EP1682815A2 - Systeme de stockage concu pour stocker un milieu et procede pour charger/decharger un systeme de stockage avec un milieu de stockage - Google Patents

Systeme de stockage concu pour stocker un milieu et procede pour charger/decharger un systeme de stockage avec un milieu de stockage

Info

Publication number
EP1682815A2
EP1682815A2 EP04802672A EP04802672A EP1682815A2 EP 1682815 A2 EP1682815 A2 EP 1682815A2 EP 04802672 A EP04802672 A EP 04802672A EP 04802672 A EP04802672 A EP 04802672A EP 1682815 A2 EP1682815 A2 EP 1682815A2
Authority
EP
European Patent Office
Prior art keywords
storage
container
medium
storage system
loading
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04802672A
Other languages
German (de)
English (en)
Inventor
Walter Schütz
Florian Michl
Wolfgang Polifke
Ricardo Paggiaro
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technische Universitaet Muenchen
Futurecarbon GmbH
Original Assignee
Future Camp GmbH
Technische Universitaet Muenchen
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Future Camp GmbH, Technische Universitaet Muenchen filed Critical Future Camp GmbH
Publication of EP1682815A2 publication Critical patent/EP1682815A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • Storage system for storing a medium and method for loading / unloading a storage system with a storage medium
  • the present invention initially relates to a storage system for storing a medium according to the preamble of patent claim 1. Furthermore, the invention relates to a method for loading / unloading a storage system with a storage medium according to the preamble of patent claim 14.
  • Such a storage system can be designed, for example, as an adsorption storage system for adsorbing a medium and can have a storage container, which can be designed, for example, as a so-called adsorption storage.
  • a storage container in particular an inner container and an outer container, is used to store a medium to be stored, for example a gas, a liquid or possibly also a filling to take up a solid.
  • the present invention relates to the technical field of hydrogen storage, which has recently become significantly more important.
  • Hydrogen is considered a zero-emission fuel (in terms of emissions of toxic or climate-influencing process gases) because when it is used, for example in thermal internal combustion engines, in fuel cell applications or the like, only water is generated. Consequently, the creation of suitable storage means for the efficient storage of hydrogen is an important goal which must be achieved before widespread use of hydrogen as a fuel can occur.
  • adsorption means the accumulation of gases or solutes at the interface of a solid or liquid phase, the adsorption material.
  • the adsorption material thus serves as a storage material for the hydrogen.
  • the storage material is preferably in a storage container, the
  • Adsorption storage in which the hydrogen is stored is stored.
  • the hydrogen is extracted via desorption. This is the back reaction of the adsorption. If the process of adsorption is referred to in the further course of the description, the process of desorption should of course also always be taken into account. During the desorption, the hydrogen adsorbed on the adsorption material is detached from the adsorption material with the application of energy.
  • the problem with the adsorption of media on adsorption materials often lies in the management of the heat effects that occur, that is to say adsorption energies or desorption energies during adsorption or desorption. This can lead to local cooling or overheating of the adsorber material, or the kinetics of adsorption and desorption can be blocked, since the adsorber materials, such as activated carbon with a high specific surface area, have only poor thermal conductivities. Convection as a means of Heat transport in the gas phase is severely restricted due to the large friction losses on the pore walls of the adsorber material.
  • adsorber materials are mostly very porous, that is to say they have a high specific surface area. They are therefore very poorly thermally conductive. If you now adsorb hydrogen or another gas on it, heat of adsorption occurs, which in turn causes the material to be heated and the adsorbed gas to be partially desorbed again. One must therefore try to transport the heat away. The same applies to desorption. In this one, heat has to be brought to the adsorption materials in order to accomplish the desorption.
  • the heat transfer at the connections is an essential problem in the previously known storage containers mentioned at the outset.
  • the present invention is based on the object of further developing a storage system and a method of the type mentioned at the outset in such a way that an efficient energy supply or dissipation can be achieved therewith.
  • a storage system for storing a medium in particular an adsorption storage system for adsorbing a medium
  • a storage container in which a storage material is provided for storing, in particular for adsorbing a medium, and with a container connection for loading / unloading of the storage tank.
  • the storage system is characterized in that at least one circulation circuit is provided for the storage medium, by means of which energy is dissipated and / or supplied in the storage container, that the storage medium serves as an energy carrier, and that the storage container is at least temporarily integrated in the circulation circuit.
  • the medium to be stored for example a gas to be adsorbed - such as hydrogen - with its own good heat transport properties to use as an energy source.
  • the storage container in which the medium (the adsorbent) is located is at least temporarily integrated in a circulation circuit of the medium to be stored.
  • the circulation circuit can advantageously contain further components, which will be explained in more detail in the further course of the description.
  • the temperature of the storage system and of the medium to be stored is advantageously reduced to a so-called cryogenic area in order to achieve higher storage capacities.
  • T liquid nitrogen temperature
  • At least one heat exchanger can advantageously be provided in the circulation circuit.
  • At least one heat exchanger for cooling the storage medium can be provided in the circulation circuit.
  • the storage medium such as a gas
  • the heat exchanger is cooled in the heat exchanger with liquid nitrogen (LN 2 ).
  • At least one heat exchanger for heating the storage medium can be provided in the circulation circuit.
  • the storage medium can advantageously be heated via this heat exchanger, for example using ambient air, the waste heat from an energy converter or the like.
  • a separate heat exchanger can be used for cooling and heating. It is of course also possible that, with a corresponding design of the heat exchanger, only a single heat exchanger is required, via which both the cooling and the heating of the storage medium can take place.
  • the storage medium After cooling or heating in the heat exchanger, the storage medium is introduced into the storage container, as a result of which its storage space (interior) with storage material, free space and container walls is cooled or heated.
  • the storage medium is in
  • Circulation circuit circulates until the desired temperature is reached.
  • the storage container in which the medium to be stored is located is integrated, for example, in the circulation circuit, which also has at least one cryogenically operable heat exchanger.
  • the storage medium flowing through is cooled to cryogenic temperatures during storage, for example during adsorption, and the storage medium flowing through can also be present in the liquid phase.
  • heat is extracted from the heat capacities in the storage space and, like the heat of adsorption, is dissipated in the outflow.
  • the kinetics of desorption can be improved by the recirculation of cryogenically stored gas, which in particular can also be removed from the gas phase coexisting in the pores at the beginning of the desorption and is heated in the heat exchanger.
  • air heat exchangers are advantageous as heat exchangers, which extract the heat from the ambient air flowing past.
  • the flow can be influenced both by an external constraint, such as airflow or ventilation, and by natural convection.
  • Unused waste heat from the consumer which can be a fuel cell or internal combustion engine or a gas turbine or the like, can be transferred directly or via the heat transfer to a heat transfer medium via a heat exchanger to the recirculating storage medium.
  • the heat capacity stored in the gas is fed to the storage container, as a result of which the interior thereof with the parts adsorbent and free space, including the tank walls, is cooled or heated.
  • the pipelines leading out of the storage container should advantageously be designed in such a way that both the requirements of the consumer are met and it is ensured that the return flow of the storage medium - for example, the hydrogen - into the tank again System introduced heat flow which compensates for the amount of heat extracted during the desorption of the environment. If the system is left to itself during desorption without heat being introduced, the temperature inside the system is significantly reduced. In the case of the adsorbent / adsorbate combination AC - H2, temperature drops of> 20 K are characteristic. With the indirect proportionality between temperature and storage capacity, this lowering of the temperature binds further gas to the surfaces of the adsorbent, which would sooner or later cause the gas flow to the consumer to dry up.
  • At least one conveying device for example a pump or the like, can be provided in the circulation circuit.
  • the storage medium is preferably circulated via such a conveying device, which can be connected upstream and / or downstream of the at least one heat exchanger.
  • the storage container can advantageously have at least one further container connection for loading and / or unloading the storage medium, via which the storage medium can be refilled or removed.
  • the heat transfers at the connections for example a tank connection for loading / unloading the storage tank, represent a major problem.
  • Container connection for loading / unloading the inner container may be provided that the container connection has an inner socket connected to the inner container and an outer socket connected to the outer container, and that a coupling is provided which is designed in such a way that a separable coupling is established between the inner socket and the outer socket will or can be produced.
  • the storage container has an inner container for the medium to be stored and an outer insulation container, that at least one switchable thermal bridge is provided between the inner container and the outer container and that the at least one thermal bridge is designed such that for the purpose of the heat exchange, a thermal connection between the inner container and the outer container is at least temporarily established or can be produced.
  • a container connection can thus be made available which only creates a mechanical connection between the inner container and the outer container when required.
  • the invention is not limited to a specific embodiment of the clutch.
  • the coupling should generally be a type of locking mechanism, the actuation of which creates a connection between the inner container and the outer container, so that the storage space of the inner container can be accessed.
  • the inner container is mechanically decoupled from the outer container and can thus be optimally insulated against external heat influences. If the medium stored in the storage container is requested by a downstream consumer, the clutch is actuated and a suitable gas line is coupled by coupling the inner socket and the outer socket. In addition to the supply or discharge of the medium, this then also enables heat conduction via the corresponding heat-conducting ro walls.
  • thermal bridges between the inner container and the outer container for example to support the necessary supply of heat for the removal of the medium, for example hydrogen.
  • the storage container also has at least one switchable thermal bridge between the inner container and the outer container, and that the at least one thermal bridge is designed such that a thermal connection between the inner container and the outer container is made at least temporarily for the purpose of heat exchange or is producible.
  • thermal bridge The purpose of such a thermal bridge is to create a defined heat conduction between the inner container and the outer container if necessary. For example, heat can thus be supplied from the outside into the inner container. Such a procedure makes sense if the medium has to be desorbed from a storage material in the container when medium is removed from the container, for which purpose an activation energy is required. If the ambient temperature of the outer container is lower than the temperature inside the inner container, heat removal from the inner container can of course also be achieved in this way.
  • the present invention is not limited to a specific number of thermal bridges. Rather, the appropriate number depends on the amount of heat to be supplied or removed. Realizations are therefore conceivable in which the storage container has two or more such thermal bridges. Likewise, the invention is not restricted to a specific configuration of the thermal bridge (s). In the further course, some non-exclusive examples will be explained in more detail.
  • An insulation intermediate space can advantageously be formed between the inner container and the outer container.
  • the at least one switchable thermal bridge is then preferably arranged in this insulation space.
  • a vacuum can be formed in the interspace of the insulation.
  • an insulation material in the form of an insulation gas, in the form of powder insulation or foil insulation or the like can be provided in the insulation space.
  • the inner wall of the container and / or the outer wall of the inner container and / or the outer container is / are at least partially coated with an insulating material, in particular with an insulating film.
  • the container connection can also be coated at least in regions with an insulation material, in particular with an insulation film.
  • the coupling is designed for mechanical or pneumatic or magnetic coupling between the inner socket and the outer socket.
  • a non-exclusive example of a suitable clutch is explained in more detail below.
  • the coupling is designed for magnetic coupling between the inner socket and the outer socket.
  • the inner socket can, for example, be formed at least in regions from a magnetic material or have a magnetic material.
  • a device for generating a magnetic field can then be provided, a separable coupling between the inner connector and the outer connector being produced or being producible when the magnetic field is generated.
  • the device for generating a magnetic field can be, for example
  • electromagnet which is switched if necessary. It is of course also possible to use permanent magnets, which are then brought into a desired position, for example rotated or pivoted, if necessary.
  • a return spring can advantageously be provided for the inner socket.
  • the thermal bridge can preferably be designed to be mechanically or pneumatically or magnetically actuable.
  • an advantageous, non-exclusive embodiment of a thermal bridge is explained in more detail below.
  • the thermal bridge can be magnetically actuated.
  • the thermal bridge preferably has a heat conduction element which is formed at least in regions from a magnetic material or has a magnetic material.
  • a device for generating a magnetic field is provided, with the purpose of
  • Heat exchange is at least temporarily a thermal connection between the inner container and the outer container is made or can be produced.
  • the heat conduction element is first attached to the inner container. It can, for example, be made of a good heat-conducting material, such as copper or the like, which is either the same magnetic, such as ferromagnetic, or is connected to a magnetic material.
  • the heat conduction element is initially on the outer surface of the inner container. When a magnetic field, in particular an external magnetic field, is applied, the heat conduction element extends outwards to the inner one Surface of the outer container folded, resulting in a thermally conductive connection between the inner container and the outer container.
  • the thermal bridge can advantageously have at least one return spring for the heat conduction element. If, as described above, the storage system is designed as an adsorption storage system and the storage container is an adsorption storage, this advantageously has a storage material on which the medium to be stored, for example hydrogen, can be adsorbed. A storage material for adsorbing a medium can therefore advantageously be provided in the inner container.
  • the storage material is designed in the form of one or more pressed composites of storage material.
  • a composite material for adsorbing a medium can advantageously be provided as the storage material, the composite material having a carbon-based adsorption material and the adsorption material having admixtures of at least one additional material with high thermal conductivity.
  • the invention is not restricted to specific values for the thermal conductivity. It is only important that the thermal conductivity of the additional material is greater than that of the adsorption material. Some non-exclusive examples of suitable additional materials are explained in more detail in the further course of the description.
  • a basic feature is to add admixtures of material with high thermal conductivity to the adsorbent. These materials are admixed to the adsorption material and do not negatively influence the adsorption properties, of course also the desorption properties, as well as the gas diffusion or the diffusion of the medium. However, it can be influenced in a positive way. However, even if only a few percent are added, they bring about a significant improvement in the thermal conductivity of the material. This leads to the fact that heat effects occurring can be compensated for much more quickly and, for example, the loading and unloading process, for example a refueling process or the delivery of gas from a storage container, can take place much faster.
  • the present invention is not limited to a certain percentage of additional material in the adsorbent material. It has proven to be advantageous if the amount of the additional material is less than or equal to 10% by weight, preferably less than or equal to 5% by weight, particularly preferably less than or equal to 3% by weight, in each case based on the amount of the adsorbent material. It is particularly preferred if the amount of the additional material is 1.5% by weight or approximately 1.5% by weight.
  • the additional material in the adsorption material forms a network structure, in particular a spatial network structure.
  • the stability and / or the conductivity, for example the thermal or electrical conductivity, of the composite material can be further improved, for example, as will be explained in more detail in the further course of the description.
  • the adsorption material is in the form of pure and functionalized graphite and / or in the form of material with a graphite-like carbon structure and / or in the form of activated carbon.
  • the adsorption material is also conceivable. It is only important that this is based on carbon.
  • the additional material to be used can be designed in a wide variety of ways, so that the invention is not restricted to specific materials.
  • additional materials are described below.
  • a single material can be used as additional material.
  • different materials, which are then combined with one another, can also form the additional material.
  • the additional material is in the form of at least one nanoscale additive.
  • the additional material can be a carbon nanomaterial and / or a carbon micromaterial.
  • Carbon micromaterial is a material that has particles whose dimensions are in the range of micrometers.
  • Carbon nanomaterial is a material that has particles whose dimensions are in the range of nanometers.
  • Such carbon materials have a high thermal conductivity, are light in weight and can easily be incorporated into the adsorption material. They are also able to adsorb some of the medium, such as hydrogen.
  • the carbon nanomaterial and / or the carbon micromaterial is / are in the form of carbon fibers (fibers) and / or carbon tubes (tubes). Such materials in particular show good thermal conductivity.
  • SWNT single-wall carbon nanotubes
  • Nanotubes can be formed. Both types are also available in modifications metallic or semiconducting coating. The metallic modification should be used advantageously because it has a high thermal and electrical conductivity.
  • carbon nanofibers are of course also possible, but their electrical and thermal conductivity are somewhat lower compared to the carbon nanotubes. So-called carbon nanoshells can also be used.
  • the carbon nanomaterial and / or the carbon micromaterial can advantageously be used in the form of oriented material, or else have a directional structure.
  • the materials are helical.
  • This helical structure can be described by way of example with the shape of a “spiral staircase”.
  • the helical structures can initially have an outer structure running in a longitudinal direction in the form of a helical line and additionally an inner structure.
  • This inner structure which in the exemplary example of the “spiral staircase "which would form the individual steps comprises individual carbon levels.
  • Such a structure has considerable advantages because of its many edges (edges).
  • the additional material can advantageously be pretreated in such a way that it contributes at least slightly to the adsorption of the medium.
  • the composite material can preferably have at least one further additive to increase the stability of the composite material.
  • This additive can also be, for example, the carbon materials described above.
  • Carbon nanomaterials or carbon micromaterials can namely increase the mechanical stability of the composite material.
  • carbon nanofibers in addition to carbon nanotubes, carbon nanofibers (so-called herring-bone fibers or platelet fibers or other modifications such as, for example, helical carbon nanofibers) are also considered here.
  • the additional materials for example carbon nanotubes and nanofibers.
  • This is done, for example, by a thermal aftertreatment after the synthesis of the materials (for example heating to about 1000 ° C. under inert conditions). Such treatment reduces defects in the material.
  • the additional material is / is chemically modified to improve the connection with the adsorption material. This enables a good connection to be established between the adsorption material and the additional material. This can be done, for example, by functionalization (attaching suitable side groups to the additional materials). It must be ensured that the originally desired properties (good conductivity and mechanical stability) of the additional materials are not impaired.
  • At least one flow channel for the medium to be adsorbed is provided in the composite material.
  • the composite material is advantageously brought into a specific shape.
  • the adsorption material is often in the form of a powder and, in order to be able to be used in a technical system, must first be pressed into a composite, for example in the form of pellets, granules and the like.
  • the adsorbent material is now mixed with the additional material before the pressing process.
  • a spatial network is advantageously formed which prevents the micro- or nanoporosities from collapsing during the pressing process, for example a pelleting process. Due to the high strength and elasticity of the additional materials, such as carbon nanofibers or carbon nanotubes, the free spaces are protected, similar to a structure.
  • the composite material can consequently advantageously be designed in the form of at least one pressed composite. It can be provided that the pressed composite has at least one flow channel for the medium to be adsorbed.
  • a storage container which can be a pressure tank, for example, it is also advantageous to provide sufficiently large flow channels through the storage material. This can equally be done in that the raw form of the compacts is such that the gas flow can take place in the cavities.
  • the same functionality can also be produced in that compacts fill the entire cross-section of the adsorption storage, but are permeable to the gas flow at one, preferably at several, bores.
  • a reasonable ratio of the cross sections of composite material to flow channels is, for example, between 2: 1 and 4: 1.
  • the composite material can advantageously be in the form of pellets and / or granules and / or a granulate bed and / or a powder bed, the invention of course not being limited to the examples mentioned.
  • the storage container advantageously has a storage material in the form of one or more pressed composites made of composite material.
  • this can have a storage material in the form of two or more pressed composites made of composite material, the height of a composite being five to ten times the diameter of a composite.
  • the storage system and here in particular the storage container has a device for passing an electrical current through the storage material.
  • an electric current through the storage material (for example a mixture of additional material and adsorption material), desorption can be facilitated. This electrical current heats up the material (resistance heating).
  • the additional materials especially carbon nanotubes, are also very good electrical conductors. By introducing carbon nanotubes into, for example, activated carbon (common adsorber material, which may be too electrically insulating), the electrical
  • Controlling the overall resistance of the system in a targeted manner This is done by varying the content and distribution of nanotubes in the adsorber material. This means that a material with a defined electrical resistance can be produced.
  • Microwaves can be provided in the storage material.
  • the desorption must Desorption energy can be entered.
  • another option is to couple a microwave heating.
  • a major advantage here is the local limitation of the energy input to the adsorbent material. From there, the energy is transported to the adsorbed storage medium. The type and morphology of the receiver is decisive for the coupling of microwaves. It should be noted that carbon materials or materials based on carbon compounds are in principle well suited for heating with microwaves. Microwaves are particularly good at carbon materials or materials based on
  • Base carbon compounds couple. Due to the poor coupling of metallic materials, the heat capacities of the adsorption storage are not operated, which on the one hand increases the efficiency of the heat input and on the other hand reduces the boil-off losses due to subsequent heat input from the heat capacities.
  • the coupling of microwaves is also possible with carbon-based nanomaterials, especially CNFs and CNTs (Carbon Nano Fibers, Carbon Nano Tubes). In conjunction with the good thermal conductivity, this results in an advantageous possibility of energy input and an acceleration of the desorption.
  • a method for loading / unloading a storage system with a storage medium, which has a storage container in which the temperature is lowered at least in the storage container for loading the storage container and in which the storage medium is unloaded the storage container, the temperature is increased at least in the storage container.
  • the method is characterized in that the temperature is set within a circulation step in which the storage medium is transported through the storage container by means of a circulation circuit and that the storage medium serves as an energy carrier by means of which energy is dissipated and / or supplied in the storage container.
  • the method can advantageously have steps for operating a storage system according to the invention as described above, so that in this regard reference is also made to the above statements and reference is made.
  • the method for loading / unloading an adsorption storage system can advantageously be used.
  • the storage medium When loading the storage container, the storage medium can preferably be cooled in the circulation circuit and then fed into the storage container. In a further embodiment, when the storage container is unloaded, the storage medium in the circulation circuit can be heated and then fed into the storage container.
  • a storage system according to the invention as described above can be used in particular for storing hydrogen.
  • a method according to the invention as described above can also be used in particular for loading / unloading a storage system with hydrogen.
  • the invention is not limited to the storage of hydrogen. So that other media, in particular gases, can also be stored with the present invention.
  • the present invention can be part of a system for mobile hydrogen storage, in particular in vehicles with an integrated energy converter for individual and public transport.
  • the present invention is also particularly advantageous in terms of energy.
  • p 4> 0bar
  • the configuration of the apparatus structure corresponds to the storage system shown in FIG. 4.
  • the heat of adsorption makes up the largest part of the energy balance for activated carbon (> 10000 kJ). For other materials - such as nanotubes - this size is reduced accordingly.
  • the hydrogen is used to transport energy out of the storage container, the difference between the enthalpies is offset against the sum of the above partial energies, since the enthalpy of the hydrogen increases due to the warming in the interior of the storage container. (Enthalpy difference about 5000 kJ). It should be noted that this value changes depending on the adsorbent or the associated heat of adsorption.
  • the temperature of the recirculating hydrogen is set to, for example, 50 K in order to accelerate the logarithmic approach to the 77K at the end of the filling and thus also the entire filling process.
  • the total weight of storage material (composite material) in the storage container (adsorption storage) can be approximately 100-130 kg for the goal of storing 6 kg of hydrogen in the storage container (adsorption storage). This corresponds to a gravimetric storage density of approximately 4.5. ... 9 percent by weight.
  • FIG. 1 shows a schematic view of a storage container in the form of an adsorption storage which is filled with a storage material in the form of a composite material
  • Figures 2 and 3 in a schematic view a storage container in the form of an adsorption storage, in which the inner container can be decoupled from the outer container; and
  • FIG 4 is a schematic view of a storage system with a storage container in the form of an adsorption storage, in which the adsorption storage is at least temporarily integrated in a circulation circuit of the medium to be stored.
  • 1 to 4 each show a storage container 10 which is intended to store hydrogen.
  • the storage container 10 is filled with a storage material 30, on which the hydrogen is adsorbed.
  • the storage container 10 is thus an adsorption storage, for example a hydrogen tank. If the hydrogen is to be removed from the storage container 10, this takes place in the context of the desorption, which is a kind of back reaction of the adsorption.
  • the storage container 10 shown in the figures initially has an inner container 11, in the storage space 12 of which the storage material 30 is arranged. Furthermore, the storage container 10 has an insulating outer container 13. Between the inner container 11 and the outer container 13 there is an insulation intermediate space 14, in which a suitable insulation material can be located. The loading / unloading of the storage container 10 takes place via a container connection 15.
  • the container connection 15 has a
  • the two sockets are coupled to one another at least temporarily, as will be explained in more detail in connection with FIGS. 2 and 3.
  • the storage material 30 can be in the form of one or more pressed composites 31 and can be accommodated in the storage container 10 or in its storage space 12.
  • the pressed composites 31 can be pellets, granules and the like, for example.
  • the problem with the adsorption of media on adsorbent materials often lies in the management of the heat effects that occur, that is to say adsorption energies or desorption energies during adsorption or desorption. So it can Kinetics of adsorption or desorption are blocked because the highly porous adsorption materials, for example activated carbon with high specific surfaces, have insufficient thermal conductivity properties. Convection as a means of heat transport in the gas phase is also severely restricted due to the large friction losses on the pore walls. In order to prevent this, admixtures of material (additional material) with high thermal conductivity, preferably nano- or micromaterials based on carbon, are added to the adsorbent material.
  • a storage material 30 is thus provided, which is designed as a composite material, consisting of an adsorption material based on carbon and admixtures of at least one additional material with high thermal conductivity.
  • the additional material should have a thermal conductivity that is at least greater than the thermal conductivity of the adsorption material.
  • the thermal conductivity is increased through the formation of a network, without the storage capacity of the. Due to the low percolation threshold (typically 1 to 5% by weight)
  • Storage material 30 is significantly reduced. With appropriate pretreatment of the CNTs, they also contribute to a smaller extent to the storage.
  • a homogeneous distribution of the temperatures while avoiding “hot spots” also has a positive effect on the overall kinetics of the process in powder or granulate beds of storage material 30.
  • the link between individual particles via a pronounced nanofiber network fulfills this function in cooperation with the heat transport in the gaseous medium. This also applies in particular to compressed powder or granulate fillings.
  • a spatial network is formed which prevents the collapse of the micro- and nanoporosities, for example during a pelletizing process. Due to the high strength and elasticity of the CNFs (Carbon Nano Fibers) and CNTs (Carbon Nano Tubes), the free spaces are protected similar to a structure.
  • CNFs Carbon Nano Fibers
  • CNTs Carbon Nano Tubes
  • the discharge by means of the supply of heat should preferably be used.
  • the occurrence of heat effects can also be compensated for much more quickly in the case of desorption by means of the thermal conductivity of the additional materials added.
  • a device 32 can advantageously be provided for passing an electrical current through the composite material 30.
  • an electric current through the composite material 30 (mixture of additional material and adsorption material), desorption can be facilitated. This electrical current heats up the material (resistance heating).
  • the additional materials especially carbon nanotubes, are also very good electrical conductors.
  • carbon nanotubes into activated carbon, for example (common adsorber material that may be too electrically insulating), you can control the total electrical resistance of the system. This is done by varying the content and distribution of nanotubes in the adsorber material. So you have to produce a material with a defined electrical resistance.
  • a device 33 for generating and coupling microwaves into the composite material 30 can also be provided.
  • the desorption energy must be entered during the desorption.
  • another option is to couple a microwave heating.
  • a major advantage here is the local limitation of the energy input to the adsorbent material. From there, the energy is transported to the adsorbed storage medium.
  • FIGS. 2 and 3 show an advantageous construction of a storage container 10, the basic construction of which initially corresponds to the storage container 10 shown in FIG. 1, so that reference is made to the corresponding statements.
  • cryogenic tanks which typically consist of an inner container 11 and an outer insulation container 13, are the heat transfers at the container connections 15.
  • These container connections 15 represent the essential heat leaks, since the inner container 11 is directly mechanically connected to the outer container 13 and thus one direct heat conduction is possible.
  • a container connection 15 is shown in FIGS. 2 and 3, which creates a mechanical connection between the inner container 11 and the outer container 13 only when required.
  • the container connection 5 is in turn formed by an inner socket 16 assigned to the inner container 11 and an outer socket 17 assigned to the outer container 13. Furthermore, a coupling 20 is provided, which is designed in such a way that a separable coupling can take place between the inner socket 16 and the outer socket 17.
  • the coupling 20 can advantageously be designed as a magnetic coupling.
  • a device 21 for generating a magnetic field is initially provided.
  • the inner socket can be formed from a magnetic material or, at least in regions, can have a magnetic material. If a magnetic field is now generated, the inner socket 16 is pulled in the direction of the outer socket 17, so that a coupling of the two sockets 16, 17, and thus a container connection 15, is created, via which the inner container 11 or its storage space 12 is loaded and / or can be unloaded.
  • the inner socket 16 can also be equipped with a return spring (not shown), via which the inner socket 16 is in an initial position is withdrawn separately from the outer socket 17 as soon as the magnetic field is switched off.
  • a return spring not shown
  • a connection is established between the inner container 11 and the outside of the tank, for example via a magnetic or pneumatic coupling 20.
  • the mechanical decoupling is associated with an increase in the degrees of freedom of the inner container 11.
  • the fixation of the inner container 11 in the room, that is to say the storage, is advantageously produced by means of resilient powder insulation which completely or partially fills the evacuated intermediate space 14. A combination with super-insulating film insulation windings is possible if the support elements based on powder insulation are packed in vacuum-tight films and are thus gas-tightly separated from the environment.
  • the inner container 11 is mechanically decoupled from the outer container 13 and can thus be optimally insulated against external heat influences.
  • the clutch 20 which is generally a type of locking mechanism, is actuated and the corresponding gas lines (not shown) are coupled. In addition to the gas supply and gas discharge, this also enables heat conduction via the heat-conducting tube walls.
  • Such a thermal bridge 22 initially consists of a heat conduction element 23 which is connected to the inner container 11. Furthermore, that can Heat conduction element 23 consist of magnetic material, or, as shown in FIGS. 2 and 3, have a head 24 made of magnetic material at its free end facing away from the inner container 11. Again, a device 25 for generating a magnetic field is provided. If a magnetic field is now generated, the magnetic head 24 of the heat-conducting element 23 is attracted, so that a thermal connection between the inner container 11 and the outer container 13 is established via the heat-conducting element 23, which can consist, for example, of copper or another material with good thermal conductivity properties. This can now be used to exchange heat. If the magnetic field is switched off, the thermal bridge 22 is interrupted by the
  • Heat conduction element 23 is released from the outer container 13. This process can be accomplished or supported by a suitable return spring 26.
  • a storage system 40 for example a
  • Such a storage system is shown in FIG. 4.
  • the storage system 40 initially has a storage container 10 in which a storage medium 30, for example in the form of pressed composites 31, is located.
  • the loading / unloading of the storage container 10 takes place via a container connection 15 which is connected to a corresponding line 45 to a consumer.
  • a container connection 15 which is connected to a corresponding line 45 to a consumer.
  • An essential feature of this method is to use the gas to be adsorbed and preferably hydrogen with its good heat transfer properties as an energy source.
  • the storage container 10 in which the medium to be stored
  • a circulation circuit 41 which further includes at least one conveyor 44 in the form of a pump and at least one heat exchanger 43, which can also be operated cryogenically.
  • the individual components of the circulation circuit 41 are connected to one another via a suitable circulation line 42. This is shown in Figure 4.
  • an additional container connection 18 can also be provided in the storage container 10 in order to refill or remove the storage medium (hydrogen).
  • the gas is circulated in the circulation circuit 41 preferably by means of a pump 44 which is connected upstream or downstream of the heat exchanger 43.
  • the gas flowing through is cooled to cryogenic temperatures during the adsorption, whereby the phase conversion into the liquid phase is also not excluded.
  • heat is extracted from the heat capacities in the interior and, like the heat of adsorption, is dissipated in the outflow.
  • the cooling can take place, for example, using liquid nitrogen (LN 2 ) which is passed through the heat exchanger 43.
  • the kinetics of desorption can be improved by the recirculation of cryogenic gas, that of the gas phase coexisting in the pores is removed and is heated in the heat exchanger 43.
  • Air heat exchangers for example, which extract the heat from the ambient air flowing past are suitable as heat exchangers 43.
  • the flow can be influenced both by an external constraint, such as airflow or ventilation, and by natural convection.
  • unused waste heat from the consumer which can be a fuel cell or an internal combustion engine or a gas turbine, can be transferred directly or via the heat transfer to a heat transfer medium via a heat exchanger 43 to the recirculating storage medium.
  • the heat capacity stored in the gas is fed to the storage container 10, as a result of which its interior 12 with the parts storage material 30, free gas space including tank walls (see FIGS. 1 to 3) is cooled or heated.
  • the heat exchanger 43 for cooling and heating can be designed as separate components, depending on the design. Of course, it can also be provided that only a single heat exchanger 43 is used, which can perform both functions.
  • the pipelines 42, 45 leading out of the storage tank 10 are to be designed in such a way that both the requirements of the consumer are met and it is ensured that the hydrogen flows back into the system
  • the heat flow introduced compensates for the amount of heat extracted during the desorption of the surroundings. If the system is left to itself during desorption without heat being introduced, the temperature inside the system is significantly reduced. In the case of the adsorbent / adsorbate combination AC - H2, temperature drops of> 20 K are typical. With the indirect proportionality between temperature and storage capacity, this lowering of the temperature binds further gas to the surfaces of the adsorbent, which would sooner or later cause the gas flow to the consumer to dry up.
  • Flow channels is 2: 1 to 4: 1. Since the length of the entire flow channel length is proportional to the flow resistance, an advantageous but not necessarily geometrical subdivision of the storage space makes sense.
  • the length or height of individual logical sections should therefore preferably be limited to five to ten times the diameter of the pressed composites 31.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne un système de stockage (40) conçu pour stocker un milieu, notamment un système de stockage par adsorption permettant d'adsorber un milieu. Ce système comprend un récipient de stockage (10), dans lequel se trouve une matière de stockage (30) conçue pour stocker, notamment pour adsorber un milieu, et une connexion de récipient (15) permettant de charger/décharger le récipient de stockage (10). Afin d'effectuer une alimentation en énergie et/ou une évacuation d'énergie efficaces, au moins un circuit de circulation (41) pour le milieu de stockage permet d'effectuer une alimentation en énergie et/ou une évacuation d'énergie dans le récipient de stockage (10), le milieu de stockage est utilisé comme source d'énergie et le récipient de stockage (10) est intégré au moins par moments au circuit de circulation (41). La présente invention concerne également un procédé pour charger/décharger un système de stockage (40) avec un milieu de stockage.
EP04802672A 2003-11-05 2004-11-04 Systeme de stockage concu pour stocker un milieu et procede pour charger/decharger un systeme de stockage avec un milieu de stockage Withdrawn EP1682815A2 (fr)

Applications Claiming Priority (2)

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DE10351500 2003-11-05
PCT/DE2004/002441 WO2005044454A2 (fr) 2003-11-05 2004-11-04 Systeme de stockage concu pour stocker un milieu et procede pour charger/decharger un systeme de stockage avec un milieu de stockage

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EP1682815A2 true EP1682815A2 (fr) 2006-07-26

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US (1) US20080020250A1 (fr)
EP (1) EP1682815A2 (fr)
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WO (1) WO2005044454A2 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004048201B4 (de) * 2004-09-30 2009-05-20 Infineon Technologies Ag Halbleiterbauteil mit Haftvermittlerschicht, sowie Verfahren zu deren Herstellung
EP1707867A1 (fr) * 2005-03-30 2006-10-04 Northrop Grumman Corporation Réservoir cryogénique à évaporation réduite
US7484540B2 (en) * 2006-01-27 2009-02-03 Gm Global Technology Operations, Inc. Liquid hydrogen storage tank with reduced tanking losses
CA2649670A1 (fr) * 2006-05-04 2007-11-15 Linde, Inc. Procedes de stockage d'hydrogene et de refrigeration
US7611566B2 (en) * 2006-05-15 2009-11-03 Gm Global Technology Operations, Inc. Direct gas recirculation heater for optimal desorption of gases in cryogenic gas storage containers
US7648568B2 (en) * 2007-01-11 2010-01-19 Gm Global Technology Operations, Inc. Hydrogen storage tank system based on gas adsorption on high-surface materials comprising an integrated heat exchanger
DE102007033368B4 (de) 2007-06-27 2009-10-01 BLüCHER GMBH Verfahren zum Bereitstellen eines Sorptionsmaterials für einen Speicherbehälter
DE202007009992U1 (de) 2007-06-27 2008-07-31 BLüCHER GMBH Speicherbehälter für gasförmige Kraftstoffe
DE102008023481B4 (de) * 2008-05-14 2013-10-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wärmeleitfähige Komposit-Adsorbentien sowie Verfahren zu deren Herstellung und deren Verwendung
US9472819B2 (en) * 2012-04-27 2016-10-18 Hamilton Sundstrand Corporation Warming feature for aircraft fuel cells
US9243754B2 (en) 2012-10-09 2016-01-26 Basf Se Method of charging a sorption store with a gas
DE202013105891U1 (de) * 2013-12-20 2015-01-05 Carsten Scherney Wärmespeichervorrichtung sowie Wärmetauschervorrichtung
CN114832575B (zh) * 2021-06-07 2023-05-02 长城汽车股份有限公司 一种空气滤清系统、控制方法及车辆

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4173625A (en) * 1976-05-04 1979-11-06 Billings Energy Corporation Hydrogen purification and storage system
US4343770A (en) * 1977-12-19 1982-08-10 Billings Energy Corporation Self-regenerating system of removing oxygen and water impurities from hydrogen gas
JPS5953201B2 (ja) * 1979-12-18 1984-12-24 松下電器産業株式会社 水素ガスの精製方法
JPS63140200A (ja) * 1986-12-03 1988-06-11 Mitsubishi Heavy Ind Ltd 水素吸蔵合金貯蔵装置
US5202195A (en) * 1990-12-14 1993-04-13 International Fuel Cells Corporation Method of and arrangement for replenishing hydrogen consumed by a fuel cell device
US5360461A (en) * 1993-08-23 1994-11-01 United Technologies Corporation Polymeric storage bed for hydrogen
US5882623A (en) * 1996-05-13 1999-03-16 Hydro Quebec Method for inducing hydrogen desorption from a metal hydride
JP2001322801A (ja) * 2000-03-08 2001-11-20 Denso Corp 水素貯蔵装置
JP4432239B2 (ja) * 2000-09-05 2010-03-17 トヨタ自動車株式会社 水素吸蔵合金の活性化装置と活性化方法
CA2424861A1 (fr) * 2000-10-02 2003-03-13 Tohoku Techno Arch Co., Ltd. Procede d'absorption/desorption pour alliage de stockage d'hydrogene, alliage de stockage d'hydrogene et pile a combustible faisant appel a ce procede
US6918430B2 (en) * 2002-08-14 2005-07-19 Texaco Ovonic Hydrogen Systems Llc Onboard hydrogen storage unit with heat transfer system for use in a hydrogen powered vehicle
US6986258B2 (en) * 2002-08-29 2006-01-17 Nanomix, Inc. Operation of a hydrogen storage and supply system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005044454A2 *

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WO2005044454A2 (fr) 2005-05-19
DE202004017036U1 (de) 2005-01-13
DE112004002629D2 (de) 2006-10-05
US20080020250A1 (en) 2008-01-24
DE102004053353A1 (de) 2005-06-09
WO2005044454A3 (fr) 2005-07-14

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