Method and reactor assembly for pyrolyzing hydrocarbon-containing fluids, and reactor assembly
Patent Information
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- THYSSENKRUPP UHDE GMBH
- Filing Date
- 2024-07-30
- Publication Date
- 2026-06-17
Smart Images
Figure EP2024071554_13022025_PF_FP_ABST
Abstract
Description
[0001] Description
[0002] Process and reactor arrangement for the pyrolysis of hydrocarbon-containing fluids and reactor arrangement
[0003] The invention relates to a method at least for the pyrolysis of hydrocarbon-containing fluids, at least for the production of at least hydrogen-containing fluids. The hydrocarbon-containing fluids are fed into a reactor shaft of a reactor in counterflow to a moving bed of particles in the reactor. At least the particles of the moving bed and the hydrocarbon-containing fluids are heated to a defined temperature in the range between 800 and 1600 °C. Moving bed particles are introduced at a reactor head and removed at a reactor bottom. The hydrocarbon-containing fluids are introduced into the reactor from below, and the particles are introduced by gravity from above.
[0004] In addition, the invention relates to a reactor arrangement at least for the pyrolysis of hydrocarbon-containing fluids at least for the production of at least hydrogen-containing fluids with a reactor, wherein the reactor has a reactor shell and a reactor shaft 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 shaft through the reactor head.
[0005] The thermal pyrolysis of methane, the simplest hydrocarbon-containing fluid, is a highly endothermic reaction that, kinetically and thermodynamically, preferentially proceeds in a temperature range of 1000–1500 °C. 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 represents an additional valuable product. If carbon particles are present, the methane pyrolyzes on the particles. The particle sizes after deposition are adjustable by varying the size of the particles and the specific carbon deposition. Therefore, the carbon can be formulated during the reaction step. Electrical heat input is particularly suitable for providing the reaction enthalpy.The reactor is resistance heated via at least one pair of electrodes arranged in the particle bed.
[0006] The electrical current flows through the carbon bed and, due to the electrical resistance of the particle bed, dissipates into thermal energy. The electrical resistance results from the contact points between the particles and the small transfer surfaces, while the carbon particles themselves possess 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. Consequently, 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 the formation of hotspots.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 specifying a reactor and a process in which instabilities in the electrical heat input during methane pyrolysis for the production of hydrogen and pyrolysis carbon can be prevented. The adjustment of the particle size distribution is crucial for stabilizing a homogeneous heat input. This object is achieved in the present invention by the features of the characterizing part of patent claim 1, firstly in that the particle size of the particles of the moving bed are conditioned after discharge from the reactor sump, that the particles subjected to conditioning are at least partially introduced at the reactor head, and that the particles introduced at the reactor head have a uniform, average particle size x1, wherein the uniform particle size has a grain range.
[0008] The particle size range is a particle size distribution, or rather, a grain size distribution. Strictly speaking, it is impossible to create a uniform particle size. The particle size fluctuates within a grain size distribution. In this case, the grain size range is narrow, meaning the scatter of the grain size distribution is small compared to the particle diameter. The particle sizes of the particles introduced at the reactor head are therefore very close to one another, so that one can speak of a uniform particle size.
[0009] The uniform average particle size x1 is preferably in the range of 2-4 mm, particularly preferably in the range of 2.5-3.5 mm. The uniform average particle size corresponds to the maximum of the particle size distribution.
[0010] The grain band preferably corresponds to a scatter of + / - 0.75 mm around the uniform particle size x1, wherein at least 90 wt.% and preferably at least 95 wt.% of the particles have a diameter within the grain band.
[0011] The parameters of the grain size distribution, such as the uniform, average particle size and the grain size range, can be determined, for example, by sieve analysis. Stacked sieves can be used to form grain size fractions and create a histogram of the grain size distribution. The maximum of the grain size distribution corresponds to the average, uniform particle size. Sieves with openings the size of the grain size range boundaries can be used to separate the particle fraction with the uniform particle size x1, which encompasses the corresponding grain size range. The weight proportion of the particle fraction in the total sample can then be determined by weighing. Details on the sieve analysis of particulate materials can be found, for example, in the IFDC S-107 standard of the International Fertilizer Development Center (IFDC).
[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] Conditioning can, for example, involve sieves in a screening device and / or a mill in a comminution device. This allows particles of the desired size to be obtained. This minimizes the risk of hotspots forming in the moving bed of the reactor, which would prevent even heat distribution. Furthermore, blockages caused by bridging can be minimized.
[0014] Various well-known conveying systems can be used for conveying. In addition to conveyor belts and bucket elevators, air- or gas-powered conveying systems are also conceivable.
[0015] Further preferred embodiments of the invention emerge from the remaining features mentioned in the subclaims.
[0016] In a first embodiment of the method according to the invention, it is provided that the conditioning comprises at least one classification or at least one comminution of particles. Through the classification, at least two partial quantities of the original solid mixture can be obtained. Through the comminution, the particle size distribution can be adjusted accordingly. For this purpose, in a further embodiment of the method according to the invention, it can be provided that particles larger than x1 from a first classification are comminuted in a comminution unit, that the comminuted particles are classified in a second classification, wherein after the second and / or first classification, particles with a size of x1 are at least partially fed to the reactor. In this way, the grain size range of the particles fed into the reactor can be made narrower.Particles can be crushed accordingly and fed back into the reactor with the size x1.
[0017] Additionally or alternatively, in a further embodiment of the method according to the invention, it can be provided that particles with a size greater than x1 which leave the comminution unit are at least partially returned to the comminution unit after the second classification.
[0018] In an alternative embodiment of the method according to the invention, it is provided that the particles from the reactor sump are fed to a comminution unit and at least partially comminuted, wherein the comminuted particles are classified in a first sieve and wherein particles with a size of x1 are fed to the reactor, characterized in that the particles smaller than x1 and larger than x1 are at least partially discharged from the process and wherein particles with a size of x1 can also be partially discharged.
[0019] In addition, in a further embodiment of the invention, it can be provided that particles with a size greater than x1 which leave the comminution unit are at least partially returned to the comminution unit after classification.
[0020] In a further alternative embodiment of the method according to the invention, it is provided that the particles are classified in a first screening after being discharged from the reactor and that particles with a size of x1 are at least partially fed to the reactor head, particles smaller than x1 are discharged from the process and particles larger than x1 are comminuted in a comminution unit, characterized in that the particles from the comminution unit are at least partially returned to the first screening.The above object is also achieved by a reactor arrangement at least for the pyrolysis of hydrocarbon-containing fluids at least for the production of at least hydrogen-containing fluids with a reactor, wherein the reactor has a reactor shell and a reactor shaft arranged within the reactor shell, wherein the reactor has a reactor head and a reactor sump, wherein the reactor head and the reactor sump can each have at least one at least temporarily closable feed opening and outlet 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 shaft through the reactor head. It is provided that the reactor is in an operative connection with the reactor sump by means of a first conditioning system.Conditioning can, for example, involve sieves in a screening device or a mill in a crushing device.
[0021] The device for conditioning particles preferably comprises at least one classifying device configured to classify particles removed from the reactor sump and to separate a particle fraction with a uniform particle size x1, which has a grain size range, for return to the reactor head. The classifying device can be designed, for example, as a screening device. In the simplest case, the screening device can comprise two screens, with which particles outside the grain size range, i.e., those with a diameter larger or smaller than the uniform particle size x1, can be removed.
[0022] The uniform particle size x1 is preferably in the range of 2-4 mm, particularly preferably in the range of 2.5-3.5 mm. The particle size range preferably corresponds to a scatter of + / - 0.75 mm around the uniform particle size x1, with at least 90% by weight and preferably at least 95% by weight of the particles having a diameter within the particle size range. The reactor arrangement can be designed to carry out a process according to the invention. The above statements regarding the process according to the invention also apply accordingly to the reactor arrangement according to the invention.
[0023] In a first embodiment of the reactor arrangement according to the invention, the reactor is operatively connected to a first screening device or to a comminution unit. The screening device allows at least two portions of the original solid mixture to be obtained. The comminution unit can crush particles whose particle size exceeds a desired size, thus achieving a narrow particle size distribution. This allows for more stable reactor operation, which can improve reactor handling.
[0024] For this purpose, in a further embodiment of the reactor arrangement according to the invention, a first classification can be operatively connected to a comminution unit in such a way that particles larger than x1 from the first classification can be comminuted in the comminution unit, and the comminution unit can in turn be operatively connected to a second classification in such a way that the comminuted particles can be classified in the second classification, wherein the second and / or first classification is operatively connected to the reactor in such a way that particles with a size of x1 can be at least partially fed to the reactor. In this way, the grain size band of the particles fed into the reactor can be made narrower. Particles that are initially larger than x1 can be comminuted accordingly and at least partially fed back into the reactor with the size x1.
[0025] Additionally or alternatively, in a further embodiment of the reactor arrangement according to the invention, the second classification can be in a further operative connection with the comminution unit in such a way that particles with a size greater than x1 which leave the comminution unit can be at least partially returned from the second classification to the comminution unit.In an alternative embodiment of the reactor arrangement according to the invention, it is provided that the reactor sump is operatively connected to a comminution unit in such a way that the particles from the reactor sump can be fed to a comminution unit and partially comminuted, wherein the comminution unit is operatively connected to a first sieve in such a way that the particles can be classified in the first sieve and wherein the first sieve is operatively connected to the reactor in such a way that particles with a size of x1 can be fed to the reactor, characterized in that the particles smaller than x1 and larger than x1 are at least partially discharged from the process and wherein particles with a size of x1 can also be partially discharged.
[0026] In addition, in a further embodiment of the invention, it can be provided that the comminution unit is in an operative connection with the first classification in such a way that particles with a size greater than x1 that leave the comminution unit can be at least partially returned from the first classification into the comminution unit.
[0027] In a further alternative embodiment of the reactor arrangement according to the invention, it is provided that the reactor is in an operative connection with a first sieve in such a way that the particles are classified in a sieve after being discharged from the reactor and that particles with a size of x1 can be at least partially fed to the reactor head, particles smaller than x1 can be discharged from the process and the first sieve is in an operative connection with a comminution unit in such a way that particles larger than x1 can be comminuted in the comminution unit, characterized in that the comminution unit is in an operative connection with the first sieve in such a way that particles from the comminution unit can be fed to the first sieve.
[0028] The various embodiments of the invention mentioned in this application can be advantageously combined with one another, unless otherwise stated in individual cases. The invention is explained below in exemplary embodiments with reference to the accompanying drawings. They show:
[0029] Figure 1 is a schematic representation of an embodiment of a reactor arrangement for the pyrolysis of hydrocarbon-containing fluids,
[0030] Figure 2 is a schematic representation of a further embodiment of a reactor arrangement for the pyrolysis of hydrogen-containing fluids and
[0031] Figure 3 shows a third schematic representation of a further embodiment of a reactor arrangement for the pyrolysis of hydrogen-containing fluids.
[0032] Figure 1 shows a schematic representation of a flow diagram of a process for methane pyrolysis. It comprises a reactor 1, wherein hydrocarbon-containing particles are fed in counterflow to a moving bed of reactor 1 consisting of particles. The particles of the moving bed and the hydrocarbon-containing fluids are heated to a defined temperature in the range between 800-1600 °C. Particles of the moving bed are introduced at a reactor head 2, and particles of the moving bed are discharged at a reactor bottom 3. Reactor 1 is operatively connected to reactor bottom 3 by a first screening device 4 for classifying particles. The first screening device 4 serves to classify the particles in at least a first stage, so that particles with a desired particle size, or particles of a first fraction, can be returned to reactor 1.
[0033] The screening device 4 thus forms a classifying apparatus designed to classify particles removed from the reactor sump 3 and to separate a particle fraction having a uniform particle size x1, which has a grain size range, for return to the reactor head 2. The uniform particle size x1 can preferably be in the range of 2 - 4 mm, particularly preferably in the range of 2.5 - 3.5 mm. The grain size range preferably corresponds to a scatter of + / - 0.75 mm around the uniform particle size x1, wherein at least 90% by weight and preferably at least 95% by weight of the particles have a diameter within the grain size range.
[0034] Figure 1 shows that the first screening device 4 is operatively connected to a comminution unit 5 for comminuting at least a fraction of the classified particles. The comminution unit 5 can subsequently comminute particles whose particle size exceeds a desired size, thus achieving a narrow particle size range in the particle distribution.
[0035] The first screening device 4 comprises at least one sieve for classifying the particles. The first screening device 4 is connected to the reactor head 2 in such a way that particles with a size x1 can be fed from the first screening device 4 to the reactor 1. Particles of the desired size x1 can thus be returned directly to the reactor 1. Various known conveying devices (not shown here) can be used for conveying. In addition to conveyor belts and bucket elevators, air- or gas-driven conveying devices are also conceivable. Furthermore, the first screening device 4 is operatively connected to the comminution unit 5 in such a way that particles with a size greater than x1 can be fed from the first screening device 4 to the comminution device 5.Larger particles can thus be crushed and fed back into the screening device 4, so that particles of the desired size x1 can be continuously conveyed into the reactor 1 without particles having to be directly discharged from the process.
[0036] Additionally, a second screening device 6 is provided. The second screening device 6 is connected to the reactor head 2 such that particles with a fraction x1 can be fed from the second screening device 6 to the reactor 1. The second screening device 6 is also operatively connected to the comminution unit 5, so that particles with a fraction greater than x1 can be fed from the second screening device 6 to the comminution device 5.
[0037] The particle size is adjusted uniformly in the recirculation by sieving and grinding, i.e. within a narrow grain range based on the particle diameter. For this purpose, the particles are classified in the first sieving device 4 after particle discharge from reactor 1, and then particles with a specified size x1 are fed back into reactor 1. To close the mass and particle balance, the comminution unit 5 is provided, which comminses particles larger than x1. The material from the comminution unit 5 is classified in the second sieving device 6, with large particles larger than x1 being partially fed back into the mill. Particles with a size of x1 are fed back into reactor 1. The product fraction can be composed of particles with a size of less than x1 mm, x1 mm and larger than x1.
[0038] Figure 2 shows an alternative embodiment of a reactor arrangement with a reactor (1). The reactor (1) is operatively connected to a comminution unit (5), which in turn is operatively connected to a classifier (6). The classified particles can be fed at least partially to both the comminution unit (5) and the reactor (1).
[0039] Figure 3 shows an alternative embodiment. The particulate material from the reactor sump is fed to a first screening device 4, whereby particles larger than x1 can be fed to a comminution unit 5, which adjusts the particles to a size smaller than x1 and returns them to the first screening device 4 for classification by means of a suitable conveyor. The medium fraction x1 is at least partially fed to reactor 1, and the smaller particles smaller than x1 are removed from the process.
[0040] List of reference symbols
[0041] 1 reactor
[0042] 2 reactor head
[0043] 3 reactor sump
[0044] 4 First screening device 5 Crushing unit
[0045] 6 Second screening device
Claims
Patent claims 1. 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 shaft of a reactor (1) in counterflow to a moving bed of the reactor (1) consisting of particles, wherein at least the particles of the moving bed and the hydrocarbon-containing fluids are heated to a defined temperature in the range between 800-1600 °C, wherein particles of the moving bed are introduced at a reactor head (2) and wherein particles of the moving bed are discharged at a reactor sump (3), characterized in that the particles of the moving bed are conditioned after being discharged from the reactor sump (3), that the particles subjected to the conditioning are at least partially introduced at the reactor head (2), and that the particles introduced at the reactor head (2) have a uniform particle size x1,where the uniform particle size has a grain band., 2. Method according to claim 1, characterized in that the conditioning comprises at least one classification.
3. Method according to claim 1 or 2, characterized in that the conditioning comprises at least one comminution of particles.
4. Method according to one of claims 1 to 3, characterized in that particles are classified in a first screening device and particles larger than x1 are crushed in a crushing unit (5), that the crushed particles are classified in a second conditioning unit (6), wherein after the second conditioning, particles with a size of x1 are at least partially fed to the reactor (1).
5. Method according to claim 4, characterized in that particles with a size greater than x1 which leave the comminution unit (5) are at least partially returned from the second conditioning (6) into the comminution unit (5).
6. The method according to any one of claims 1 to 3, characterized in that the particles from the reactor sump (3) are fed to a comminution unit (5) and comminuted, the comminuted particles being classified in a first screening device (4) and particles having a size of x1 being at least partially fed to the reactor (1), characterized in that the particles smaller than x1, larger than x1 are at least partially discharged from the process and remaining particles of size x1.
7. The method according to claim 6, characterized in that particles with a size greater than x1 which leave the comminution unit (5) are at least partially returned from the screening device (4) into the comminution unit (5).
8. Method according to one of claims 1 to 3, characterized in that the particles are classified after discharge in a first screening device (4) and that particles with a size of x1 are at least partially fed to the reactor head (2), particles smaller than x1 are discharged from the process and particles larger than x1 are crushed in a comminution unit (5), characterized in that the particles from the comminution unit (5) are fed to the first screening device (4).
9. Process according to one of claims 1 to 8, characterized in that the uniform particle size x1 is in the range of 2 - 4 mm, preferably in the range of 2.5 - 3.5 mm.
10. The method according to any one of claims 1 to 9, characterized in that the grain size band corresponds to a scatter of + / - 0.75 mm around the uniform particle size x1, wherein at least 90% by weight and preferably at least 95% by weight of the particles have a diameter within the grain size band.
11. Reactor arrangement at least for the pyrolysis of hydrocarbon-containing fluids at least for the production of at least hydrogen-containing fluids, with a reactor (1), wherein the reactor (1) has a reactor shell and a reactor shaft arranged within the reactor shell, wherein the reactor (1) has a reactor head (2) and a reactor sump (3), wherein the reactor head (2) and the reactor sump (3) 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 through the reactor head (2) particles are at least temporarily continuously introduced into the reactor shaft, characterized in that the reactor (1) is in operative connection with the reactor sump (3) by means of a device for conditioning particles.
12. Reactor arrangement according to claim 11, characterized in that the device for conditioning particles comprises at least one classifying device (4, 6) which is designed to classify particles taken from the reactor sump (3) and to separate a particle fraction with a uniform particle size x1, which has a grain band, for return to the reactor head (2).
13. Reactor arrangement according to claim 12, characterized in that the uniform particle size x1 is in the range of 2 - 4 mm, preferably in the range of 2.5 - 3.5 mm.
14. Reactor arrangement according to claim 12 or 13, characterized in that the grain band has a scatter of + / - 0.75 mm around the uniform particle size x1, wherein at least 90 wt.% and preferably at least 95 % by weight of the particles have a diameter within the grain range.
15. Reactor arrangement according to one of claims 11 to 14, characterized in that the reactor (1) is operatively connected to the reactor sump (3) with a device for conditioning particles with at least one first screening device.
16. Reactor arrangement according to one of claims 11 to 15, characterized in that the reactor (1) is operatively connected to the reactor sump (3) with a device for conditioning particles with at least one comminution unit (5) for comminuting at least some of the particles.
17. Reactor arrangement according to one of claims 11 to 16, characterized in that the conditioning has a first screening device (4) for classifying the particles, which is in operative connection with a comminution unit (5), which in turn is in operative connection with a second screening device (6), characterized in that the second screening device (6) is in operative connection with the reactor head (2).
18. Reactor arrangement according to claim 17, characterized in that the second screening device (6) is operatively connected to the comminution unit (5) in such a way that particles with a size greater than x1 can be fed from the second screening device (6) to the comminution device (5).
19. Reactor arrangement according to one of claims 11 to 16, characterized in that the reactor (1) is operatively connected to the reactor sump (3) with a device for conditioning with a comminution unit (5), which is operatively connected to a first screening device (4), wherein the comminuted particles can be classified in the first screening device (4), wherein the first screening device (4) is operatively connected to the reactor head (2), and wherein particles with a size of x1 can be fed at least partially to the reactor (1), characterized in that particles can be discharged at various points during conditioning.
20. Reactor arrangement according to claim 19, wherein the first screening device (4) is operatively connected to the comminution unit (5) in such a way that particles with a size greater than x1 leaving the comminution unit (5) can be at least partially returned to the comminution unit (5).
21. Reactor arrangement according to one of claims 11 to 16, characterized in that the reactor (1) is operatively connected to the reactor sump (3) with at least one first screening device (4) in such a way that particles with a size of x1 can be fed to the reactor head (2), characterized in that the first screening device (4) enables particles to be discharged, characterized in that the first screening device (4) is operatively connected to a comminution unit (5) in such a way that particles can be fed to the comminution unit (5), characterized in that the first screening device (4) is operatively connected to the comminution unit (5) in such a way that particles from the comminution unit (5) can be fed to the first screening device (4).