Reactor and method for the pyrolysis of hydrocarbon-containing fluids
Patent Information
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- THYSSENKRUPP UHDE GMBH
- Filing Date
- 2024-07-24
- Publication Date
- 2026-06-17
Smart Images
Figure EP2024071053_13022025_PF_FP_ABST
Abstract
Description
[0001] Description
[0002] Reactor and process for the pyrolysis of hydrocarbon-containing fluids
[0003] The invention relates to a reactor at least for the pyrolysis of hydrocarbon-containing fluids at least for the production of at least hydrogen-containing fluids, wherein the reactor has a reactor shell and a reactor space arranged within the reactor shell, wherein the reactor has a reactor head and a reactor sump, wherein the reactor head and the reactor sump each have at least temporarily closable feed openings and discharge openings through which at least fluids or solids, in particular particles, are to be introduced or discharged, so that in order to produce a moving bed, particles are at least temporarily continuously introduced into the reactor space through the reactor head.
[0004] In addition, the invention relates to a method at least for the pyrolysis of hydrocarbon-containing fluids at least for producing at least hydrogen-containing fluids, wherein the hydrocarbon-containing fluids are fed to a reactor chamber of a reactor in counterflow to a moving bed of the reactor consisting of particles, wherein at least the particles of the moving bed or the hydrocarbon-containing fluids are heated to a defined temperature in the range between 800-1600°C by means of electrodes arranged in the reactor chamber to generate thermal energy, wherein particles of the moving bed are introduced at a reactor head and wherein particles of the moving bed are discharged at a reactor sump.
[0005] The thermal pyrolysis of methane is a highly endothermic reaction that, kinetically and thermodynamically, occurs preferentially in a temperature range of 1000°C - 1500°C and pressures up to 40 bar. The equilibrium shifts toward the reactant side at higher pressures. For economic reasons, a pressure between 5 and 15 bar, preferably between 10 and 25 bar, is selected. In addition to hydrogen, the thermal cracking also produces pyrolysis carbon, which is an additional valuable product. Carbon can be formulated during the reaction step. If carbon particles are present, the methane pyrolyzes preferentially on the particles. The particle sizes can be adjusted by modifying the size of the particles and the specific carbon deposition. Electrical heat input is particularly suitable for providing the reaction enthalpy.The reactor is resistance-heated by at least one pair of electrodes arranged axially in the particle bed. The electrodes can also be arranged horizontally, for example, on a reactor wall, rather than axially in the fluidized bed.
[0006] The electrical current flows over the carbon bed and, due to the electrical resistance of the particle bed, dissipates into thermal energy. The electrical resistance results from the particle bed or the transfer surfaces, while the carbon particles possess a high electrical conductivity. For a homogeneous heat input into the heating volume, a homogeneous electrical resistance across the entire cross-sectional area of the reactor is required. If paths with differing electrical resistance occur, the electrical current flows preferentially in the areas of low electrical resistance. As a result, the conversions in these areas are higher due to the higher temperatures. Due to the deposits of pyrolytic carbon, the resistance along these "preferred" paths is further reduced. The consequence is hotspots and ultimately a failure of the heating concept.Such a concept is shown, for example, in the document WO 2020 244 803 A1 .
[0007] The invention is therefore based on the object of providing a reactor and a method in which instabilities of the electrical heat input during methane pyrolysis for the production of hydrogen and pyrolysis carbon can be prevented.
[0008] This object is achieved in the present invention by the features of the
[0009] characterizing part of patent claim 1 is initially solved by the fact that in the
[0010] A plurality of conical components are arranged in the reactor chamber, wherein the conical components are hollow and have an inlet opening and an outlet opening, and wherein the inlet opening has a larger diameter than the outlet opening.
[0011] The temporarily closable feed and discharge openings can be designed in various ways. Both manual and automated opening and closing processes are conceivable. First and foremost, it must be ensured that the means used to close the feed and discharge openings are suitable for withstanding the high pressures and temperatures of pyrolysis.
[0012] A moving bed is a bed of granules or particles. It is conceivable that the entire cross-section of the reactor shell is filled. However, it is also conceivable for the moving bed to have an annular cross-section. Continuous discharge of the particles at the reactor bottom ensures a steady downward migration of the moving bed. The particles can be removed and replaced or returned to the reactor chamber at the reactor head. In this case, the reactor chamber refers to the interior of the reactor, including any inlet and outlet zones.
[0013] The conical components serve to achieve relative movement of the particles in the moving bed within the reactor chamber. This avoids paths with differing electrical resistance. The conical components can be designed as a funnel or a conical cylinder. The conical component allows flow along its longitudinal extension, but not in the radial direction.
[0014] The temporarily closable discharge openings can be designed such that they can be opened and closed independently of one another. Particularly preferably, the discharge openings are designed such that they can be opened and closed sequentially, at staggered times. In this case, each discharge opening can be connected to a conical component, so that discharge from one discharge opening occurs through the respective conical component.
[0015] Further preferred embodiments of the invention emerge from the remaining features mentioned in the subclaims.
[0016] In a first embodiment of the reactor according to the invention, the conical components are arranged parallel to one another along their longitudinal extent. This allows the fluid to flow through the conical components along their longitudinal extent, dividing the reactor space into several sections by the conical components. The flow direction is identical for each of the conical components, preventing any flow in different directions.
[0017] In a further embodiment of the reactor according to the invention, it can advantageously be provided that the outlet openings are operatively connected to at least one discharge device through which particles can be conveyed out of the reactor. The discharge device can be, for example, a discharge screw. However, other known devices suitable for discharging particles from the reactor are also conceivable. The discharge device can, for example, be arranged in its conveying direction perpendicular to the conveying direction of the outlet openings or perpendicular to the conveying direction of the conical components. In this way, the particles can be efficiently conveyed out of the active area of the reactor and either further treated or recycled.
[0018] In a further embodiment of the invention, it is provided that dividing walls are arranged in the reactor chamber and that the dividing walls extend radially from the center of the reactor chamber to the reactor shell, such that the reactor chamber is at least partially segmented by the dividing walls. By further segmenting the reactor chamber, the shearing of the particles can be shifted in the axial direction. For example, it can be provided that the dividing walls are arranged upstream of the conical components in the conveying direction or flow direction of the particles. This extends the length of the shear zone. Without the dividing walls, the shearing is more pronounced at the bottom at the discharge, whereas with the dividing walls, shearing is achieved further up in the reactor. The shear zone is above the dividing walls. The shearing (relative movement) is required in the reaction zone.
[0019] However, in a further embodiment of the reactor according to the invention, it is conceivable that the conical components are each arranged in one of the segments formed by the dividing walls. In this way, the relative movement of the particles can be intensified, with the relative movement of the particles to one another being intensified above the dividing walls.
[0020] In a further embodiment of the reactor according to the invention, at least two electrodes, in particular grid electrodes, are arranged in the reactor chamber, spaced apart from one another in the flow direction of the hydrocarbon-containing fluids, via which the reactor can be resistively heated. The required heat input into the reactor system presents a particular challenge. The prioritized reactor concept pursues direct electrical heating of the particles or the carbon bed. The advantages of the reactor according to the invention prevent inhomogeneous heat input, and the associated reduction in electrical resistance does not lead to a failure of the heating concept.
[0021] Furthermore, in a further embodiment of the invention, the conical components can be arranged behind the electrodes in the flow direction. In a reactor such as the one according to the invention, the conical components are therefore arranged below the electrodes. It has been shown that the offset particle discharge leads to a preferential relative movement of the particles in the intraelectrode space.
[0022] In a particularly advantageous embodiment of the reactor according to the invention, at least three conical components are provided, and the conical components are arranged concentrically with respect to the center of the reactor chamber. A concentric arrangement, for example, in a reactor or reactor chamber with a round cross-section, allows the conical components to promote the relative movement of the particles. The concentric arrangement allows for a uniform spatial distribution of the conical components within the reactor chamber.
[0023] The aforementioned object is also achieved by a method at least for the pyrolysis of hydrocarbon-containing fluids at least for the production of at least hydrogen-containing fluids, wherein the hydrocarbon-containing fluids are fed to a reactor chamber of a reactor in counterflow to a moving bed of the reactor consisting of particles, wherein at least the particles of the moving bed or the hydrocarbon-containing fluids are heated to a defined temperature in the range between 800 and 1600°C by means of electrodes arranged in the reactor chamber to generate thermal energy, wherein particles of the moving bed are introduced at a reactor head and wherein particles of the moving bed are discharged at a reactor sump. In the method, the invention provides that the particles pass through several conical components arranged in the reactor chamber and are then discharged from the reactor by means of discharge screws.Carbon particles can be used preferentially, which pass through the reactor as a moving bed.
[0024] In a first embodiment of the process according to the invention, it is provided that a reactor according to the invention is used. The above statements regarding the reactor according to the invention also apply accordingly to the process according to the invention.
[0025] In a preferred embodiment of the method according to the invention, the particles are discharged through the conical components at a time staggered interval. The combination of asymmetrical and staggered discharge allows for thorough mixing, thus promoting relative movement of the particles to one another. If three conical components are installed, the discharge can take place alternately, first through the first conical component, then through the second conical component, and finally through the third conical component. Thus, the alternating discharge above the optionally installed partition walls results in thorough mixing and relative movement of the particles to one another.
[0026] The various embodiments of the invention mentioned in this application can be advantageously combined with one another, unless otherwise stated in the individual case.
[0027] The invention is explained below in exemplary embodiments with reference to the accompanying drawings. They show:
[0028] Figure 1 is a schematic representation of an embodiment of a reactor for the pyrolysis of hydrocarbon-containing fluids,
[0029] Figure 2 is a schematic representation of another embodiment of a reactor for the pyrolysis of hydrogen-containing fluids,
[0030] Figure 3 shows the representation according to Figure 2 in a cross section and
[0031] Figure 4 is a schematic block diagram of an embodiment of a process for the pyrolysis of hydrocarbon-containing fluids.
[0032] Figure 1 shows a schematic representation of a reactor 1 in a longitudinal section. The reactor 1 comprises a reactor shell 2, wherein the reactor shell 2 encloses a reactor chamber 3. The reactor 1 additionally has a reactor head 4 and a reactor sump 5, wherein several feed openings 6 can be arranged at the reactor head 4, while several discharge openings 7 are located at the reactor sump 5.
[0033] Reactor 1 is designed to receive carbon particles in the form of a moving bed 8, with the carbon particles passing through reactor 1 through the feed openings 6 at the reactor head 4 and via the discharge openings 7 at the reactor bottom. In this embodiment, reactor 1 is used for the pyrolysis of methane. Methane can be admitted countercurrently and pyrolyzes on the heated carbon particles of moving bed 8. Heating of moving bed 8 is necessary because the thermal pyrolysis of methane is a highly endothermic reaction that, kinetically and thermodynamically, preferably occurs in a temperature range of 1000°C - 1500°C and at pressures preferably in the range between 10 and 25 bar.
[0034] In order to generate homogeneous heating of the moving bed 8, three concentrically arranged conical components 9 are arranged in the reactor chamber 3 in this embodiment. The conical components 9 serve to realize a relative movement of the particles of the moving bed 8 in the reactor chamber, i.e. a movement in which as many particles as possible move relative to one another. The conical components 9 are funnel-shaped. Flow can pass through the conical component in its longitudinal extent, whereas flow cannot pass through it in the radial direction. The conical components 9 each have an inlet opening 10 and an outlet opening 11, wherein the inlet opening 10 has a larger diameter than the outlet opening 11.
[0035] The conical components 9 are arranged on the reactor base 13 and also serve to discharge the carbon particles. The outlet openings 11 of the conical components 9 are connected to the discharge openings 7 of the reactor, so that the carbon particles are discharged through the conical components 9. The discharge openings 7 and the outlet openings 11 are operatively connected to a discharge screw. Particles can be transported out of the reactor 1 by the discharge screw. The discharge screw 12 is arranged in its conveying direction perpendicular to the conveying direction of the outlet openings 11 and perpendicular to the conveying direction of the conical components 9. In this way, the particles can be efficiently transported out of the active area of the reactor 1 and either further treated or returned to the reactor 1 via the feed openings 6.
[0036] Figure 2 shows a further embodiment of the reactor 1. In addition to the
[0037] In the embodiment shown in Figure 1, partition walls 14 are provided in this embodiment. In this embodiment, the partition walls 14 are arranged locally above the conical components 9, i.e., in front of the conical components 9 in the conveying direction of the carbon particles. Thus, the distance over which the direction of movement of the particles is compensated by means of internal components is extended.
[0038] The partition walls 14 extend radially from the center of the reactor chamber 3 to the reactor shell 2, so that the reactor chamber 3 is at least partially segmented by the partition walls 14. By further segmenting the reactor chamber 3, the relative movement of the particles can be intensified. The function of the partition walls 14 is to transfer the shearing of the particles, which occurs due to a displaced withdrawal of material, through the partition walls 14 into an upper zone of the reactor.
[0039] For heat input into reactor 1, two electrodes 15 are arranged in the reactor chamber 3, spaced apart from one another in the flow direction of the hydrocarbon-containing fluids, via which the reactor 1 can be resistance-heated. The required heat input into the reactor system presents a particular challenge. The reactor concept pursues direct electrical heating of the particles or the carbon bed. The advantages of the conical components 9 and the partition walls 14 prevent inhomogeneous heat input, and the associated reduction in electrical resistance does not lead to a failure of the heating concept.
[0040] Figure 3 shows the embodiment according to Figure 2 in a cross-section. Figure 3 clearly shows that the projection surfaces of the partition walls 14 and the conical components 9 do not overlap. The conical components are each arranged in cross-section in one of the segments 15 formed by the partition walls 14. In this way, the rectification of the particle movement in a section can be intensified.
[0041] Figure 4 shows a block diagram of an embodiment of a process for the pyrolysis of hydrocarbon-containing fluids using a reactor 1 according to the aforementioned figures. In step 100, hydrocarbon-containing fluids are fed into the reactor 1 in reactor chamber 3 of the reactor 1 in counterflow to a moving bed 8 consisting of carbon particles. In step 101, the particles of the moving bed 8 or the hydrocarbon-containing fluids are heated by means of electrodes 15 arranged in the reactor chamber. The defined temperature is in the range between 800°C and 1600°C.
[0042] In step 102, particles from the moving bed 8 are introduced into the reactor 1 at the reactor head 4, and the particles are discharged at the reactor sump 5 in step 103. Within the reactor, the particles pass through the aforementioned conical components 9, which are arranged in the reactor chamber 3. In step 104, the particles are transported out of the reactor by discharge screws 12, where they can be post-treated or directly returned to the reactor 1.
[0043] In the present example, the individual steps do not necessarily run one after the other, but rather the steps are carried out in parallel or simultaneously, in particular when steady-state operation of reactor 1 and moving bed 8 has been established.
[0044] List of reference symbols
[0045] 1 reactor
[0046] 2 reactor shell
[0047] 3 reactor room
[0048] 4 reactor head
[0049] 5 Reactor sump
[0050] 6 Feed opening
[0051] 7 Exit opening
[0052] 8 hiking bed
[0053] 9 Conical component
[0054] 10 Entrance opening
[0055] 11 Exit opening
[0056] 12 discharge screw
[0057] 13 Reactor floor
[0058] 14 Partition wall
[0059] 15 Electrode
[0060] 16 segments
Claims
Patent claims 1. Reactor (1) at least for the pyrolysis of hydrocarbon-containing fluids at least for the production of at least hydrogen-containing fluids, wherein the reactor (1) has a reactor shell (2) and a reactor chamber (3) arranged within the reactor shell (2), wherein the reactor (1) has a reactor head (4) and a reactor sump (5), wherein the reactor head (4) and the reactor sump (5) each have at least one at least temporarily closable feed opening (6) and discharge openings (7) through which at least fluids or solids, in particular particles, are to be introduced or discharged, so that to produce a moving bed (8) through the reactor head (4) particles are at least temporarily continuously introduced into the reactor chamber (3), characterized in that a plurality of conical components (9) are arranged in the reactor chamber (3),wherein the conical components (9) are hollow and have an inlet opening (10) and an outlet opening (11), and wherein the inlet opening (10) has a larger diameter than the outlet opening (11).
2. Reactor (1) according to claim 1, characterized in that the conical components (9) are arranged parallel to one another in their longitudinal extent (L).
3. Reactor (1) according to claim 1 or 2, characterized in that the outlet openings (11) are in operative connection with at least one discharge device (12) through which particles can be conveyed out of the reactor (1).
4. Reactor (1) according to one of claims 1 to 3, characterized in that partition walls (13) are arranged in the reactor space (3) and that the Partition walls (13) extend radially from the center of the reactor chamber (3) to the reactor shell (2), so that the reactor chamber (3) is Partition walls (13) are at least partially segmented.
5. Reactor (1) according to claim 4, characterized in that the conical components (9) are each arranged in one of the segments formed by the dividing walls (13).
6. Reactor (1) according to one of claims 1 to 4, characterized in that at least two electrodes (14), in particular grid electrodes, which are spaced apart from one another in the flow direction with respect to the flow direction of the hydrocarbon-containing fluids and via which the reactor (1) can be resistance-heated, are arranged in the reactor space (3).
7. Reactor (1) according to claim 6, characterized in that the conical components (9) are arranged behind the electrodes (14) in the flow direction.
8. Reactor (1) according to one of claims 1 to 7, characterized in that at least three conical components (9) are provided and that the conical components (9) are arranged concentrically with respect to the center of the reactor space (3).
9. A method at least for the pyrolysis of hydrocarbon-containing fluids at least for the production of at least hydrogen-containing fluids, wherein the hydrocarbon-containing fluids are fed to a reactor chamber (3) of a reactor (1) in counterflow to a moving bed (8) of the reactor (1) consisting of particles, wherein at least the particles of the moving bed (8) or the hydrocarbon-containing fluids are heated to a defined temperature in the range between 800-1600°C by means of electrodes (14) arranged in the reactor chamber (3) in order to generate thermal energy, wherein particles of the moving bed (8) are introduced at a reactor head (4) and wherein particles of the moving bed (8) are discharged at a reactor sump (5), characterized in that the particles pass through several conical components (9) which are arranged in the reactor space (3) and are then discharged from the reactor by means of at least one discharge device (12).
10. The method according to claim 9, characterized in that a reactor (1) according to one of claims 1 to 8 is used.
11. Method according to claim 9 or 10, characterized in that the particles are discharged through the conical components (9) at different times.