured catalyst is less than the length of the current path from one electrode through the structured catalyst to the next electrode. The ratio of the length of the gas channel to the length of the current path can be less than 0.6 or 0.3, 0.1 or even 0.002.

In one embodiment, the structured catalyst has electrically insulating portions that direct current through the structured catalyst in a zigzag path. In this document, the term zigzag path means a path from one conductor to another, the direction of which changes at different angles. A zigzag path is, for example, a path that goes up, turns around, and then goes down. A zigzag path may have many turns, it may go up and then down many times as it passes through the structured catalyst, even if one turn is enough to make the path zigzag.

It should be noted that insulating parts designed to increase the current path are not necessarily associated with a ceramic coating on an electrically insulating material, although this ceramic coating is also considered electrically insulating, it does not change the length of the current path between conductors connected to the electrically conductive material.

In one embodiment of the invention, the macroscopic structure has a plurality of parallel channels, a plurality of non-parallel channels, and/or a plurality of labyrinthine channels, wherein the channels are limited by walls. Thus, several different forms of macroscopic structure can be used as long as the surface area of the structured catalyst exposed to the gas is maximized. In a preferred embodiment, the macroscopic structure has parallel channels, since such parallel channels provide a very small pressure drop in the structured catalyst. In a preferred embodiment, the parallel longitudinal channels are arranged at an angle with respect to the longitudinal axis of the macroscopic structure. Thus, gas molecules entering through the macroscopic structure will hit the walls inside the channels rather than simply flowing straight through the channel without making contact with the wall. The size of the channels must be such as to provide sufficient resistance to the macroscopic structure. For example, the channels may be square (in a cross section perpendicular to the channels) with a side length of 1-3 mm, but channels with a maximum cross-sectional extent of up to about 4 cm are also possible. The wall thickness may, for example, be 0, 2-2 mm, eg approximately 0.5 mm, and the thickness of the ceramic coating located on the walls is 10-500 µm, eg 50-200 µm, eg 100 µm. In another embodiment, the macroscopic structure of the structured catalyst has transverse corrugation.

In general, when the macroscopic structure is made by extrusion or 3D printing, the pressure drop from the inlet to the outlet of the reactor system can be significantly reduced compared to a reactor in which the catalyst material is in the form of pellets.

In one of the embodiments of the invention, the reactor system further includes a layer of the second catalytic material in the course of the process before the structured catalyst inside the pressure vessel. In this document, the term upstream means upstream in the direction of flow of the source gas. Thus, as used herein, the term downstream means that the feed gas is passed through the bed of the second catalyst material prior to being fed into the structured catalyst. This provides a situation where such a second catalyst material can be used to prepare the feed stream. The layer of the second catalytic material does not require special heating, however, indirect heating of the layer of the second catalytic material can be carried out if it is in close proximity to the structured catalyst. Alternatively, indirect heating of the second catalytic material can be carried out. To clarify the terminology used herein, it should be noted that the term structured catalyst may also refer to the first catalyst material to distinguish it from the second and/or third and/or fourth catalyst material.

In one of the embodiments of the invention, the reactor system further includes a third catalyst material in the form of catalyst grains, extrudates or catalyst granules, which are loaded into the channels of the macroscopic structure. Thus, in this embodiment, the reactor system will have the catalytically active material in the macroscopic structure coating and the third catalyst material in the form of catalyst grains, extrudates or catalyst pellets within the channels of the macroscopic structure. The grains, for example, may be of a size that approximates the size of the channels so as to form a single chain of grains stacked on top of each other within the channel of the macroscopic structure. Alternatively, the grains, extrudates or granules may be substantially smaller than the size of the channel to form a compacted layer within each channel. As used throughout the present invention, the term grain refers to any defined structure having a maximum external dimension in the range of millimeters or centimeters, while the terms extrudate and granulate define a catalyst material with a maximum external dimension in a specific range.

In one of the embodiments of the invention inside the pressure vessel after the specified structured catalyst is placed a layer of the fourth catalytic material. Such fourth catalyst material may be in the form of grains, extrudates, or catalyst pellets.

In one embodiment, the first, second, third, and fourth catalyst materials are catalyst materials suitable for a steam reforming reaction, a pre-reforming reaction or a water gas shift reaction, a dehydrogenation reaction, a methanol cracking reaction, an ammonia cracking reaction, or a hydrogen cyanide synthesis reaction. In a configuration where the reactor system includes a combination of second, third and fourth catalyst material, the catalyst of each catalyst material may be different.

In one of the embodiments of the invention, the geometric surface area of the macroscopic structure is in the range of 100-3000 m ² /m ³ for example 500-1100 m ² /m ³ .

In one of the embodiments of the invention, the material of the macroscopic structure is selected in such a way that by heating the material with a resistance, a heat flux of 500-50000 W/m ² is created. Preferably, the resistance heating of the material provides a heat flux in the range of 512 kW/m ² , for example in the range of 8-10 kW/m ² . Heat flux is defined as the amount of heat per geometric surface area exposed to the gas.

In one of the embodiments of the invention, the reactor system further includes a control system configured to control the supply of electricity so that the temperature of the gas leaving the pressure vessel is within a predetermined range and/or so that the degree of conversion of hydrocarbons in the source gas is in predefined range. Power supply control is the control of electrical power from a power source. The control of the power supply may, for example, be carried out as control of the voltage and/or current supplied from the power supply, as control by switching on/off the power supply, or by a combination of these methods. The structured catalyst may be supplied with alternating or direct current.

The specific temperature range for the gas exiting the pressure vessel/reactor system is between 200 and 1300°C, depending on the endothermic reaction taking place.

- 9 041440

In order to control the reaction temperature, it is necessary to balance the heat supplied to the reactor system or removed from the reactor system with the heat consumed/produced during the chemical reaction. Heat supply/removal must be balanced by the reaction rate and, in particular, by the temperature approaching equilibrium conditions, defined by β, where β is the ratio between the reaction coefficient and the equilibrium constant of the reaction. If the value of β approaches 1, this means that the reaction mixture is close to equilibrium, and values approaching 0 mean that the reaction mixture is far from equilibrium. In general, it is desirable to have as high a reaction rate as possible, which is achieved at low β, provided that the temperature can be controlled in parallel sufficiently to balance the added energy.

In the case of an endothermic methane steam reforming reaction, it is necessary to supply additional heat to continue the reaction, because otherwise the reaction will be balanced, the value of β will approach 1, and the reaction will slow down. However, on the other hand, it is desirable that the temperature increase be consistent with the rate of reaction, since exposing unreacted hydrocarbons to high temperatures can lead to carbon formation. One can effectively monitor this by approaching equilibrium conditions. The temperature approaching the equilibrium conditions of the steam reforming reaction is determined first by calculating the reaction coefficient (Q) for a certain gas:

h

I _Q ^ Uso ' Un _{2 p2}

Usn ₄ 'un ₂ o

Here yj is the mole fraction j of the compound and P is the total pressure value in bar. This equation is used to determine the equilibrium temperature (Teq) at which a given reaction coefficient equals the equilibrium constant:

Q — KsMR(Teq) where K _SMR is the thermodynamic equilibrium constant of the methane steam reforming reaction. Temperature approaching equilibrium conditions (ΔТ _αin , _SMR ) of the methane steam reforming reaction is determined as follows:

△Trav, SMR = T - T _eq where T is the mass average temperature of the gas surrounding the catalytic material used, such as a structured catalyst.

To ensure good performance of the steam reforming catalyst, it is desirable that the catalyst be continuously operated in the direction of decreasing ΔT _equal , _SMR . Historically, large-scale industrial SMRs have had near-equilibrium temperatures of 5-20°C at the outlet.

The use of the present invention allows the heat flux to be controlled and matched directly to the kinetic characteristics of the structured catalyst, since they are somewhat independent.

In one embodiment, in said reactor system, the ratio between the equivalent diameter of the horizontal cross-sectional area of the structured catalyst and the height of the structured catalyst is in the range of 0.1-2.0. The equivalent cross-sectional area diameter of a reactor system is defined as the diameter of a circle with an area equivalent to the cross-sectional area. When the ratio between the equivalent area diameter and the height of the structured catalyst is 0.1-2.0, the pressure vessel housing the structured catalyst can be relatively small compared to other endothermic reaction reactor systems, for example compared to existing SMRs. .

Typically, the gas flows through the reactor system in an upward or downward direction, so that the gas flows through channels in the structured catalyst in the height direction of the structured catalyst. When the structured catalyst includes several macroscopic structures or a set of macroscopic structures, individual macroscopic structures within the array may be placed side by side, on top of each other, or there may be a combined arrangement of macroscopic structures. It is emphasized that when a structured catalyst includes more than one macroscopic structure, the dimensions of the structured catalyst are determined by the dimensions of several macroscopic structures. Thus, for example, if a structured catalyst consists of two stacked macroscopic structures, each having a height h, the height of the structured catalyst is 2h.

The volume of the structured catalyst is selected based on the desired degree of conversion and/or the temperature at the outlet of the reactor system, correlated with the heat generating capacity of the electrically conductive material.

In one of the embodiments of the invention, the height of the reactor system is 0.5-7 m, more preferably 0.5-3 m. The height of the reactor system can be, for example, less than 5 m, preferably less than 2 or even 1 m. structured catalyzate

- 10 041440 RA within the reactor system are interconnected. Obviously, due to the pressure vessel and thermal insulation layer, the reactor system is somewhat larger than the structured catalyst itself. By comparison, industrial scale SMRs are typically constructed with catalyst tubes of 10 m or more in length to maximize the outer surface area of the tubes. The present invention has the advantage that the design of the reactor system does not have such limitations.

Another aspect of the invention relates to a method for carrying out an endothermic feed gas reaction in the described reactor system. This method includes the following steps:

supplying said feed gas to the reactor system by introducing said process gas at a point adjacent to the front of the pressure vessel;

providing an endothermic reaction of the source gas over the heated structured catalyst and the removal of the gaseous product from the reactor system, and the specified gaseous product exits at a point located near the rear of the pressure vessel; and supplying current through conductors connecting a power source located outside said pressure vessel to said structured catalyst, which allows current to be passed through said electrically conductive material, thereby heating at least a portion of the structured catalyst to a temperature of at least 200 °C.

The method provides the same advantages as described for the reactor system. However, the process may include additional steps in which the gaseous product will be processed, for example, purification, pressurization, heating, cooling, etc., to obtain the final gaseous product, which will be used in the process after the reactor system according to the invention .

It should be noted that the feed gas may contain separate feed gases, and that the step of compressing the feed gas may include compressing the individual feed gases. In addition, it should be noted that the steps of the method do not have to be performed in the specified order, for example, two steps or multiple steps may be performed simultaneously, or the order may be different from the above order.

In one embodiment, the method further comprises the step of compressing the feed gas upstream of the pressure vessel to a pressure of at least 2 bar and supplying said compressed feed gas to the reactor system by introducing said compressed feed gas at said point adjacent front of the high pressure housing. The selected operating pressure is determined by the endothermic reaction and the process steps in which the reactor is built.

In one of the embodiments of the method according to the invention, the temperature of the source gas entering the reactor system is 100-700°C. However, in all embodiments, the feed gas temperature and pressure are controlled to ensure that the feed gas temperature is above the dew point.

In one of the embodiments of the method according to the invention, the structured catalyst is heated in such a way that the maximum temperature of the structured catalyst is in the range of 200-1300°C. The temperature used will depend on the endothermic reaction. The maximum temperature of the structured catalyst depends on the material of the electrically conductive material. Thus, if the electrically conductive material is made from a Fecralloy® whose melting point is 1380-1490°C (depending on the actual properties of the alloy), the maximum temperature should be somewhat below the melting point, for example approximately 1300°C if the melting point of the electrically conductive material is approximately 1400°C, as the material will become soft and ductile as it approaches the melting point. The maximum temperature may be further limited by the wear resistance of the catalyst material, coating and catalytically active material.

In one embodiment, the method of the present invention includes the step of supplying refrigerant gas through an inlet in the pressure housing so that refrigerant gas can pass through at least one conductor and/or fitting. The cooling gas may preferably be hydrogen, nitrogen, steam, carbon dioxide, or any other gas suitable for cooling the region or zone around the at least one conductor. Part of the feed gas can be fed into the pressure vessel as cooling gas.

In one embodiment of the invention, the method further includes the step of supplying refrigerant gas through an inlet in the pressure housing so that refrigerant gas can pass through at least one conductor and/or fitting. Any suitable gas may be used as the cooling gas, for example the cooling gas may be hydrogen, nitrogen, steam, carbon dioxide, or mixtures thereof.

Coolant gas can flow through the conductors and cool them from the inside, in which case the conductors must be hollow to accommodate the cooling gas.

In one embodiment, the endothermic reaction is the dehydrogenation of hydrocarbons. The reaction proceeds according to equation (viii). The catalytic material for the reaction may be Pt/Al2O ₃ or Pt-Sn/Al2O ₃ . The catalytically active material may be Pt. The maximum temperature of the reactor may be 500-700°C. The pressure of the source gas can be 2-5 bar.

In one of the embodiments of the invention, the endothermic reaction is the cracking of methanol. The reaction proceeds according to equations (v), (ix) and (x). The catalytic material for the reaction may be Ni/MgAl ₂ O ₃ or Cu/Zn/Al ₂ O ₃ . The catalytically active material may be Cu or Ni. The maximum temperature of the reactor may be 200-300°C. The feed gas pressure may be 2-30 bar, preferably about 25 bar.

In one embodiment, the endothermic reaction is the steam reforming of hydrocarbons. The reaction proceeds according to equations (i)-(v). The catalytic material for the reaction may be Ni/Al ₂ O ₃ , Ni/MgAl ₂ O ₃ , Ni/CaAl ₂ O ₃ , Ru/MgAl ₂ O ₃ or Rh/MgAl ₂ O ₃ . The catalytically active material may be Ni, Ru, Rh, Ir, or a combination thereof. The maximum temperature of the reactor may be 850-1300°C. The feed gas pressure may be 15180 bar, preferably about 25 bar.

In one embodiment, the endothermic reaction is ammonia cracking. The reaction proceeds according to equation (xi). The catalytic material for the reaction may be Fe, FeCo or Ru/Al ₂ O ₃ . The catalytically active material may be Fe or Ru. The maximum temperature of the reactor may be 400-700°C. The feed gas pressure may be 2-30 bar, preferably about 25 bar.

In one embodiment, the endothermic reaction is a hydrogen cyanide synthesis or an organic nitrile synthesis process. The reaction proceeds according to equation (vi) and (vii). The catalytic material for the reaction may be Pt/Al2O3. The catalytically active material may be Pt, Co or SnCo. The maximum temperature of the reactor may be 700-1200°C. The feed gas pressure may be 2-30 bar, preferably about 5 bar.

In one embodiment, the endothermic reaction is the aromatization of hydrocarbons. Preferably, the endothermic reaction is the aromatization of higher hydrocarbons.

The following is a detailed description of embodiments of the present invention with reference to the accompanying drawings. Exemplary embodiments are described in sufficient detail to illustrate the invention. However, such a detailed description does not limit possible modifications of the embodiments; on the contrary, the aim is to cover all possible modifications, equivalents and alternatives that fall within the spirit and scope of the present invention, as defined in the appended claims.

Brief description of the figures

In FIG. 1a is a cross-sectional view of a reactor system of the invention with a structured catalyst comprising a set of macroscopic structures, in accordance with one embodiment of the invention;

in fig. 1b shows a reactor system which is also shown in FIG. 1a, while in FIG. 1b part of the pressure vessel and thermal insulation layer has been removed;

in fig. 2 is an enlarged view of part of the reactor system;

in fig. 3a and 3b are cross-sectional views of a reactor system including a structured catalyst, in accordance with one embodiment of the invention;

in fig. 4 and 5 show an embodiment of a structured catalyst with a set of macroscopic structures, top and side views, respectively;

in fig. 6 shows an embodiment of the structured catalyst of the invention;

in fig. 7, 8 and 9 show embodiments of a structured catalyst with connectors;

in fig. 10 shows the required maximum temperature in the reactor system according to the invention as a function of pressure; and in FIG. 11 is a graph of the approach to equilibrium conditions (AT _app , _SMR ) of the methane steam reforming reaction for various rates of gas flow through the structured catalyst.

Detailed description of the figures

Throughout the figures, reference numbers refer to the respective elements.

In FIG. 1 is a cross-sectional view of a reactor system 100 in accordance with one embodiment of the invention. The reactor system 100 includes a structured catalyst 10 arranged as a set of macroscopic structures 5. Each macroscopic structure 5 in the set has a ceramic coating impregnated with a catalytically active material. In addition, the reactor system 100 includes conductors 40, 40' connected to a power source (not shown in the figures) and to a structured catalyst 10, namely to a set of macroscopic structures. The conductors 40, 40' pass through the wall of the pressure vessel 20 containing the structured catalyst and through the insulating material 30 on the inside of the pressure vessel through fittings 50. The conductors 40' are connected to the set of macroscopic structures 5 via conductor busbars 41.

In one of the embodiments of the invention, a power supply with a voltage of 26 V and a current of 1200 A is used. In another embodiment of the invention, a power supply with a voltage of 5 V and a current of 240 A is used. and the current passes through the structured catalyst 10 from a single conductor bar 41, for example from a conductor bar which in FIG. 1a is shown on the left, up to another conductor bar 41, for example a conductor bar, which in FIG. 1a is shown on the right. The current may be variable and, for example, flow alternately in both directions, or it may be constant and flow in one of the two directions.

The macroscopic structures 5 are made of an electrically conductive material. Particularly preferred is a kanthal alloy consisting of aluminium, iron and chromium. The ceramic coating, such as an oxide, deposited on the structured catalyst 5 is impregnated with a catalytically active material. The conductors 40, 40' are made of materials such as iron, aluminium, nickel, copper or their alloys.

During operation, the source gas is fed into the reactor system 100 from above, as indicated by arrow 11, and exits the reactor system from below, as indicated by arrow 12.

In FIG. 1b shows a reactor system 100, which is also shown in FIG. 1a, while in FIG. 1b, part of the pressure vessel 20 and the thermal insulation layer 30 have been removed, and in FIG. 2 is an enlarged view of a portion of reactor system 100. FIG. 1b and 2 the connections between the conductors 40' and the contact bars 41 of the conductor are shown more clearly than in FIG. 1a. In addition, it can be seen that the conductors 40 pass through the walls of the pressure vessel by means of the fitting 50, and that inside the pressure vessel one conductor 40 is divided into three conductors 40'. It should be noted that any suitable number of conductors 40' may be used, for example less than three or more than three conductors may be used.

In the reactor system shown in FIG. 1a, 1b and 2, the conductors 40, 40' pass through the wall of the pressure vessel 20 containing the structured catalyst and through the insulating material 30 on the inside of the pressure vessel through the fittings 50. The steam reforming feed gas is fed into the reactor system 100 through the inlet opening at the top of reactor system 100, shown by arrow 11, and the reformed gas leaves reactor system 100 through an outlet at bottom of reactor system 100, shown by arrow 12. preferably one or more additional inlets are located (not shown in Figs. 1a-2). Such additional inlets allow refrigerant gas to pass through, around, adjacent to, or within at least one conductor within said pressure vessel to reduce heating of the fitting. The cooling gas may, for example, be hydrogen, nitrogen, steam, carbon dioxide or mixtures thereof. The temperature of the cooling gas at the supply to the pressure vessel may be, for example, approximately 100°C.

In the reactor system 100 shown in FIG. 1a-2, between the bottom of the structured catalyst 10 and the bottom of the pressure vessel there is predominantly an inert material (not shown in FIGS. 1a-2). Moreover, an inert material is preferably present between the outer sides of the structured catalyst 10 of the macroscopic structures 5 and the insulating material 30. Thus, one side of the insulating material 30 faces the inside of the pressure vessel 20 and the other side of the insulating material 30 faces the inert material. The inert material is, for example, a ceramic material. The inert material may be in the form of granules. The inert material assists in controlling the pressure drop across the reactor system 100 and controlling the flow of gas through the reactor system 100 so that the gas flow flows over the surfaces of the structured catalyst 10.

In FIG. 3a and 3b show a schematic cross-sectional view of a reactor system 100', 100' comprising a structured catalyst 10' in accordance with one embodiment of the invention. The structured catalyst 10' may be comprised of a single ceramic-coated macroscopic structure that acts as a support for the catalytically active material, or the structured catalyst may include two or more macroscopic structures. Each of the reactor systems 100', 100' includes a pressure vessel 20 and a heat insulating layer 80 between the structured catalyst 10' and the pressure vessel 20. An inert material 90 may be used to fill the gap between the structured catalyst 10' and the heat insulating layer or pressure vessel 20. In FIG. 3a and 3b, inert material 90 is indicated by hatching; the inert material 90 may be in any suitable form, such as inert granules, and may be, for example, a ceramic material. The inert material 90 helps control the pressure drop in the reactor system and control the gas flow through

- 13 041440 reactor system. In addition, the inert material generally has a heat-insulating effect.

From FIG. 3a and 3b it can be seen that the reactor systems 100', 100 additionally comprise an inner tube 15, heat exchange between it and the structured catalyst 10'. The inner tube 15 is adapted to withdraw the gaseous product from the structured catalyst 10' in such a way that the gaseous product entering through the inner tube or pipes is heat exchanged with the gas entering over the structured catalyst; however, the inner tube 15 is electrically isolated from the structured catalyst 10' by an insulating layer 80 or an inert material 90 or a gap, or a combination thereof. This configuration is referred to as a bayonet reactor system. In this configuration, the product gas in the inner tube contributes to the heating of the process gas entering through the macroscopic structure. In the configurations shown in FIG. 3a and 3b, the feed gas is fed into the reactor system 100', 100 as indicated by arrow 11 and enters the structured catalyst 10' as indicated by arrows 13. While the feed gas passes over the structured catalyst 10', a feed gas steam reforming reaction is carried out. The gas exiting the structured catalyst 10' is at least partially reacted in the reforming reaction. The at least partially reformed gas flows from the structured catalyst 10' into the inner tube 15 as indicated by arrows 14 and exits the inner tube as indicated by arrows 12. Even though there is a thermal insulation layer 80, there will be some heat transfer from the gas inside the inner tube 15 and the gas inside the structured catalyst 10' or downstream of the structured catalyst 10'. In the embodiments shown in FIG. 3a and 3b, the feed gas flows down through the structured catalyst 10' and then up through the inner tube 15; however, the reverse configuration is also possible so that the feed gas will flow upwards through the structured catalyst 10' and downwards through the inner tube 15.

In FIG. 4 and 5 show an embodiment of a structured catalyst including a set of macroscopic structures, top and side views, respectively. In FIG. 4 shows a structured catalyst 10 including a set of macroscopic structures 5, viewed from above, namely the view along the direction of the arrow 11 in FIG. 1a and 1b. This set has 6 rows, namely 1a, 1b, 1c, 1d, 1e and 1f of five macroscopic structures 5. Macroscopic structures 5 in each row are connected to an adjacent macroscopic structure in the same row, and the two extreme macroscopic structures in each row are connected to contact bus 41 conductor. Neighboring macroscopic structures 5 in a row of macroscopic structures are connected to each other by means of a connecting element 3.

In FIG. 5 shows a structured catalyst 10 having the set of macroscopic structures 5 shown in FIG. 4, side view. In FIG. 5 it can be seen that each macroscopic structure 5 extends in the longitudinal direction perpendicular to the cross section shown in FIG. 4. Each macroscopic structure 5 has a slot 60 cut in the longitudinal direction relative to the macroscopic structure (see Fig. 5). Therefore, the current from the power supply is fed into the set of macroscopic structures 5 through the conductor strip 41, passes through the first macroscopic structure 5 down to the bottom of the slot 60 and then is supplied upwards to the connecting element 3. The current follows a corresponding zigzag path down and up through each macroscopic structure 5 in each row 1a-1f of macroscopic structures 5 in the set 10. The advantage of this configuration is that in this case the resistance increases compared to the structured catalyst 10.

In FIG. 6 shows a perspective view of the structured catalyst 10' of the present invention. Structured catalyst 10' contains a macroscopic structure that has a ceramic coating impregnated with a catalytically active material. Within the structured catalyst there are channels 70 extending in the longitudinal direction (shown by an arrow labeled h in FIG. 6) of the macroscopic structure 5, these channels are delimited by walls 75. In the embodiment shown in FIG. 6, walls 75 form a series of parallel square channels 70 as viewed from the direction of flow indicated by arrow 12. Structured catalyst 10' has a substantially square (when viewed from above) perimeter defined by edges e1 and e2. However, the perimeter can also be circular or have a different shape.

The walls 75 of the structured catalyst 10 are made of an extruded or 3D printed material with a ceramic coating, such as an oxide, deposited on a macroscopic structure in the form of a coating. The ceramic coating is not shown in the figures. The ceramic coating is impregnated with a catalytically active material. A ceramic coating, and hence catalytically active material, is present on each wall of the structured catalyst 10', which carries a gas flow during reactor operation and interacts with the heated surface of the structured catalyst and catalytically active material.

Thus, in a steam reforming reactor system, the hydrocarbon feed gas passes through channels 70 and interacts with the heated surface of the structured catalyst and with the catalytically active material located on the ceramic coating substrate.

- 14 041440

In the structured catalyst 10 shown in FIG. 6, there is a slot 60. Due to this slot 60, the current flows inside the macroscopic structure in a zigzag way (in this case down and then up), as a result of which the current path increases and therefore the resistance increases and therefore the amount of heat increases, which is given to the macroscopic structure. An insulating material may be incorporated into slot 60 within the macroscopic structure to ensure that no current flows in a direction transverse to slot 60.

The channels 70 in the structured catalyst 10 are open at both ends. When using a structured catalyst in a reactor system, the hydrocarbon feed gas flows through the plant in the direction shown by arrows 11 and 12 in FIG. 1a and 1b and is heated by contact with the walls 75 of the channels 70 and by radiation heating. Due to the heat, the necessary steam reforming process is initiated. The thickness of the walls 75 of the channels 70 may be, for example, 0.5 mm, and the thickness of the ceramic coating applied to the walls 75 may be, for example, 0.1 mm. While arrows 11 and 12 (see FIGS. 1a and 1b) indicate that the hydrocarbon feed gas flow is directed downward, the opposite direction of flow is also possible, namely the flow may be directed upward.

In FIG. 7 is a view of the structured catalyst 10 of FIG. 1a and 1b are perspective views with connectors 7 attached. Each connector 7 connects a portion of the structured catalyst 10 to a conductor 40. Both conductors 40 are connected to a power source (not shown). Each of the connectors 7 is connected to the top of the structured catalyst. When the conductors 40 are connected to a power source, the current is supplied to the corresponding connector 7 through the conductor and passes through the structured catalyst 10. The slot 60 prevents the passage of current in the transverse direction (horizontal direction in Fig. 7) along its entire length along the height h of the structured catalyst 10. Therefore, the current flows in downwards, as shown in Fig. 7 in the portion of the structured catalyst along slot 60, then it extends perpendicular to the longitudinal axis of the structured catalyst under slot 60 as shown in FIG. 7, and finally the current flows upward, parallel to the longitudinal axis of the structured catalyst, to another connector 7. The connectors 7 in FIG. 7 are mechanically attached to the structured catalyst, in particular by means of mechanical fasteners such as screws and bolts. However, additional or alternative fasteners are possible. In one of the embodiments of the invention, a power supply with a voltage of 3 V and a current of 400 A is used. The conductors 7 are made, for example, from materials such as iron, aluminum, nickel, copper, or their alloys.

As already indicated, the structured catalyst 10 has a ceramic coating, such as an oxide, which acts as a support for the catalytically active material. However, the parts of the structured catalyst 10 that are connected to the connectors 7 must not be coated with oxide. Instead, the macroscopic structure of the structured catalyst must be in direct contact with or connected to the connectors 7 in order to provide the necessary electrical contact between the macroscopic structure and the connector.

When the connectors 7 and hence the conductors 40 are connected to one part of the structured catalyst 10, i. e. towards the top, as shown in Fig. 7, the gas fed into the reactor system containing the structured catalyst 10 will be able to cool the connectors 7 and the conductors 40. will allow connectors 7 and conductors 40 to reach temperatures much higher than this temperature.

In FIG. 8 shows an alternative embodiment of a structured catalyst 10' with connectors 7' attached. The structured catalyst 10' shown in FIG. 8 has a square cross section like the structured catalyst 10 shown in FIG. 6 and 7, but the structured catalyst 10' in FIG. 8 has no slots. At the top and bottom of the macroscopic structure 10' is a conductor 40. The conductor 40 may be made of nickel, for example. Alternatively, other suitable metals or alloys such as FeCrAlloy can be used as current distributors. To direct the current through the structured catalyst 10', ie through the macroscopic structure, connectors 7', 7 in the form of electrically conductive bars are used. Connectors 7', 7 are attached to conductors 40 and structured catalyst 10' by means of mechanical fasteners; however, additional or alternative fasteners are also possible.

The connectors 7 at the bottom of the structured catalyst 10' and the connectors 7' at the top of the structured catalyst 10' can be made from various materials, as shown in FIG. 2. For example, connectors 7' may be copper and connectors 7 nickel. Since the conductivity of nickel is lower than that of copper, the connectors 7 are larger than the connectors 7'.

The embodiment shown in FIG. 8, suitable for temperatures below 800°C, such as 600-700°C.

In FIG. 9 shows another embodiment of a structured catalyst 10' with connectors 7'. The structured catalyst 10' is, for example, a structured

- 15 041440 the catalyst shown in FIG. 6. Each of the connectors 7' has three holes at its top for connection to conductors (not shown). Inside the slot 60 of the structured catalyst 10' is a piece of electrically insulating material 61 (see Fig. 6).

In FIG. 10 shows the required maximum temperature within the reactor system of the invention as a function of pressure for pressures in the range of approximately 30-170 bar during steam reforming of a feed gas of 30.08% CH ₄ , 69.18% H2O, 0.09% H2, 0.45% CO2, 0.03% Ar, 0.02% CO, 0.15% N2 until a methane conversion of 88% is achieved at 10°C under near-equilibrium methane steam reforming conditions. The required maximum temperature increases with increasing pressure due to Le Chatelier's principle. This shows that due to the high temperatures that can be used in the present invention, significantly higher pressures can be used than those used in traditional SMR where, due to external heating of the tubes, temperatures above 950°C cannot be used. A temperature of 950°C corresponds to 27 barg. in fig. 10. The reactor system according to the invention can use, for example, a maximum temperature of 1150°C, which provides a pressure of up to 146 barg. while maintaining the above degree of methane conversion.

The general trend for all curves in Fig. 11 is that the temperature for near-equilibrium conditions continuously decreases from entering the structured catalyst until pseudo-equilibrium is reached, when heat supply and heat consumption are approximately equal to each other. From this point on, the temperature of approach to equilibrium conditions remains practically constant or slightly increases due to the general increase in the temperature of the reactor system. For example, at a flow rate of 150,000 Nm ³ /h, the temperature approaching equilibrium drops below 60°C for about 80% of the length of the reactor system, but subsequently increases to about 60°C.

Examples

The invention is illustrated by the description of various embodiments and examples, and although these embodiments and examples are described in some detail, the Applicant does not intend to limit the scope of the appended claims to such a detailed description. Additional advantages and possible modifications will be apparent to those skilled in the art. Therefore, the invention in general aspects is not limited to the given specific details, typical methods and illustrative examples. Accordingly, deviations from such details are permissible without distorting the essence or scope of the Applicant's general inventive concept.

All the examples described below refer to compact reactor systems. This is possible due to the fact that the reactor systems contain compact structured catalysts with a high heat flux when electrically heated. In addition, it should be noted that the dimensions of the structured catalysts can be chosen relatively freely, so that the structured catalyst may have an almost cubic external shape, or its width may be greater than its height.

All examples describe high pressure operating conditions in the range of 28-182 bar. Such high pressures are possible due to the design of the reactor system because the structured catalyst within the reactor system has a high heat flux when electrically heated, it is thermally insulated to some extent from the pressure vessel, and there is no pressure drop or a very low pressure drop in the structured catalyst. In a reactor system, the structured catalyst will have the highest temperature, while the pressure vessel will have a significantly lower temperature due to the thermal insulation layer between the macroscopic structure and the pressure vessel. Ideally, the temperature of the pressure vessel should not exceed 500°C. When a high pressure product gas, such as 30 bar or higher, is required, the product gas leaving the reactor system can often be used directly without the use of compressors. This is possible due to the stage of compression of the source gas during the process before the reactor system according to the invention.

In all of the examples below, steam reforming is used as an example, where the feed gas enters the reactor system and passes through the structured catalyst inside it. When the reactor system has a heat insulating material, the heat insulating material typically occupies most of the space between the structured catalyst and the pressure vessel along the walls of the pressure vessel, so that when passing through the pressure vessel, the feed gas is forced to flow along the walls of the macroscopic structure.

All of the examples below (with the exception of the comparative example) refer to a structured catalyst reactor system for steam reforming. The structured catalysts described in these examples include one or more macroscopic structures. In the examples below, one or more macroscopic structures are provided with a ceramic coating, said ceramic coating acting as a support for the catalytically active material. Preferably, almost the entire surface of the macroscopic structure has a ceramic coating acting as a substrate for the catalytically active material; however, at connection points, for example, at the junction point of two adjacent macroscopic structures or at the junction point of a macroscopic structure and a conductor, the macroscopic structure may not

- 16 041440 have a ceramic coating to simplify the connection between the conductor and the macroscopic structure.

Example 1

In table. 1 below is an example of calculating the parameters of the method according to the invention. The reactor system of the invention is fed with a hydrocarbon feed stream containing, among other things, hydrocarbon gas, hydrogen and steam. The feed stream entering the reactor system is at a pressure of 28 kg/cm-g and has a temperature of 500°C. The structured catalyst is placed inside the reactor system as a set of nine macroscopic structures with a square cross section, and each macroscopic structure has a size of 0.53x0.53x2.3 m. Each macroscopic structure additionally has 17778 channels with a square cross section and with a side or edge length of 0, 32 cm. Each macroscopic structure has slots parallel to its longitudinal direction, so that 5 groups of 5 channels are formed. Each group of channels is isolated from the next, except for the end portions, so that the current flows through the structured catalyst in a zigzag path. Each macroscopic structure in the reactor system of the invention is subjected to a current of 200 A and a voltage of approximately 5.5 kW to heat the structured catalyst and hence the gas passing through the structured catalyst, corresponding to an input power of 9899 kW.

The total internal diameter of the reactor system in this configuration may be 3.2 m and the total internal height 5.5 m if the reactor system is cylindrical with spherical heads. In this particular configuration, the macroscopic structures are arranged in a square with a diagonal length of 2.3 m. In all the examples described here, except for the comparative example, an inert material is located around the structured catalyst, closing the gap between the insulating material adjacent to the pressure vessel. The insulating material in example 1 has a cylindrical shape with an inner diameter of 2.5 m and a thickness of 0.35 m.

During the passage of the feed gas through the reactor system, the feed gas is heated by the heat of the structured catalyst, and a steam reforming reaction is carried out to obtain a gaseous product with an outlet temperature of 963°C.

Table 1

Structured Catalyst Size: Edge length [m] 0.53 Height [m] 2.3 Quantity macroscopic structures 9 Total volume [l] 5888 T[°C] Pressure [kg/ ^cm2g ] CO2 [ ^nm3 /h] N2 [ ^nm3 /h] CH4 [ ^nm3 /h] H2 [ ^nm3 /h] CO [ ^nm3 /h] Feed gas 500 27.97 168 26 2630 590 1 Gaseous product 963 27.47 727 26 164 8545 1907 H2O [nm ³ /h] 8046 5022 Total flow (nm ³ /h) 11461 16391 AT _paBHj sMR [°C] 10 Power [kW] Heat flow [kW/m ² ] 9899 2.2

Example 2

In table. 2 below is an example of calculating the parameters of the method according to the invention. The reactor system of the invention is fed with a hydrocarbon feed stream containing, among other things, hydrocarbon gas, hydrogen and steam. The initial stream entering the reactor system is under pressure of 28 kg/cm ² -g and has a temperature of 500°C. Inside the reactor system, a structured catalyst is placed in the form of a single macroscopic structure with a square cross section with a size of 0.4x0.4x0.35 m. The structured catalyst additionally has 10,000 channels with a square section and with a side or edge length of 0.32 cm. The structured catalyst has slots parallel to its longitudinal direction, so that 5 groups of 5 channels are formed. Each group of channels is isolated from the next, except for the end portions, so that the current flows through the structured catalyst in a zigzag path. The structured catalyst in the reactor system of the invention is subjected to a current of 200 A and a voltage of approximately 500 V to heat the structured catalyst and hence the gas passing over the structured catalyst, corresponding to an input power of 99 kW.

- 17 041440

The overall internal diameter of the reactor system in this configuration may be 1.2 m and the overall internal height 1.5 m if the reactor system is cylindrical with spherical heads. In this particular configuration, the diagonal of the structured catalyst has a length of 0.6 m. Surrounding the structured catalysts is an inert material covering the gap between an insulating material with an internal diameter of 0.6 m and a thickness of 0.3 m.

During the passage of the feed gas through the reactor system, the feed gas is heated by the heat of the structured catalyst, and a steam reforming reaction is carried out to obtain a gaseous product with an outlet temperature of 963°C.

table 2

Structured Catalyst Size: Edge length [m] 0.4 Height [m] 0.35 Number of macroscopic structures 1 Total volume [l] 55.4 source gas gaseous product T[°C] 500 963 Pressure [kg/ ^cm2g ] 27.97 27.47 CO2 [nm ³ /h] 1.7 7.3 N2 [nm ³ /h] oh, s oh, s CH4 [nm ³ /h] 26.3 1.6 H2 [nm ³ /h] 5.9 85.4 CO [nm ³ /h] 0 19.1 H2O [nm ³ /h] 80.5 50.2 Total flow (nm ³ /h) 114.7 163.9 ATp; _IP ,HS\1R [°C] 10 Power [kW] Heat flow [kW/m ² ] 99 2.2

Example 3

In table. 3 below is an example of calculating the parameters of the method according to the invention. The reactor system of the invention is fed with a hydrocarbon feed stream containing, among other things, hydrocarbon gas, hydrogen and steam. The feed stream entering the reactor system is at a pressure of 97 bar, i.e. 97 kg/cm-g and has a temperature of 500°C.

A structured catalyst is placed inside the reactor system with a set of nine macroscopic structures with a square cross section, and each macroscopic structure has a size of 0.53x0.53x2.3 m. Each macroscopic structure additionally has 17778 channels with a square cross section and with a side or edge length of 0, 32 cm. Each macroscopic structure has slots parallel to its longitudinal direction, so that 5 groups of 5 channels are formed. Each group of channels is isolated from the next, except for the end portions, so that the current flows through the structured catalyst in a zigzag path. Each macroscopic structure in the reactor system of the invention is subjected to a current of 200 A and a voltage of approximately 5.5 kW to heat the structured catalyst and hence the gas passing over the structured catalyst, corresponding to an input power of 9899 kW.

The total internal diameter of the reactor system in this configuration may be 3.2 m and the total internal height 5.5 m if the reactor system is cylindrical with spherical heads. In this particular configuration, the structured catalysts are arranged in a square with a diagonal length of 2.3 m. Around the structured catalysts is an inert material that closes the gap between the insulating material with an internal diameter of 2.5 m and a thickness of 0.35 m.

During the passage of the feed gas through the reactor system, the feed gas is heated by the heat of the structured catalyst, and a steam reforming reaction is carried out to obtain a gaseous product with an outlet temperature of 1115°C. From Table. 3 it can be seen that the total flow rates of the source gas and the gaseous product in example 3 are lower compared to example 1.

Since the product gas leaving the reactor system has a pressure of 97 bar, it is not necessary to use compressors downstream of the reactor system during the process if a high pressure product gas is required. This greatly reduces the overall cost of the installation with the reactor system according to the invention.

- 18 041440

Table 3

Structured Catalyst Size: Edge length [m] 0.53 Height [m] 2.3 Quantity macroscopic structures 9 Total volume [l] 5888 source gas gaseous product T [°C] 500 1115 Pressure [kg/ ^cm2g ] 96.97 96.47 CO2 [nm ³ /h] 111 510 N2 [nm ³ /h] 23 23 CH4 [nm ³ /h] 2337 143 H2 [nm ³ /h] 372 7354 CO [nm ³ /h] 1 1796 H2O [nm ³ /h] 7111 4518 Total flow (nm ³ /h) 9955 14344 AT _paBH ,sMR [°C] 10 Power [kW] Heat flow [kW/m ² ] 9899 2.2

Example 4

In table. 3 below is an example of calculating the parameters of the method according to the invention. The reactor system of the invention is fed with a hydrocarbon feed stream containing, among other things, hydrocarbon gas, hydrogen and steam. The feed stream entering the reactor system is at a pressure of 28 bar, i.e. 28 kg/cm ² -g and has a temperature of 500°C.

A structured catalyst is placed inside the reactor system with a set of 25 macroscopic structures with a square cross section, and each macroscopic structure has a size of 0.24x0.24x1.8 m. Each macroscopic structure additionally has 4702 channels with a square cross section and with a side or edge length of 0, 33 cm. Each macroscopic structure has slots parallel to its longitudinal direction, so that 10 groups of 10 channels are formed. Each group of channels is isolated from the next, except for the end portions, so that the current flows through the structured catalyst in a zigzag path. Each macroscopic structure in the reactor system of the invention is subjected to a current of 500 A and a voltage of approximately 792 kW to heat the structured catalyst and hence the gas passing over the structured catalyst, corresponding to an input power of 9899 kW.

The total internal diameter of the reactor system in this configuration may be 2.3 m and the total internal height 4.1 m if the reactor system is cylindrical with spherical heads. In this particular configuration, the structured catalysts are arranged in a square with a diagonal length of 1.7 m. Around the structured catalysts is an inert material that closes the gap between the insulating material with an internal diameter of 1.8 m and a thickness of 0.25 m.

During the passage of the feed gas through the reactor system, the feed gas is heated by the heat of the structured catalyst, and a steam reforming reaction is carried out to obtain a gaseous product with an exit temperature of 963 °C. From Table. 4 shows that the structured catalyst according to example 4 has a slightly smaller size than the structured catalyst according to examples 1 and 3 due to the higher current strength. The total flow rates of feed gas and product gas correspond to those of Example 1.

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Table 4

Structured Size catalyst: Edge length [m] 0.24 Height [m] 1.8 Number of macroscopic structures 25 Total volume [l] 2562 source gas gaseous product T[°C] 500 963 Pressure [kg/ ^cm2g ] 27.97 27.47 CO2 [nm ³ /h] 168 727 N2 [nm ³ /h] 26 26 CH4 [nm ³ /h] 2630 164 H2 [nm ³ /h] 590 8545 CO [nm ³ /h] 1 1907 H2O [nm ³ /h] 8046 5022 Total flow (nm ³ /h) 11461 16391 ATpaBH.SMR [°C] 10 Power [kW] Heat flow [kW/m ² ] 9899 3.6

Example 5

In table. 4 below is an example of calculating the parameters of the method according to the invention. The reactor system of the invention is fed with a hydrocarbon feed stream containing, among other things, hydrocarbon gas, hydrogen and steam. The feed stream entering the reactor system is at a pressure of 182 bar and has a temperature of 500°C.

A structured catalyst is placed inside the reactor system with a set of nine macroscopic structures with a square cross section, and each macroscopic structure has a size of 0.53x0.53x2.3 m. Each macroscopic structure additionally has 17778 channels with a square cross section and with a side or edge length of 0, 32 cm. Each macroscopic structure has slots parallel to its longitudinal direction, so that 5 groups of 5 channels are formed. Each group of channels is isolated from the next, except for the end portions, so that the current flows through the structured catalyst in a zigzag path. Each macroscopic structure in the reactor system of the invention is subjected to a current of 200 A and a voltage of approximately 5.5 kW to heat the structured catalyst and hence the gas passing over the structured catalyst, corresponding to an input power of 9899 kW.

The total internal diameter of the reactor system in this configuration may be 3.2 m and the total internal height 5.5 m if the reactor system is cylindrical with spherical heads. In this particular configuration, the structured catalysts are arranged in a square with a diagonal length of 2.3 m. Around the structured catalysts is an inert material that closes the gap between the insulating material with an internal diameter of 2.5 m and a thickness of 0.35 m.

During the passage of the feed gas through the reactor system, the feed gas is heated by the heat of the structured catalyst, and a steam reforming reaction is carried out to obtain a gaseous product with an outlet temperature of 1236°C. The overall flow rates of the source gas and the gaseous product are lower compared to examples 1 and 4.

Since the gaseous product leaving the reactor system is already at a pressure of 181 bar, it can be fed, for example, to an ammonia plant without further compression. Thus, compressors are not required between the reactor system and the ammonia synthesis loop. This significantly reduces the overall cost of the installation with the reactor system according to the invention and the ammonia synthesis loop.

-20041440

Table 5

Structured Size catalyst: Edge length [m] 0.53 Height [m] 2.3 Number of macroscopic structures 9 Total volume [l] 5888 source gas gaseous product T[°C] 500 1236 Pressure [kg/ ^cm2g ] 181.97 181 CO2 [nm ³ /h] 86 395 N2 [nm ³ /h] 21 21 CH4 [nm ³ /h] 2116 96 H2 [nm ³ /h] 278 6648 CO [nm ³ /h] 0 1711 H2O [nm ³ /h] 6425 4096 Total flow (nm ³ /h) 8926 12967 4Tpa _BH ,SMR [°C] 10 Power [kW] Heat flow [kW/m ² ] 9899 2.2

Example 6

Example 6 refers to a reactor system containing a structured catalyst in the form of a macroscopic structure with 78540 channels with a total wall length of each channel in cross section of 0.00628 m and a wall length of 2 m, thus the total surface area of the catalyst is 987 m ² . For a reactor system with such a structured catalyst, simulations were performed with varying gas flow over a structured catalyst, with gas with the following composition used in all calculations: 8.8% H ₂ , 56.8% H ₂ O, 0.2% N ₂ , 0.1% CO, 2.3% CO ₂ , and 31.8% CH ₄ . In each simulation, a kinetic model was used for steam reforming and water gas shift, and changing the surface energy flux (Q) from the electrically heated structured catalyst to 920°C was performed to control the temperature of the gaseous product leaving the reactor system containing the structured catalyst. . A kinetic model was used similar to that used by Xu and Froment, (J. Xu and GF Froment, Methane steam reforming, methanation and water-gas shift: I. intrinsic kinetics. American Institution of Chemical Engineers Journal, 35:88-96, 1989.). In FIG. 11 shows the temperature approaching equilibrium conditions along the length of the reactor system at various total flow rates. The figure shows that at low feed gas flow rates (10,000 Nm ³ /h), the temperature approaching equilibrium conditions at the outlet of the reactor system is less than 5°C, because of this, the degree of hydrocarbon conversion is 77%, while at high flow rate (150,000 nm ³ /h), the temperature approaching equilibrium conditions is more than 60°C, which corresponds to a degree of hydrocarbon conversion of only 64%, so the use of hydrocarbons is less efficient. Thus, due to the precise control of the heat flow, the present invention provides control of the temperature approaching equilibrium conditions along the entire length of the reactor system. The general trend for all curves in Fig. 11 is that the temperature for conditions close to equilibrium is continuously reduced until pseudo-equilibrium is reached, when the heat supply and heat consumption are approximately equal to each other. From this point on, the temperature approaching equilibrium conditions remains practically constant or increases slightly due to the overall increase in the temperature of the reactor system.

Example 7

In table. 6 below is an example of calculating the parameters of the method according to the invention. The reactor system of the invention is fed with a hydrocarbon feed stream containing, among other things, hydrocarbon gas and hydrogen. The feed stream entering the reactor system is at a pressure of 3.2 bar, i.e. 3.2 kg/cm ² -g and has a temperature of 500°C.

A structured catalyst is placed inside the reactor system with a set of 25 macroscopic structures with a square cross section, and each macroscopic structure has a size of 0.24x0.24x1.8 m. Each macroscopic structure additionally has 4702 channels with a square cross section and with a side or edge length of 0, 33 cm. Each macroscopic structure has slots parallel to its longitudinal direction, so that 10 groups of 10 channels are formed. Each group of channels is isolated from the next, except for the end parts, so that the current flows through

Claims (18)

structured catalyst in a zigzag path. Each macroscopic structure in the reactor system of the invention is subjected to a current of 500 A and a voltage of approximately 787 kW to heat the structured catalyst and hence the gas passing over the structured catalyst, corresponding to an input power of 9858 kW. The overall internal diameter of the reactor system in this configuration is 2.3 m and the overall internal height is 4.1 m if the reactor system is cylindrical with spherical heads. In this particular configuration, the structured catalyst is located in a square with a diagonal length of 1.7 m. Around the structured catalyst is an inert material that closes the gap between the insulating material with an internal diameter of 1.8 m and a thickness of 0.25 m. During the passage of the feed gas through the reactor system, the feed gas is heated by the heat of the structured catalyst, and propane dehydrogenation reaction and thermal cracking are carried out to obtain a gaseous product with an outlet temperature of 600°C. Table 6 Structured catalyst size: Edge length [m] Height [m] Number of macroscopic structures Total volume [l] T [°C] Pressure [kg/cm ² g] C ₃ H ₈ [nm ³ /h] N ₂ [nm ³ /h] N ₂ [nm ³ /h] CsN ₆ [nm ³ /h] 0.24 1.8 25 2562 Feed gas 500 3.24 18918 0.0 9450 0 Product gas 600 2.73 14747 0.0 12739 3721 CH ₄ [nm ³ /h] 43 487 C ₂ H ₆ [nm ³ /h] 1338 1767 C ₂ H ₄ [nm ³ /h] 19 33 Total flow (nm ³ /h) 29770 33495.8 DTarrl [°C] Power [kW] Heat flux [kW/ ^m2 ] 9858 3.59 CLAIM 1. A reactor system for carrying out an endothermic reaction of the source gas, including a structured catalyst designed to catalyze the specified endothermic reaction of the specified source gas, while the specified structured catalyst contains a macroscopic structure of an electrically conductive material, while a ceramic coating is located on the specified macroscopic structure, while the specified the ceramic coating acts as a support for the catalytically active material; a high pressure housing in which said structured catalyst is located; a heat-insulating layer between said structured catalyst and said pressure vessel; and at least two conductors electrically connected to said structured catalyst and to a power source that is located outside of said pressure vessel, said power source being configured to heat at least a portion of said structured catalyst to a temperature of at least 200° C by passing an electric current through said electrically conductive material; wherein said pressure vessel includes an inlet for introducing a process gas and an outlet for removing a gaseous product, wherein said inlet is located adjacent to the front of the pressure vessel and the outlet is located adjacent to the rear of the pressure vessel, wherein at least at least two conductors are connected to the structured catalyst at a point on the structured catalyst closer to the inlet than to the outlet; and moreover, the structured catalyst has electrically insulating parts located between the conductors, preventing the passage of the specified current through some part of the structured catalyst. 2. The reactor system according to claim 1, characterized in that the design pressure of the high pressure vessel is - 22 041440 The range is 2-30 bar. 3. Reactor system according to claim 1, characterized in that the design pressure of the pressure vessel is in the range of 30-200 bar. 4. Reactor system according to any one of claims 1 to 3, characterized in that the resistivity of the electrically conductive material is in the range of 10' ⁵ -10' ⁷ Qm. 5. Reactor system according to any one of claims 1 to 4, characterized in that said at least two conductors pass through the pressure vessel in the fitting in such a way that at least two conductors are electrically isolated from the pressure vessel. 6. The reactor system according to claim 5, characterized in that said pressure vessel further includes one or more inlets located adjacent to or in combination with at least one fitting to allow the passage of cooling gas through, around, adjacent to or inside the at least one conductor inside said pressure vessel. 7. Reactor system according to any one of claims 1 to 6, characterized in that it further comprises an inner tube between which heat exchange takes place and the structured catalyst, but which is electrically isolated from the structured catalyst, said inner tube being configured to remove gaseous product from the structured catalyst. catalyst in such a way that between the gaseous product entering through the inner tube, heat exchange is carried out with the gas entering through the structured catalyst. 8. Reactor system according to any one of claims 1 to 7, characterized in that the connection between the structured catalyst and said at least two conductors is a mechanical connection, a welded connection, a soldered connection, or a combination thereof. 9. The reactor system according to any one of claims 1 to 8, characterized in that the electrically conductive material contains a macroscopic structure, which is made by 3D printing technology or by extrusion and sintering, while a ceramic coating is located on said macroscopic structure, while said ceramic coating acts as a support for the catalytically active material. 10. Reactor system according to any one of claims 1 to 9, characterized in that the structured catalyst comprises a set of macroscopic structures electrically connected to each other. 11. Reactor system according to any one of claims 9 or 10, characterized in that said macroscopic structure has a plurality of parallel channels, a plurality of non-parallel channels and/or a plurality of labyrinthine channels. 12. Reactor system according to any one of claims 1 to 11, characterized in that it further comprises a layer of a second catalytic material in the course of the process in front of said structured catalyst inside said pressure vessel. 13. The reactor system according to claim 11 or 12, characterized in that it additionally contains a third catalyst material in the form of catalyst grains, extrudates or catalyst granules, which are loaded into the channels of the specified macroscopic structure. 14. The reactor system according to any one of claims 1 to 13, characterized in that it further includes a control system configured to control the supply of electricity to ensure that the temperature of the gas exiting the pressure vessel is within a predetermined range and/or to ensure finding the degree of conversion of the source gas in a predetermined range. 15. Reactor system according to any one of claims 1 to 14, characterized in that in said reactor system the ratio between the equivalent diameter of the horizontal cross-sectional area of the structured catalyst and the height of the structured catalyst is in the range of 0.1-2.0. 16. Reactor system according to any one of claims 1 to 15, characterized in that the height of the reactor system is 0.5-7 m, more preferably 0.5-3 m. 17. The method for carrying out an endothermic reaction of the source gas in the reactor system according to any one of claims 1 to 16, including the following steps: supplying said feed gas to the reactor system by introducing said process gas at a point adjacent to the front of the pressure vessel; providing an endothermic reaction of the source gas over the structured catalyst and the removal of the gaseous product from the reactor system, and the specified gaseous product exits at a point located near the rear of the pressure vessel; and supplying current through conductors connecting a power source located outside said pressure vessel to said structured catalyst, which allows current to be passed through said electrically conductive material, whereby at least a portion of the structured catalyst is heated to a temperature of at least 200 °C 18. The method of claim 17 further comprising compressing said feed gas to a pressure of at least 2 bar and supplying said compressed feed gas to the reactor system by introducing said compressed feed gas at said point adjacent the front -