METHOD AND DEVICE FOR THE CATALYTIC RELEASE OF A GAS FROM A CARRIER MATERIAL

Description

[0001] The present patent application claims priority over German patent application DE 10 2021 203 887.5, the contents of which are incorporated herein by reference.

[0002] The invention relates to a method and a device for the catalytic release of a gas from a carrier material.

[0003] RU 261 732 C1 discloses a process for the production of alkoxysilanes.

[0004] From DE 10 2015 219 305 A1, a device for the catalytic release of hydrogen gas from a hydrogen carrier material is known. A catalyst is required for the release reaction. Investigations have shown that the activity of the catalyst decreases with increasing use. In particular, the activity of the catalyst can be reduced to a value between 2% and 80% of the initial activity of a fresh catalyst. As a result of the loss of activity, the reactor power decreases. The volumetric and gravimetric power density during hydrogen release is reduced, and consequently, the technical performance is diminished.

[0005] The invention is based on the objective of improving the catalytic release of a gas from a carrier material, in particular increasing the efficiency and especially increasing the volumetric and / or gravimetric power density during the release reaction. This objective is achieved according to the invention by a method with the features of claim 1 and by a device with the features of claim 9.

[0006] The core of the invention lies in the fact that catalyst particles of a catalyst material are moved, particularly in a pulsed manner, and thereby reactivated. It has been found that the decrease in the performance of the catalyst material can be due to the catalyst material, and in particular its pores, filling with liquid support material, thus hindering gas release. Specifically, it has been found that the capillary pressure in the pores is so high that bubble formation, which is necessary for the release of gas from the support material, and / or gas bubbles formed in the pores, cannot displace the liquid. The liquid remains in a pore network formed by the catalyst particles.

[0007] It was surprisingly discovered that the catalyst material can be reactivated by moving the catalyst particles within the reactor housing, particularly in a controlled manner. Specifically, the catalyst particles are moved relative to the reactor housing. Specifically, at least a portion of the catalyst particles, in particular at least 10%, in particular at least 20%, in particular at least 50%, and in particular at least 70%, are moved within the reactor housing. It is advantageous to move as many catalyst particles as possible, and in particular all of them, to achieve the most complete reactivation of the catalyst material. This movement abruptly alters the metastable gas-liquid distribution within the pore network of the catalyst particles.Gas bubbles from the dissolved gas can nucleate, and the gas bubbles that are located inside the catalyst particles and / or are produced there can escape to the outside, especially unhindered.

[0008] Studies have shown that by reactivating the catalyst particles, the activity can be increased to over 90% of the initial activity of fresh catalyst material, in particular to at least 95% of the initial activity, in particular to at least 98% of the initial activity, in particular to at least 99% of the initial activity and in particular to 100% of the initial activity.

[0009] In particular, the movement of the catalyst particles can take place under conditions where the catalyst particles have a comparatively lower reaction rate, especially at reduced reaction temperatures, with a reduced loading of the catalyst particles with catalytically active material and / or with a reduced degree of hydrogenation of the support material.

[0010] The reduced reaction temperature is, in particular, at most 300 °C, in particular at most 270 °C, in particular at most 250 °C, and in particular at most 200 °C. The reduced loading of the catalyst particles with catalytically active material, i.e., a reduced catalytic noble metal loading, is at most 1 wt.% based on a catalyst support, in particular at most 0.5 wt.%, in particular at most 0.3 wt.%, and in particular at most 0.1 wt.%. The reduced degree of hydrogenation of the support material is, in particular, at most 80%, in particular at most 60%, and in particular at most 40%.

[0011] In particular, the movement of the catalyst particles can take place under conditions where the catalyst particles have a comparatively low reaction rate, especially at reduced reaction temperatures, with a reduced loading of the catalyst particles with catalytically active material and / or with a reduced degree of hydrogenation of the support material.

[0012] In particular, it was found that the effect of moving the catalyst particles reactivates them for a comparatively long period, specifically at least ten minutes. This is especially true when the support material still contains a sufficient amount of chemically bound gas. Specifically, the degree of hydrogenation of the support material must be at least 10%, at least 20%, and at least 30%. The effort required, especially for repeated movements of the catalyst particles, is reduced. Moving the catalyst particles results in a sustained reactivation of the catalyst particles.

[0013] The process has been found to be particularly advantageous for a hydrogen carrier material. Hydrogen can be reversibly chemically bound to and released from the hydrogen carrier material. A liquid organic hydrogen carrier (LOHC) is a particularly suitable hydrogen carrier material. A carrier material present in a form at least partially loaded with hydrogen, such as perhydro-dibenzyltoluene (H₁₈DBT), perhydro-benzyltoluene (H₁₂BT), and / or dicyclohexane, has proven especially suitable. The use of a mixture of carrier material in the form of perhydro-diphenylmethane and perhydro-biphenyl, at least partially loaded with hydrogen, is also possible. These compounds can be dehydrogenated to diphenylmethane and biphenyl. A mixture of biphenyl to diphenylmethane in a ratio of 30:70, particularly 35:65, and especially 40:60, is particularly advantageous.

[0014] The catalyst material comprises a metal, in particular platinum, palladium, nickel, rhodium, and / or ruthenium. The catalyst material is arranged on and, in particular, attached to a catalyst support. The catalyst support is, in particular, aluminum oxide, silicon oxide, titanium oxide, and / or zirconium oxide. The catalyst support is, in particular, a porous oxide support. The catalyst support material has pores with a diameter of at least 10 nm, in particular at least 20 nm, in particular at least 50 nm, and in particular at least 100 nm. It has been found that this promotes bubble formation within the pores. The catalyst support is, in particular, inert. The weight fraction of the catalyst material, relative to the catalyst support, is between 0.1% and 10%.

[0015] The catalyst material comprises a variety of catalyst particles, in particular catalyst support particles, which are especially in the form of pellets. The catalyst particles have an average particle size of 0.5 mm to 10 mm, especially 1 mm to 8 mm and particularly 2 mm to 4 mm.

[0016] The catalyst particles are arranged in particular in the form of a fixed bed, through which the support material, which is in particular liquid, flows.

[0017] In particular, it was found that the process enables a consistently high volumetric power density during gas release. The process enhances LOHC as a carrier material with a high volumetric power density. The process and the device according to the invention are suitable for applications in the mobility sector, for example, for releasing hydrogen gas in a vehicle, in particular a ship, a train, a truck, and / or a car. The process exhibits, in particular, a volumetric power density of at least 400 kW / m³, more specifically at least 600 kW / m³, at least 800 kW / m³, and more specifically at least 1000 kW / m³.

[0018] A method in which the movement of the catalyst particles is time-controlled after a variable, definable time interval enables the targeted reactivation of the catalyst material. The time interval required for this can be variably defined. For example, the time interval could be ten minutes.

[0019] A method according to claim 2 enables the straightforward implementation of the movement of the catalyst particles. A mechanical impulse can be applied to the catalyst particles by means of an actuating element. In particular, the mechanical impulse is at least 0.05 Ns, in particular 0.1 Ns, in particular 0.2 Ns, in particular at least 0.3 Ns, and in particular at least 0.5 Ns. A specific mechanical impulse related to the mass of the catalyst particles is in particular at least 1.0 x 10³ < m / s, in particular at least 5.0 x 10³ < m / s, in particular 1.0 x 10⁴ < m / s, in particular 5.0 x 10⁴ < m / s, and in particular 1.0 x 10⁵ < m / s.

[0020] The actuating element provides a positioning motion, particularly a linear one, which is directly transmitted to the catalyst material and causes the catalyst particles to move. The actuating element is, in particular, a shock generator that provides the force required for the movement, especially by means of an actuator. The actuator is, for example, a hydraulic, pneumatic, and / or electric linear actuator, in particular a hydraulic cylinder, a pneumatic cylinder, and / or an electrically driven spindle drive. The actuating element can also be designed as a piezoelectric shock generator and / or as an ultrasonic probe. It is particularly conceivable to use several actuating elements, which are arranged, in particular, on an outer surface of the catalyst particle bed and / or within the catalyst particle bed, especially at least partially. The piezoelectric shock generators are driven, in particular, by induction.It was found that the heat generated during the operation of the piezo impulse generators can be used advantageously for the endothermic release reaction.

[0021] The catalyst material, in particular the fixed bed, is arranged in a catalyst container located within the reactor housing. The catalyst container can be fixed within the reactor housing so that movement of the reactor housing directly causes movement of the catalyst container. Alternatively, the catalyst container can be arranged within the reactor housing in such a way that relative movement of the catalyst container within the reactor housing, particularly along a spatial direction, is possible. For example, the catalyst container can be arranged within the reactor housing on a sliding plane, a sliding track, or on a rail guide.

[0022] The catalyst container is enclosed, particularly around its circumference, ensuring that the catalyst material is reliably contained within it. Unintentional leakage of the catalyst material from the container is prevented. The catalyst container can be, for example, cubic or cylindrical. Other shapes are also possible. An advantageous design is one in which the catalyst container has a longitudinal axis and is hollow along this axis, with the contour of the profile geometry also being triangular, pentagonal, or hexagonal.

[0023] The catalyst container has at least one side wall, which is designed to be fluid-permeable, particularly in certain areas. This ensures that the support material and / or the released gas can be supplied to and discharged from the catalyst container.

[0024] A mechanical impulse can be applied additionally or alternatively by means of an impulse source. The impulse source can be, for example, a vehicle on or in which the device is mounted and on which the process is carried out. The impulse source is therefore, in particular, a moving platform, especially a ship, a train, a bus, a truck, or a car. The platform's movements are directly transferred to the reactor housing and to the catalyst material arranged therein. These movements can be caused by acceleration and / or braking maneuvers and / or steering movements. Such a design is particularly simple, since, in particular, additional actuating elements for applying the movement are unnecessary.

[0025] The momentum source can also be implemented as an energy storage element. This energy storage element can, for example, include at least one mechanical spring element, such as a leaf spring and / or a coil spring. In this configuration, the reactor housing and / or the catalyst container can be mounted on a rail arrangement, a sliding plane, or a sliding track. The reactor housing and / or the catalyst container are mechanically coupled to the energy storage element in this case. In this configuration, a movement causes the reactor housing and / or the catalyst container to shift due to inertia along the rail direction, along the sliding track, or on the sliding plane. The energy storage element ensures that, after the movement has ceased, the reactor housing and / or the catalyst container returns to its original position.This displacement then causes the catalyst particles to move within the reactor housing. The energy storage element acts as a return mechanism.

[0026] Packing materials can be added to the bed of catalyst particles. These packing materials are non-reactive, particularly with respect to the catalytic release reaction. The packing materials have a geometry that differs from that of the catalyst particles. They act as impactors within the bed of catalyst particles, thereby increasing the number of collisions between individual particles. This enhances the efficiency of catalyst particle movement. The mean diameter of the packing materials is, in particular, larger than the mean diameter of the catalyst particles. The packing materials are made, in particular, of ceramic or metal, especially stainless steel. The geometry of the packing materials is, in particular, hollow and, in particular, tubular.

[0027] A motor drive, in particular an electric motor and / or an internal combustion engine, a pump, in particular a liquid pump, and / or a compressor can also serve as a source of impulse. Such components are already present on the mobile platform and emit mechanical oscillations and / or vibrations that can be transmitted to the reactor housing and / or the catalyst container to move the catalyst particles. The transmission of the mechanical vibrations is advantageously carried out via the moving platform itself, in particular a chassis or frame of the moving platform. Additionally or alternatively, mechanical coupling elements can be provided.

[0028] A method according to claim 3 simplifies the targeted movement of the catalyst particles. The catalyst particles of the catalyst material can be conveyed by means of a conveying element, particularly within the reactor housing and especially within the catalyst container. The conveying element enables, in particular, continuous conveying of the catalyst material. The conveying element can also be used for intermittent conveying, i.e., alternating phases in which conveying takes place and intermittent conveying does not. Intermittent conveying is discontinuous. The conveying element serves, in particular, to circulate and / or distribute the catalyst material. A conveying element is, for example, a circulating screw and / or an agitator. The conveying is carried out, in particular, such that the catalyst material, i.e., the entire mass of the catalyst material, is circulated within a variable, predefinable time period.In particular, this time period shall be at most 5 min, in particular at most 3 min, in particular at most 2 min and in particular at most 1 min.

[0029] A method according to claim 4 is mechanically simple. It has been found that movement of the catalyst particles can also, and in particular exclusively, be achieved by means of a pressure change, particularly a targeted one, within the reactor housing, especially within the catalyst container. By applying targeted pressure changes, pressure pulses are exerted on the catalyst material, leading to the release of gas bubbles from the pores of the catalyst particles. For example, a pressure increase of at least 1.0 bar, in particular at least 1.5 bar, in particular at least 2.0 bar, and in particular 2.5 bar is applied within a definable time period. This time period is in particular at most 1 s, in particular at most 800 ms, in particular at most 500 ms, in particular at most 300 ms, and in particular at most 100 ms.The pressure increase is achieved in particular by supplying a pressurized gas, especially hydrogen gas and / or an inert gas, and subsequently releasing the pressure, for example by means of a suitable valve. A pressure pulse can also be achieved by a pressure decrease, especially by means of a suitable valve, to effect pressure relief, in order to subsequently achieve a renewed pressure increase as a result of the reaction process.

[0030] A method according to claim 5 makes it possible to carry out a time control with which the movement of the catalyst particles is repeated in a straightforward manner.

[0031] A method according to claim 6 optimizes the reactivation of the catalyst material. In particular, it has been found that parameters of the method itself can be used to initiate the reactivation of the catalyst material by movement. One parameter can be, for example, the number of operating cycles and / or operating hours during which the catalyst material is used. Another parameter of the method can be the activity of the catalyst material, wherein, in particular, the movement of the catalyst material is initiated when a minimum activity is reached or fallen below. For this purpose, a sensor, which in particular detects the activity of the catalyst material, can be in signal communication with a control unit. The control unit is in signal communication with the movement element and generates a corresponding control signal when, for example, the minimum value for the activity of the catalyst material is reached.The process can be carried out in a regulated manner, in particular in a fully automated way.

[0032] For example, the amount of hydrogen gas released can be measured. Additionally or alternatively, the degree of hydrogenation of the at least partially dehydrated support material can be measured. Additionally or alternatively, the heating power, in particular the decrease in heating power supplied to maintain the required reaction temperature in the dehydration reactor, can also be measured.

[0033] A method according to claim 7 enables a further increase in volumetric power density. Such a method exhibits improved efficiency. It has been found that it is advantageous to heat the catalyst material in the reactor housing, particularly directly, by means of at least one or more heating elements. For this purpose, a heat pipe is used, in particular, which is located within the reactor housing and, in particular, is at least partially surrounded directly by the catalyst material. In particular, the heating element is embedded in the catalyst material. The heating element can also be plate-shaped.

[0034] A method according to claim 8 enables a particularly efficient heat transfer from the heating element to the catalyst material.

[0035] In particular, it is possible to increase the efficiency of heat transfer with a compact reactor casing design. The volumetric power density is also increased.

[0036] A device according to claim 9 essentially has the advantages of the method according to claim 1, to which reference is hereby made.

[0037] Moving elements, in particular the actuating element and / or the impulse source, which are directly coupled to the catalyst material and / or to the catalyst container, can be guided to the catalyst material from outside the reactor housing via sleeve-like channels. The sleeve-like channels are appropriately sealed. The device according to the invention has, in particular, a feed opening for supplying the support material and a discharge opening for removing the released gas and / or the support material. The fluid flow direction, in particular of the support material through the reactor housing, is oriented from the feed opening to the discharge opening.

[0038] The device has a control unit that is in signal communication with the moving element.

[0039] A sensor enables the detection of the device's operating state in order to initiate a sensor-controlled reactivation of the catalyst material. For this purpose, the sensor communicates with the control unit. A time sensor can also be used, triggering a time-controlled movement of the catalyst material.

[0040] The design of the movement element according to one of claims 10 to 12 enables the advantages according to claims 2 to 4.

[0041] A device according to claim 13 or 14 provides the advantages of the method according to claim 7 or 8, to which reference is hereby made. In particular, a heat transfer tube through which a heat transfer medium flows serves as the heating element. The heating of the heat transfer medium takes place, in particular, outside the reactor housing. Thermal oil serves, in particular, as the heat transfer medium.

[0042] Additionally or alternatively, hydrogen combustion, particularly catalytic hydrogen combustion, can take place in the heat transfer pipe. Specifically, a catalyst can be applied to the inner surface of the heat transfer pipe to promote hydrogen combustion. A bed of catalyst particles and / or a coating of the inner pipe surfaces has proven advantageous. Platinum and / or palladium are particularly suitable as catalyst materials.

[0043] Instead of hydrogen, other fuels, in particular biomethane, bioethanol, propane and / or butane, can also be burned in the heat transfer tube.

[0044] For heat generation in the heat transfer tube of the heating element, catalytic oxidation, in particular of a support material and especially of a hydrogen carrier material, particularly the hydrogen carrier material that has been discharged from the reactor housing, can also be used. The catalytic oxidation reaction is in particular a partial oxidation reaction, which is carried out in particular without the release of carbon dioxide (CO₂). This ensures that the proportion of carbon dioxide is not additionally increased by the oxidation reaction.

[0045] It is essential that the respective longitudinal axis of the heating elements is oriented transversely, and in particular perpendicularly, to the fluid flow direction of the support material. The angle of inclination between the longitudinal axis of a heating element and the fluid flow direction is at least 60°, in particular at least 70°, in particular at least 80°, in particular at least 85°, and in particular at least 90°.

[0046] Additionally or alternatively, the at least one heating element can also be designed as an electric heating element, in particular by means of heating resistance and / or induction.

[0047] Both the features specified in the claims and the features specified in the exemplary embodiments of a system according to the invention are each suitable, individually or in combination with one another, for further developing the subject matter of the invention. The respective combinations of features do not constitute a limitation with regard to the further development of the subject matter of the invention, but are essentially merely exemplary.

[0048] Further features, advantages, and details of the invention will become apparent from the following description of exemplary embodiments with reference to the drawings. The drawings show: Fig. 1 a schematic representation of a device according to the invention in a first embodiment with loosely arranged catalyst material, Fig. 2 a Fig. 1 Fig. 3 shows a corresponding representation of a device according to a second embodiment with a catalyst container, Fig. 3 a schematic representation of the arrangement of a heating element in a reactor housing, Fig. 4 a sectional perspective view of a device with several heating elements, Fig. 5 a schematic longitudinal sectional view of a device according to a third embodiment, and Fig. 6 a sectional view along section line VI-VI. Fig. 5 .

[0049] One in Fig. 1 The device, designated as a whole by 1, serves to release hydrogen gas H₂ from a liquid organic hydrogen carrier medium. The hydrogen carrier medium is also referred to as LOHC. According to the illustrated embodiment, perhydrodibenzyltoluene serves as the hydrogen carrier medium. The carrier material 2 is a liquid.

[0050] The device 1 comprises a reactor housing 3, which, according to the illustrated embodiment, is essentially cylindrical and has a longitudinal housing axis 4. The reactor housing 3 is connected at its, in Fig. 1 The lower end is closed by a housing base 5. At the in Fig. 1 At its upper end, the reactor housing 2 has an opening 6. The opening 6 serves to supply the carrier material 2 into the reactor housing 3 and to discharge the carrier material 2 and the released hydrogen gas from the reactor housing 3. The opening 6 forms a supply opening and a discharge opening.

[0051] A power storage element 7 is arranged at the base of the housing 5, which, according to the illustrated embodiment, is made of steel wool. The power storage element 7 can also be a mechanical spring element, in particular a coil spring or a leaf spring.

[0052] In the reactor housing 3, catalyst material 8 is arranged in the form of a packed bed. The catalyst material 8 comprises a multitude of catalyst particles that incorporate catalyst support material. The catalyst support material 8 consists of porous aluminum oxide pellets impregnated with platinum as the catalyst material.

[0053] The catalyst material 8 is loosely arranged between two limiting disks 9, which are designed in particular as perforated disks. The two limiting disks 9 are not connected to each other. The limiting disks 9 are arranged independently of each other in the reactor housing 3. The catalyst material 8 is axially supported on the energy storage element 7 via the lower limiting disk 9, which faces the bottom of the housing 5.

[0054] The catalyst material 8 is completely contained within the support material 2. In particular, the level of the liquid support material 2 is located above the upper limiting disk 9.

[0055] The device 1 comprises a moving element in the form of an actuating element 10. The actuating element 10 is designed as a pneumatic working cylinder with a plunger 11. The actuating element 10 is arranged on the reactor housing 3 such that the plunger 11 is guided through the opening 6 into the reactor housing 3 and can contact the upper limiting disk 9 facing the opening 6. It is also conceivable that a cover element (not shown) is provided at the opening 6, which has a corresponding through-opening through which the plunger 11, in particular sealed, is guided into the reactor housing 3. The actuating element 10 is a linear actuating element and can perform an actuating movement along the direction of movement 12.

[0056] The device 1 has an external heating unit 13, which is arranged, in particular, in the area of ​​the reactor housing 3 in which the support material 2 and / or the catalyst material 8 are located. According to the illustrated embodiment, the external heating unit 13 is designed in the form of a jacket and is arranged on an outer surface of the reactor housing 3, in particular completely.

[0057] The following describes in more detail a method for releasing hydrogen gas from the carrier material LOHC in the device 1.

[0058] To carry out the release reaction, the reactor housing 3 is heated by means of the external heating unit 13.

[0059] At a temperature of 300°C, hydrogen gas is released when the support material 2 comes into contact with the catalyst material 8. The released hydrogen gas is discharged through the upper opening 6 and can be made available for further use.

[0060] The release is terminated, in particular by ceasing the supply of heat via the external heating unit 13. Before the release reaction is repeated in the device 1, a mechanical impulse is exerted on the catalyst material 8 by means of the actuating element 10. For this purpose, the actuating element 10 is moved from the Fig. 1 The arrangement shown is activated such that the plunger 11 moves along the longitudinal axis 4 of the housing, according to Fig. 1 downwards, towards the catalyst material 8. The impact of the plunger 11 on the upper limiting disk 9 exerts a sudden shock on the catalyst material 8. This shock moves the catalyst particles and releases gas bubbles from their pores. This reactivates the catalyst material 8, allowing it to be used for another release reaction. The catalyst material 8 is reactivated by the release of the gas bubbles from its pores.

[0061] The energy storage element 7 serves on the one hand to absorb the mechanical impulse and on the other hand to redistribute the catalyst material 8 back into its original position. Fig. 1 Position shown.

[0062] The in Fig. 1 The device shown is particularly suitable for carrying out the process in batch operation.

[0063] The following refers to Fig. 2 A second embodiment of the invention is described. Structurally identical parts are given the same reference numerals as in the first embodiment, to which reference is hereby made. Structurally different, but functionally similar, parts are given the same reference numerals with a trailing "a".

[0064] One difference compared to the previous embodiment is that the catalyst material 8 is arranged in a catalyst container 14. According to the illustrated embodiment, the catalyst container 14 is designed as a metal basket, with openings in the basket mesh allowing the support material 2 and / or released hydrogen gas to flow through the catalyst container 14.

[0065] The catalyst container 14 is rigid in itself. Applying the mechanical impulse generated by the actuating element 10 to the catalyst container 14 does not cause any deformation of the catalyst container 14.

[0066] One difference compared to the previous embodiment is that the reactor housing 3 has a housing cover 15 at its upper end, the end furthest from the housing base 5. The reactor housing 3 is closed at each end. The plunger 11 of the actuating element 10 is guided axially displaceable along the longitudinal axis 4 of the housing and sealed by the housing cover 15.

[0067] The plunger 11 is in particular directly connected to the catalyst container 14, so that a displacement of the plunger 11 directly causes a displacement of the catalyst container 14 and the catalyst material 8 arranged therein.

[0068] According to the illustrated embodiment, the energy storage element 7 is designed as a spring element, in particular as a helical spring.

[0069] The reactor housing 3 has a feed opening 16 for supplying the support material 2. According to the illustrated embodiment, the feed opening 16 is arranged in the cylindrical shell wall of the reactor housing 3, in particular in an area adjacent to the housing cover 15.

[0070] The reactor housing 3 has a first discharge opening 17 for the discharge of the at least partially discharged carrier material LOHC.

[0071] The reactor housing 3 also has a second discharge opening 18 to remove released hydrogen gas from the reactor housing 3. It is also conceivable that only a single discharge opening is provided, through which the at least partially discharged support material and the hydrogen gas can be removed together.

[0072] An arrangement of the device 1 is particularly advantageous such that the longitudinal axis 4 of the housing is oriented horizontally and the second discharge opening 18 is arranged on the upper side of the reactor housing 3. This simplifies the discharge of the released hydrogen gas via the second, then upper, discharge opening 18.

[0073] The following section explains in more detail a procedure for operating device 1a.

[0074] After heating the carrier material 2 using the in Fig. 2 Hydrogen gas is released from the support material in the external heating unit (not shown in detail). The released hydrogen gas can be discharged via the second discharge opening 18. The at least partially discharged support material can be discharged from the reactor housing 2 via the first discharge opening 17. New, at least partially loaded support material 2 can be fed into the reactor housing 3 via the feed opening 16. To prevent a decrease in the activity of the catalyst material 8, a mechanical impulse is exerted on the catalyst material 8 by the actuating element 10. For this purpose, an actuating movement from the actuating element 10 is transmitted directly to the catalyst container 14 by means of the plunger 11.

[0075] Because the catalyst container 14 is rigid, the actuating movement of the actuating element 10 is exerted equally on the entire catalyst material 8, i.e., on the entire packing. In particular, this prevents the catalyst material 8 from being compacted, at least partially, in the area where the plunger 11 of the actuating element 10 engages the catalyst material, thus avoiding any compensation of the actuating movement. This ensures that all catalyst particles within the catalyst container 14 are moved and thereby reactivated. The device 1a according to Fig. 2 is particularly suitable for a continuous release reaction.

[0076] The following refers to Fig. 3 and 4Another embodiment is described. Structurally identical parts receive the same reference numerals as in the first two embodiments, to whose description reference is hereby made. Structurally different, but functionally similar, parts receive the same reference numerals with a trailing "b".

[0077] The device 1b has a substantially cuboid reactor housing 3b. The reactor housing 3b is oriented such that its longitudinal axis 4 is vertical. The feed opening 16 of the reactor housing 3b is located on a lower end wall. The lower end wall forms the housing base 5. The first discharge opening 17 for removing carrier material 2 is located on a side wall of the reactor housing 3b, particularly in an upper region of the reactor housing 3b, and specifically facing away from the feed opening 16. The second discharge opening 18 is located on the upper end wall, i.e., on the housing cover 15. The first discharge opening 17 can also be located on the upper end wall opposite the lower end wall, which specifically forms the housing cover 15.

[0078] The inlet opening 16 and the outlet openings 17, 18 define a fluid flow direction 19, which is oriented along the longitudinal axis 4 of the housing. The fluid flow direction 19 is directed vertically upwards.

[0079] A difference compared to the previous embodiments is that several, specifically forty-two according to the illustrated embodiment, heating elements 20 are arranged in the reactor housing 3b. More or fewer than forty-two heating elements 20 may also be provided. The heating elements 20 are each rod-shaped, tubular, or plate-shaped. Each heating element 20 has a longitudinal axis 21 oriented perpendicular to the fluid flow direction 19. The heating elements 20 are arranged in the reactor housing 3b in a regular grid pattern. In particular, the heating elements 20 are spaced apart from one another. The respective longitudinal axes 21 of the heating elements 20 are oriented perpendicular to the longitudinal axis 4 of the reactor housing 3b.

[0080] In Fig. 4 For illustrative purposes, the catalyst material 8 is not shown in its entirety. The figure depicts an upper and a lower cover surface 22 of the packed bed of catalyst material 8. It is particularly evident that the first discharge opening 17 is located above the upper cover surface 22. The upper discharge opening 17 is not covered by the catalyst material 8.

[0081] According to the illustrated embodiment, all heating elements 20 are located within the bed of catalyst material 8. In particular, the heating elements 20 are embedded in the catalyst material 8.

[0082] The tubular or rod-shaped heating elements 20 have an outer heat transfer surface 27, which, according to the embodiment shown, is cylindrical. It is also possible for the heating elements 20 to have a different outer contour, in particular a rectangular, especially a square, hexagonal or octagonal contour.

[0083] The heat elements 20 allow heat to be transferred directly to the catalyst material 8 in the reactor housing 3b.

[0084] The advantageous heat transfer conditions are particularly due to Fig. 3 This is evident, as the flow conditions are depicted very schematically. Fig. 3 Figure 1 shows a cross-section of a heating element 20, i.e., in a plane perpendicular to the longitudinal axis 21. The catalyst material 8 surrounding the heating element 20 is also shown symbolically. The catalyst material 8, heated by the heating element 20, is exposed to a flow from the support material. This is symbolized by the flow arrow 23. Furthermore, hydrogen gas flows over the catalyst material 8, symbolized by the flow arrow 24. This is either hydrogen gas already released in the reactor housing 3b and / or hydrogen gas that is present, particularly in a physically dissolved state, in the support material.

[0085] When the support material 2 comes into contact with the catalyst material 8 and the catalyst material 8 is heated at the heat transfer surface 27, hydrogen gas is released from the support material. The flow of the at least partially discharged support material is symbolized by the flow arrow 25. The flow arrow 26 symbolizes the hydrogen gas flow. Because hydrogen gas has also been released from the catalyst material 8 surrounding the heating element 20, the flow arrow 26 is shown larger than the flow arrow 24. Since the heat transfer surface 27 is oriented transversely and, in particular, perpendicular to the fluid flow direction 19, an advantageous flow around the heat transfer surface 27 is possible. This improves the heat transfer from the heating element 20 to the support material 2 and, in particular, to the catalyst material 8.In particular, this design enables both convective heat transport and simultaneous hydrogen release.

[0086] The following refers to Fig. 5 and 6 A third embodiment of the invention is described. Structurally identical parts are given the same reference numerals as in the previous embodiments, to whose description reference is hereby made. Structurally different, but functionally similar, parts are given the same reference numerals with a trailing "c".

[0087] In device 1c, the reactor housing 3c is essentially cylindrical. The reactor housing 3c is placed on the base by means of support feet 28 and oriented such that the longitudinal axis 4 of the housing is horizontal. At the in Fig. 5 On the right-hand end face of the reactor housing 3c, a through-opening 29 is arranged through which a distribution pipe 30 leads into the reactor housing 3c. The distribution pipe 30 extends parallel to the longitudinal axis 4 of the housing in a lower region through the reactor housing 3c and is located, in particular, below the catalyst container 14. The distribution pipe 30 has outlet openings spaced apart from one another along the longitudinal axis 4 of the housing, through which loaded carrier material, referred to as LOHC-H, can be fed into the reactor housing 3c. Each outlet opening forms a feed opening 16.

[0088] Several distribution pipes 30, in particular two distribution pipes 30, can also be arranged in the reactor housing 3c. This particularly improves the distributed and uniform supply of the loaded carrier material. It is also conceivable that the distribution pipe 30 is designed non-linearly and, in particular, is arranged in a meandering shape in the bottom region of the reactor housing 3c and / or is branched.

[0089] With reference to the longitudinal axis 4 of the housing, an outflow pipe 32 is arranged diametrically opposite the inlet openings 16, which is connected to the outlet opening 17 of the reactor housing 3c.

[0090] The catalyst container 14 has a substantially hexagonal outer contour formed by several interconnected sides 31. The side walls 31 are designed such that the catalyst material 8 is reliably contained within the catalyst container 14. The side walls 31, particularly the upper side walls 31 facing the discharge opening 17 and the lower side walls 31 facing the feed openings 16, are designed to be fluid-permeable. This ensures that the support material and / or released hydrogen gas can flow through the side walls 31.

[0091] On the end face opposite the through-opening 29, the reactor housing 3c has a connecting flange 33 to which a bracket 34 is attached. The bracket 34 is flange-shaped and has a retaining plate 40, which is integrated in particular, and on which functional elements are held. According to the illustrated embodiment, heating elements 20 in the form of electric heating rods and actuating elements 10 in the form of piezoelectric pulse generators are held on the retaining plate 40. For this purpose, the retaining plate 40 can be provided with several through-openings through which the heating elements 20 and / or the actuating elements 10 are inserted into the reactor housing, in particular into the catalyst container 14, and held therein. The heating elements 20 and / or the actuating elements 10 are inserted into the reactor housing 3c through the retaining plate 40 in a sealed manner.It is possible to variably define the number of heating elements 20 and the actuating elements 10, and in particular to change the ratio of heating elements 20 to actuating elements 10.

[0092] It is possible to arrange only heating elements 20 or actuating elements 10 on the mounting plate 40.

[0093] It is additionally or alternatively possible to provide a further connecting flange on the opposite end face, where the through-opening 29 is arranged according to the illustrated embodiment, in order to provide further functional elements on the reactor housing 3c by means of an additional bracket 34. In particular, it is possible that on the in Fig. 5 The illustrated connecting flange 33 exclusively holds heating elements 20, which are inserted into the reactor housing 3c and connected to an additional, opposing connecting flange which is in Fig. 5 not shown, only actuating elements 10 are attached and inserted into the reactor housing 3c.

[0094] The heat elements 20 are arranged in a regular grid, as shown in Fig. 6 As shown, the heating elements 20 are arranged between the feed opening 16 and the discharge opening 17 such that the loaded carrier material LOHC-H, fed in via the feed opening 16, must flow around at least one heating element 20 to reach the discharge opening 17. In particular, at least one heating element 20 is arranged on the direct line connecting the feed opening 16 and the discharge opening 17. This improves heat transfer and ensures that the carrier material reliably flows around at least one heating element 20.

[0095] Instead of electric heating rods, a heat exchanger tube can also serve as a heating element, in which thermal oil and / or another heat transfer medium is conveyed, wherein the thermal oil and / or the heat transfer medium has been heated outside the reactor housing 3c.

[0096] Alternatively, the heat exchanger tubes can also be used to burn a fuel, in particular hydrogen. This is primarily a catalytic combustion process, in which a catalyst material is applied to an inner surface of the heat exchanger tube, which preferentially combusts the fuel and / or hydrogen. The hydrogen to be burned in the heat exchanger tubes can, in particular, be taken directly from the reactor housing 3c.

[0097] Alternatively, a catalytic oxidation reaction can be carried out in the heat exchanger tubes, particularly of the support material and especially of the at least partially discharged form of the support material discharged from reactor housing 3c. The oxidation reaction is exothermic and can proceed either completely, forming carbon dioxide (CO₂), or at least partially, so that the liquid oxidation product can be reduced again, particularly at a later time, and reused as support material. The oxidation reaction and any subsequent reduction are reversible and enable a closed-loop system for the support material.

[0098] In particular, it was found that it is advantageous to group the heating elements 20 into several heating element groups 35. The heating elements 20 grouped into heating element groups are in Fig. 6 symbolized by corresponding borders. The grouping of the heating elements 20 is carried out exclusively for control purposes. In particular, the heating elements 20 grouped into a heating element group 35 are not mechanically connected to each other. The individual heating element groups 35 are in signal communication with a control / regulation unit, which is shown purely schematically. The signal connection can be wireless or wired. The wireless signal connection, in particular by means of radio, is shown in Fig. 6 represented by a symbol 37. In particular, it is possible to control the individual heating elements 20 and / or the heating element groups 35 by means of the control unit 36 ​​in such a way that a homogeneous temperature distribution over the catalyst material 8 is achieved.

[0099] The control unit 36 ​​is further connected to a sensor 38, the sensor 38 being used in particular to detect an operating state of the device 1c, especially the activity of the catalyst material 8. The sensor 38 is arranged inside the reactor housing 3c. Depending on the design of the sensor 38, it can also be arranged outside the reactor housing 3c.

[0100] A gas / foam zone 39 is arranged in the reactor housing. The gas / foam zone 39 is located directly upstream of the discharge opening 17. The gas / foam zone 39 is located particularly above the catalyst material 8 and particularly above the catalyst container 14. The support material and the released hydrogen gas, which are to be discharged from the reactor housing 3c via the discharge opening 17, must flow through the gas / foam zone 39.

[0101] In the gas / foam zone 39, the foam is formed primarily from at least partially dehydrated carrier material. Released hydrogen gas can entrain at least partially dehydrated carrier material from the gas / foam zone. The gas / foam zone 39 ensures reliable phase separation between the liquid and gaseous / vaporous components of the reaction products in the reactor housing 3c. The risk of unintentional discharge of liquid components from the reactor housing 3c via the discharge opening 17 is reduced. At least partially dehydrated carrier material is either directly returned from the gas / foam zone 39 to the reactor housing 3c for further reaction and / or vaporization, or remains directly within the reactor housing 3c.

[0102] It is also possible to do without the gas / foam zone 39.

[0103] According to the illustrated embodiment, the fluid flow direction 19 is oriented perpendicular to the longitudinal axes 21 of the heating elements 20. In particular, the fluid flow direction 19 is vertically oriented. It has also been found that it is possible to arrange the heating elements 20 such that their longitudinal axes 21 are inclined relative to the fluid flow direction 19.

Claims

1. Method for catalytically releasing a gas from a carrier material, comprising the method steps of: - providing a reactor housing (3; 3b; 3c) in which catalyst material (8) is arranged as catalyst particles in bulk, - releasing the gas from the carrier material by contacting the carrier material with the catalyst material (8), - reactivating the catalyst particles by moving the catalyst particles in the reactor housing (3; 3b; 3c), wherein the movement is effected in a time-controlled manner after expiry of a variably definable time interval.

2. Method as claimed in claim 1, characterised in that the movement is effected by applying a mechanical impulse by means of an actuating element (10) and / or by means of an impulse source, wherein the actuating element (10) and / or the impulse source is mechanically coupled to the reactor housing (3; 3b; 3c) and / or to the catalyst material (8).

3. Method as claimed in any one of the preceding claims, characterised in that the movement is effected by conveying the catalyst material (8) by means of a conveying element, in particular within the reactor housing (3; 3b; 3c).

4. Method as claimed in any one of the preceding claims, characterised in that the movement is effected by applying a pressure change in the reactor housing (3; 3b; 3c).

5. Method as claimed in any one of the preceding claims, characterised in that the movement is effected uniformly after expiry of the variably definable time interval.

6. Method as claimed in any one of the preceding claims, characterised in that the movement is effected in a sensor-controlled manner.

7. Method as claimed in any one of the preceding claims, characterised by heating the catalyst material (8) by means of a heat element (20) which is arranged in the reactor housing (3; 3b; 3c) and has a heat transmission surface (27).

8. Method as claimed in claim 7, characterised in that the heat element (20) has a longitudinal axis (21) which is oriented transversely, in particular perpendicularly, to a fluid flow direction (19) of the carrier material in the reactor housing (3; 3b; 3c).

9. Device for catalytically releasing a gas from a carrier material, comprising - a reactor housing (3; 3b; 3c) in which catalyst material (8) is arranged as catalyst particles in bulk, wherein the reactor housing (3; 3b; 3c) comprises -- a supply opening (6; 16) for supplying the carrier material to the reactor housing (3; 3b; 3c), -- a discharge opening (6; 17, 18) for discharging the released gas and / or the carrier material from the reactor housing (3; 3b; 3c), -- a movement element (10) for moving the catalyst particles in the reactor housing (3; 3b; 3c), -- a control / regulating unit (36) which is in signal communication with the movement element (10), characterised by at least one sensor (38) for detecting an operating state of the device (1c), wherein the sensor (38) is in signal communication with the control / regulating unit (36) for a sensor-controlled reactivation of the catalyst material (8).

10. Device as claimed in claim 9, characterised in that the movement element is designed as an actuating element (10) and / or as an impulse source, wherein the actuating element (10) and / or the impulse source is mechanically coupled to the reactor housing (3; 3b; 3c) and / or to the catalyst material (8).

11. Device as claimed in claim 9 or 10, characterised in that the movement element is designed as a conveying element which is arranged in particular within the reactor housing (3; 3b; 3c).

12. Device as claimed in any one of claims 9 to 11, characterised in that the movement element is designed as a pressure generator.

13. Device as claimed in any one of claims 9 to 12, characterised by a heat element (20) which is arranged at least partially in the reactor housing (3b; 3c) and has a heat transmission surface (27) for heating the catalyst material (8).

14. Device as claimed in claim 13, characterised in that the heat element (20) has a longitudinal axis (21) which is oriented transversely, in particular perpendicularly, to a fluid flow direction (19) of the carrier material in the reactor housing (3; 3b; 3c).