• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a reversible H 2 storage system comprising: - a hydrogen storage tank (2) comprising an enclosure (20) containing metal hydrides integrated in a heat exchanger (21) with two fluid circuits, said primary exchanger, - a hydrogen circulation circuit (3), said first circuit, connected to the interior of the enclosure, for supplying or recovering the H2 respectively to absorb or desorbed by the metal hydrides, the part of the first circuit inside the enclosure constituting one of the exchanger circuits, - a circulation circuit of a coolant (4), said second circuit, connected to the exchanger, the part of the second circuit in the exchanger constituting the other of the exchanger circuits, the first and second circuits being sealed with respect to each other, - a pressurizing means (5) for bringing the value of the pressure in the second circuit to a value close to c she in the first circuit.
    公开号:FR3016021A1
    申请号:FR1450008
    申请日:2014-01-02
    公开日:2015-07-03
    发明作者:Albin Chaise；Olivier Gillia
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] BACKGROUND OF THE INVENTION Technical Field The present invention relates to a system for the reversible storage of hydrogen H 2 in solid form, comprising a reservoir whose enclosure contains a heat exchanger which contains metal hydrides. The present invention aims to simplify the design and construction of the integrated heat exchanger.
    [0002] The possible applications of the invention are numerous and may relate to the entire field of application of the storage of hydrogen. These may be H2 storage systems with dedicated tanks for means of transport, such as boats, submarines, cars, buses, trucks, construction equipment, two-wheeled vehicles, as well as those in the field of power supplies. transportable in energy, such as batteries for portable electronic devices (mobile phone, laptop, ...). It may also be more stationary storage and H2 storage systems such as generators, storage of H2 produced by intermittent energies (wind turbines, photovoltaic panels, geothermal energy, etc.).
    [0003] In general, the system according to the invention can be used for purposes only of transporting hydrogen, but also for an on-board storage of hydrogen for a fuel cell or heat engine or a stationary storage of hydrogen. State of the art We are looking for alternatives to oils because, in particular, the reduction of oil reserves. One of the promising vectors for these energy sources is hydrogen, which can be used in fuel cells to produce electricity. Hydrogen is a widespread element in the universe and on Earth, it can be produced from coal, natural gas or other hydrocarbons, but also by simple electrolysis of water using for example the electricity produced by solar or wind energy.
    [0004] Fuel cells operating with hydrogen are already used in some applications, for example in motor vehicles but are still uncommon, particularly because of the precautions to be taken and difficulties in storing hydrogen.
    [0005] In order to reduce the storage volume, the hydrogen can be stored in the form of compressed hydrogen gas at between 350 and 700 bar, but this densification of the energy can be further improved by integrating hydrides into the pressure vessel. To be more dense, hydrogen can also be stored in liquid form, however this storage ensures only a low storage efficiency and does not allow storage over long periods. The passage of a volume of hydrogen from the liquid state to the gaseous state under normal conditions of pressure and temperature produces an increase in its volume by a factor of about 800. Hydrogen reservoirs in the form of liquid are generally not very resistant to mechanical shock, this poses significant safety problems.
    [0006] There is also the storage of hydrogen in solid form by means of hydrides. This storage allows a large storage volume density while minimizing the energy impact of storage on the overall efficiency of the hydrogen chain, i.e. from its production to its conversion into another energy. The principle of solid storage of hydrogen in the form of hydrides is as follows: some materials and in particular some metals have the ability to absorb hydrogen to form a hydride, this reaction is called absorption. The hydrides formed can again give hydrogen gas and a metal. This reaction is called desorption. Absorption or desorption occurs as a function of hydrogen partial pressure and temperature.
    [0007] For example, a metal powder is used which is brought into contact with hydrogen, an absorption phenomenon appears and a metal hydride is formed. The hydrogen is liberated according to a desorption mechanism. Hydrogen storage is an exothermic reaction, i.e., which releases heat, while hydrogen release is an endothermic reaction, i.e., which absorbs heat. In particular, it is sought to have a rapid loading of the metal powder into hydrogen. To obtain such a fast loading, it is necessary to evacuate the heat produced during this loading to avoid braking the absorption of hydrogen on the powder or the metal matrix. When unloading hydrogen, heat is supplied. Therefore, the efficiency of cooling and warming conditions loading and unloading rates.
    [0008] In other words, it is necessary to evacuate heat during absorption and to provide heat during the desorption to facilitate the reactions and increase the efficiency of the hydride in terms of the flow of hydrogen entering or leaving the storage tank. Thus, a hydrogen reservoir in the form of metal hydrides generally comprises a chamber containing hydrides and incorporates within it a heat exchanger. The design and dimensioning of this integrated heat exchanger must meet several main criteria that can be stated as follows: - it must produce an efficient heat exchange. Indeed, in the tank, the hydride is in the form of powder with a limited thermal conductivity. The dimensioning of the tank must therefore take into account the hydrogen flow rates to be ensured; the absorption of hydrogen by the metal causes an increase in volume thereof. This has two consequences. On the one hand, because of its fragile behavior, the metallic material is pulverized and transformed into fine powder. This phenomenon is called decrepitation. On the other hand, because of the swelling, the material applies a mechanical pressure on the walls of its container. To limit these constraints, it is possible to compartmentalize the hydride in cells of suitable dimensions, and in particular to avoid making cells slender vertically, the vertical being defined by gravity. - The hydrogen pressure in the tank varies, including increases in pressure of hydrogen. The reservoir must therefore be able to withstand such variations. Another problem arises when the pressure difference between that of the hydrogen gas in the tank and that of the heat transfer fluid within the integrated heat exchanger is very different. Generally, the heat transfer fluid is at a pressure of a few bars, while the hydrogen can be at a much higher pressure, for example 350 bar.
    [0009] The high hydrogen pressure then applies outside the channels of the heat transfer fluid circuit, which is extremely mechanically demanding for these channels within the integrated heat exchanger. The existing solution requires channel material thicknesses that are very important. For example, a cylindrical tube subjected to a high external pressure is sized to buckling, the thickness of its walls are then very large, which on the one hand, weighs down and makes more expensive the storage tank of hydrogen, and on the other hand, is detrimental to a good heat transfer of the heat between the hydride and the coolant, because the thermal resistance increases with the wall thickness of coolant circulation channels. There is therefore a need to further improve reversible hydrogen storage systems with a tank containing metal hydrides and incorporating a heat exchanger therein, in particular with a view to improving the heat transfer between the hydride (s). (s) metallic (s) and hydrogen, to decrease the mass and cost of realization of the tank. The object of the invention is to at least partially meet this need. SUMMARY OF THE INVENTION To this end, the subject of the invention is a reversible hydrogen storage system comprising: a hydrogen storage tank comprising an enclosure containing metal hydrides integrated into a heat exchanger with two heating circuits; fluid, said primary exchanger, - a hydrogen circulation circuit, said first circuit, connected to the interior of the chamber, for supplying or recovering H2 hydrogen respectively absorbed or desorbed by the metal hydrides, the part of the first circuit inside the enclosure constituting one of the exchanger circuits, - a circulation circuit of a heat transfer fluid, said second circuit, connected to the exchanger, the part of the second circuit in the exchanger constituting the other circuits of the exchanger, the first and second circuits being sealed with respect to each other, - a pressurizing means for bringing the value of the pressure into the second e circuit to a value close to that in the first circuit.
    [0010] By "heat exchanger" is meant here and in the context of the invention, a device comprising at least one tube of any section in which circulates a heat transfer fluid and arranged at least partially in a bed of metal hydride powder in the pregnant. Heat conducting elements, such as fins, wires, metal foam, can be connected to a heat exchanger tube according to the invention. By "near value" is meant here and in the context of the invention, a substantially equal pressure value in the first and second circuits, with a difference typically of one bar or 2 to 3 bars, or even of the order a dozen bars.
    [0011] It is specified that the first circuit ensures a direct contact of the hydrogen with the hydride material. Thus, the invention essentially consists in reducing to low values the pressure difference between the two fluids, the hydrogen and the coolant, within the reservoir.
    [0012] In the context of the invention, the hydrogen pressure is that dimensioning in particular because it can be compressed at high pressures, typically at 350 bar or even above, typically up to 1000 bar to be stored in stationary tanks. Therefore, the invention consists in pressurizing the heat transfer fluid so that it reaches at least the hydrogen pressure.
    [0013] Reducing this pressure difference makes it possible to consider lightening the structures of the heat exchangers integrated in the hydrogen tanks, by using tubes with thinner walls. The fact of having thinner walls has two major advantages, namely on the one hand the reduction of the weight and on the other hand the reduction of the thermal resistance, because all the heat flow passes through this wall of tube. This has an undeniable advantage for onboard tanks, and in general, this brings a gain in terms of efficiency and cost. Another advantage is to be able to adopt shapes of tubes for the heat exchanger that are not circular. It is thus possible to advantageously envisage square, rectangular, triangular, oblong, cross-section, or even quad-section or multi-branched section tubes. These latter star-shaped shapes have the particular advantages of increasing the exchange surface and facilitating their integration into the heat exchanger.
    [0014] The coolant can be at a pressure close to that of hydrogen. Advantageously, for a tube of circular section, the pressure of the coolant is slightly higher than that of hydrogen. Thus, the channels (tubes) of a heat exchanger integrated within the tank are in a mechanical stress mode in internal pressure, that is to say from the inside of the outward channels within the enclosure tank, and not in external pressure that causes buckling problems. The stress in internal pressure is more easily controllable. Thus, it is preferable that the coolant be at a higher pressure than the H2 gas.
    [0015] In other words, the dimensioning of the heat exchanger is easier. In other words, thanks to the invention, there is obtained a simplification of the design and implementation of the integrated heat exchanger within the hydrogen reservoir, which can be more compact, lighter and more efficient than an exchanger according to the invention. state of the art. Preferably, the coolant is a liquid, preferably water-based, especially with glycol or the like. According to an advantageous embodiment, the pressurizing means may consist of the tube (s) of the heat exchanger, the section of the tube (s) of the exchanger being adapted to deform sufficiently for bring the value of the pressure in the second circuit to a value close to that in the first circuit.
    [0016] In other words, it is conceivable according to this mode that the pressure equalization is ensured by the deformation of the tube section of the exchanger itself, ensuring the role of a flexible membrane. For example, a star section tube has an ability to easily deform, thereby transmitting the pressure from the first circuit to the second circuit. Alternatively or cumulatively, according to another advantageous embodiment, the pressurizing means consisting of a pressure balancer consisting of an enclosure inside which is fixed a movable element sealingly separating a first chamber of a second chamber , the first chamber being connected to the first circuit, the second chamber being connected to the second circuit. The movable member may be a flexible membrane or a piston. Instead of a diaphragm or piston accumulator, it is also possible to envisage a compressor for pressurizing the circuit of the coolant. In this case, it also provides a servo circuit so that the pressure supplied by the compressor follows that of hydrogen. According to a first variant, the pressurizing means is arranged outside the storage tank of E12.
    [0017] In a second variant, the pressurizing means is arranged inside the chamber of the H2 storage tank. According to an advantageous embodiment, the second circuit comprises a first pump and another heat exchanger constituting a first secondary exchanger.
    [0018] According to this mode, the secondary fluid of the secondary exchanger is preferably a liquid, preferably water, or a gas, preferably air. The invention also relates in another of its aspects, a method of operating a system described above, comprising a permanent pressurization step, to bring the pressure value in the second circuit to a value close to that of the first circuit. . The pressurization step is preferably performed automatically. Advantageously, the pressure in the second circuit is greater than that in the first circuit. Preferably, the pressure in the first circuit is at least equal to 350 bars, that in the second circuit is greater than about 2 to 3 bars. The invention also relates to a power supply assembly comprising a fuel cell and a system described above, the first secondary heat exchanger being connected to the fuel cell so that the heat discharged by the fuel cell operating allows the desorption of hydrogen in the tank. The invention finally relates to a stationary hydrogen recharging installation of an assembly according to claim 14, comprising a second pump and a second secondary heat exchanger, the second pump and the second secondary heat exchanger being intended to be connected to the second circuit when reloading H2 tank.
    [0019] DETAILED DESCRIPTION Other advantages and characteristics of the invention will emerge more clearly from a reading of the detailed description of exemplary embodiments of the invention, given by way of illustration and without limitation with reference to the following figures among which: FIG. 1 is a schematic view of an example of a reversible storage system for hydrogen according to the invention; FIG. 2 is a schematic view of an assembly for an embedded application, such as on a motor vehicle, comprising a fuel cell and a reversible hydrogen storage system according to the invention, the connection of the assembly. in stationary application being also represented; FIGS. 3A and 3B are schematic views of alternative arrangements of the pressurizing means of a reversible hydrogen storage system according to the invention; FIGS. 4A to 4H illustrate, in cross-sectional view, different shape variants of heat exchanger tubes that can be used in a reversible hydrogen storage system according to the invention. FIG. 1 shows a system 1 for the reversible storage of hydrogen H2 according to the invention. The system 1 firstly comprises a storage tank 2 comprising an enclosure 20 containing metal hydrides, not shown and incorporating within it a heat exchanger 21 constituting a primary heat exchanger. A hydrogen circulation circuit 3 is connected to the interior of the enclosure 20, to supply or recover hydrogen H2, respectively, to be absorbed or desorbed by the metal hydrides. The part 30 of the circuit 3 inside the enclosure 20 constitutes one of the circuits of the primary heat exchanger 21. The circuit 3 ensures a direct contact of the hydrogen with the hydride material. A circulation circuit for a liquid coolant 4 is connected to the exchanger 21, the portion 40 of this circuit 4 in the exchanger constituting the other of the circuits of the exchanger 21. This circuit 4 therefore has the function of being a so-called primary cooling loop which penetrates inside the enclosure 20 and leaves. To ensure the thermal exchange with a secondary fluid, preferably a liquid, there is provided within this loop 4, a secondary heat exchanger 41. The circulation of the liquid within the loop 4 is provided by a pump 42. According to the invention, the loop 4 is pressurized at a pressure close to the hydrogen supply pressure, ie that prevailing in the circuit 3 and in the chamber 20 of the tank 2 via a balancing means pressure valve 5 arranged outside the tank 2. As illustrated in Figures 1 and 2, the pressure balancing means 5 is constituted by a flexible membrane type battery or piston. Thus, it consists of an enclosure 50 inside which is fixed a flexible membrane 51 sealingly separating two chambers 52, 53. The first chamber 52 is connected to the feed / recovery circuit 3. second chamber 53 is connected to the cooling loop 4. As an advantageous example, the system 1 shown in Figure 1 can store hydrogen in the tank 2 under a pressure of 350 bars of hydrogen. The maximum hydrogen pressure rise may be 350 bar in a time of 1 to 1.5 min. The tank 2 may have a storage capacity of the order of 1.5 kg of H2. With the membrane accumulator 5, the water circulating in the loop 4 may be at a higher pressure of the order of 2 to 3 bars more. Appropriate cooling can be achieved with a water flow rate when H2 is charged, of the order of 1 liter / second, the water temperature varying between 10 and 75 ° C. With the membrane accumulator 5 according to the invention, the pressure difference between the heat transfer circuit 4 and the hydrogen in the heat exchanger 21 integrated in the tank 2 is thus reduced.
    [0020] However, it must be ensured that the secondary heat exchanger 41 can handle a larger pressure difference because it exchanges with a low pressure circuit, for example a water or air circuit. However, this greater pressure difference to be provided on the secondary exchanger 41 does not present any drawback because: on the one hand, it contains no hydride, and therefore its design is simplified, and the same pressure differences can can easily be reached by a conventional design of conventional heat exchangers, - on the other hand, when the system according to the invention is intended to be embedded type, for example in a motor vehicle, to operate a battery to fuel, we can afford not to ship this secondary exchanger 41. It can be installed in a fixed, integral part of a hydrogen filling station. As regards the discharge of hydrogen, a secondary exchanger 41 is nevertheless necessary. However, for use of hydrogen in a fuel cell to operate a vehicle, for example, there is no need for high hydrogen flow rates, the heat flows exchanged are thus much lower, a factor 50 to 100 approximately. The secondary heat exchanger 41 to be shipped may therefore be much smaller than that for the hydrogen charging phase. A system 1 according to the invention which is embedded is therefore generally lighter. FIG. 2 shows a system 1 according to the invention for an on-board application with a fuel cell 7 with the hovering of hydrogen.
    [0021] In stationary, the management of high heat flows, i.e. high flow rates, is through an external heat exchanger 45, the technology may be usual such as a water / air exchanger for example. The flow of water in the circuit 4 is provided by a pump 44 in the loading station. Thus, in the hydrogen loading mode in the station, the valve V1 is closed, the pump 42 is stopped), the pump 44 is in operation, the connection connectors R1, R2, and R3 are connected, the connection R3 allowing the supply of hydrogen in the tank 2. In unloading mode, ie operating of the fuel cell 7 on board, the valve V1 is open, the pump 42 is in operation, the connections R1, R2 , and R3 are disconnected and sealed. The fuel cell 7 is on, the pump 60 of the secondary circuit 6 is also in operation. With such a system, the heat lost by the fuel cell 7 is used to desorb the hydrogen of the hydride material in the tank 2, through the secondary circuit 6. Other variants and improvements can be provided without depart from the scope of the invention. Thus, if in the systems 1 shown in FIGS. 1 and 2, the pressurizing means 5 is arranged outside the enclosure 20 of the storage tank 2, it can equally well be envisaged that the pressurizing means 5 is arranged inside the enclosure 20, as shown in Figures 3A and 3B. In FIG. 3A, the pressurizing means 5 consists of a pressure accumulator in the form of a movable piston 51 in the part 30 of the hydrogen circulation circuit within the chamber 2, whereas in FIG. 3B, the accumulator 5 is a flexible membrane accumulator 51 in the portion 30. The exchanger tubes 40 within the chamber 2 may have different shapes such as circular section (Figure 4A), square (Figure 4B), rectangular (FIG. 4C), triangular (FIG. 4D), oblong (FIG. 4E), cross-shaped (FIG. 4F), or even quad-branched (FIG. 4G) or multi-branched (FIG. 4H). These latter star-shaped shapes have the particular advantages of increasing the exchange surface and facilitating their integration into the heat exchanger. The invention is not limited to the examples which have just been described; it is possible in particular to combine with one another characteristics of the illustrated examples within non-illustrated variants.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. A reversible hydrogen storage system (1) comprising: - a hydrogen storage tank (2) comprising an enclosure (20) containing metal hydrides integrated in a heat exchanger (21) with two fluid circuits, said exchanger primary, - a hydrogen circulation circuit (3), said first circuit, connected to the interior of the chamber, for supplying or recovering the H2 hydrogen respectively absorbed or desorbed by the metal hydrides, the part (30) ) of the first circuit inside the enclosure constituting one of the exchanger circuits, - a circulation circuit of a coolant (4), said second circuit, connected to the exchanger, the portion (40) of the second circuit in the exchanger constituting the other circuit of the exchanger, the first and second circuits being sealed with respect to each other, - a pressurizing means (5) for bringing the value of the pressure into the second circuit has a value of oche of the one in the first circuit.
    [0002]
    2. System according to claim 1, the heat transfer fluid being a liquid, preferably water-based, in particular with glycol or the like.
    [0003]
    3. System according to claim 1 or 2, the pressurizing means consisting of the tube (s) (400) of the heat exchanger (21), the section of the tube (s) of 20 exchanger being adapted to deform sufficiently to bring the value of the pressure in the second circuit to a value close to that in the first circuit.
    [0004]
    4. System according to claim 1 or 2, the pressurizing means consisting of a pressure balancer consisting of an enclosure (50) inside which is fixed a movable element (51) sealingly separating a first (52) ) chamber 25 of a second (53) chamber, the first chamber (52) being connected to the first circuit (3), the second chamber (53) being connected to the second circuit (4).
    [0005]
    5. System according to claim 4, the movable element being a flexible membrane (51) or a piston.
    [0006]
    6. System according to one of the preceding claims, the pressurizing means (5) being arranged outside the storage tank of H2.
    [0007]
    7. System according to one of claims 1 to 5, the pressurizing means (5) being arranged inside the chamber (20) of the storage tank of Hz.
    [0008]
    8. System according to one of the preceding claims, the second circuit comprising a first pump (60) and another heat exchanger (41) constituting a first secondary heat exchanger.
    [0009]
    9. System according to claim 8, the secondary fluid of the secondary exchanger (41) being a liquid, preferably water, or a gas, preferably air.
    [0010]
    10. The method of operation of a system according to one of the preceding claims, comprising a permanent pressurization step, to bring the pressure value in the second circuit to a value close to that of the first circuit. .
    [0011]
    11. The method of claim 10, the pressurization step being performed automatically.
    [0012]
    12. The method of claim 10 or 11, the pressure in the second circuit being greater than that in the first circuit.
    [0013]
    13. The method of claim 12, the pressure in the first circuit being at least equal to 350 bars, the pressure in the second circuit being greater than about 2 to 3 bars.
    [0014]
    14. A power supply assembly comprising a fuel cell (7) and a system (1) according to claim 8 or 9, the first secondary heat exchanger (41) being connected to the fuel cell so that the heat is removed. by the fuel cell in operation allows the desorption of hydrogen in the tank (2).
    [0015]
    15. A stationary hydrogen refueling installation of an assembly according to claim 14, comprising a second pump (44) and a second secondary heat exchanger (45), the second pump and the second secondary heat exchanger being intended to be connected to the second circuit during recharging in H2 of the tank (2).
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    同族专利:
    公开号 | 公开日
    US20160327210A1|2016-11-10|
    EP3090199A1|2016-11-09|
    FR3016021B1|2016-02-05|
    DK3090199T3|2018-05-28|
    WO2015101905A1|2015-07-09|
    CA2935694A1|2015-07-09|
    JP2017509838A|2017-04-06|
    EP3090199B1|2018-02-21|
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    法律状态:
    2015-01-30| PLFP| Fee payment|Year of fee payment: 2 |
    2016-01-29| PLFP| Fee payment|Year of fee payment: 3 |
    2017-01-31| PLFP| Fee payment|Year of fee payment: 4 |
    2018-01-30| PLFP| Fee payment|Year of fee payment: 5 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1450008A|FR3016021B1|2014-01-02|2014-01-02|REVERSIBLE H2 STORAGE SYSTEM WITH PRESSURE BALANCING CONTAINING METAL HYDRIDE RESERVOIR|FR1450008A| FR3016021B1|2014-01-02|2014-01-02|REVERSIBLE H2 STORAGE SYSTEM WITH PRESSURE BALANCING CONTAINING METAL HYDRIDE RESERVOIR|
    JP2016544438A| JP2017509838A|2014-01-02|2014-12-23|Reversible H2 storage system with tank containing metal hydride in a pressure balanced state|
    US15/109,755| US20160327210A1|2014-01-02|2014-12-23|Reversible h2 storage system with a tank containing metal hydrides, with pressure balancing|
    CA2935694A| CA2935694A1|2014-01-02|2014-12-23|Reversible h2 storage system with a tank containing metal hydrides, with pressure balancing|
    PCT/IB2014/067272| WO2015101905A1|2014-01-02|2014-12-23|Reversible h2 storage system with a tank containing metal hydrides, with pressure balancing|
    DK14835517.5T| DK3090199T3|2014-01-02|2014-12-23|REVERSIBLE H2 STORAGE SYSTEM WITH RESERVOIR CONTAINING METAL HYDROIDS AND WITH PRESSURE EQUALIZATION|
    EP14835517.5A| EP3090199B1|2014-01-02|2014-12-23|Reversible h2 storage system with a tank containing metal hydrides, with pressure balancing|
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