WO2018154043A1

WO2018154043A1 - System for storing and supplying hydrogen

Info

Publication number: WO2018154043A1
Application number: PCT/EP2018/054485
Authority: WO
Inventors: Michael Francis Levy; Jorn OUBRAHAM; Carsten Pohlmann; Jean-Baptiste Dementhon
Original assignee: Aaqius & Aaqius Sa
Priority date: 2017-02-24
Filing date: 2018-02-23
Publication date: 2018-08-30
Also published as: TW201840352A; FR3063330B1; CN110573790A; FR3063330A1

Abstract

A system for storing and supplying hydrogen to a unit (130) for using hydrogen, comprising: - a first tank (110) for storing hydrogen comprising a first material (111) for metastable storage of hydrogen by sorption; and - a second tank (120) for storing hydrogen comprising a second material (121) for reversible storage of hydrogen by sorption, a hydrogen outlet (1101) from the first tank to the second tank and/or the unit for using hydrogen; - a hydrogen outlet (1201) from the second tank to the unit for using hydrogen, so as to allow the first tank to supply a first flow of hydrogen to the unit for using hydrogen, and to allow the second tank to supply a second flow of hydrogen to the unit for using hydrogen, the second flow completing and/or replacing the first flow.

Description

Hydrogen storage and supply system

Field of the Invention The invention relates to a system for storing and supplying hydrogen. The invention also relates to an associated method.

State of the art

There are hydrogen storage and supply systems. These systems may comprise at least one solid material for storing hydrogen. It can be a metastable material. This type of material makes it possible to store large quantities of hydrogen. However this type of material needs to be heated when used to provide a significant flow. Moreover, even during storage, the metastable material always releases small amounts of hydrogen over time.

These systems must obey many constraints, related to the use for which they are intended, for example a use in a motor vehicle, for example a fuel cell.

Sufficient storage capacity and throughput to ensure the intended use are required. However, in case of start-up, this flow can not be obtained with conventional systems and requires the presence of an electric battery. On the other hand, in the case of a rapid and significant increase in hydrogen demand, it may be necessary to increase the temperature of the material, which may be difficult to obtain and cause overproduction of hydrogen. .

Summary of the invention An object of the invention is to provide a system for solving at least one of the above disadvantages. An object of the invention is in particular to provide a system that can be both safe and functional.

For this purpose, there is provided a system for storing and supplying hydrogen to a unit for using hydrogen, comprising:

a first hydrogen storage tank comprising a first metastable sorption hydrogen storage material, and a second hydrogen storage tank comprising a second reversible sorption hydrogen storage material,

a hydrogen outlet from the first reservoir to the second reservoir and / or the hydrogen utilization unit,

a hydrogen outlet from the second reservoir to the unit for using hydrogen,

so as to allow the first reservoir to provide a first flow of hydrogen to the utilization unit, and the second reservoir to provide a second flow of hydrogen to the utilization unit, the second flow completing and / or replace the first stream. characteristics are advantageously supplemented by the following characteristics, taken alone or in any of their technically possible combinations:

the system is configured to allow the first reservoir to provide the first flow to the second reservoir to recharge the second reservoir with hydrogen,

the system is configured such that in at least one operating position, the first reservoir, the second reservoir and the hydrogen utilization unit are maintained in fluid communication, and where the evolution of the amount of hydrogen stored speak second material is passively controlled according to the hydrogen demand of the hydrogen utilization unit

the second material is suitable for forming a hydride, preferably a metal hydride, preferably of LaNis, FeTi, TiCr, TiV, TiZr and / or TiMn _{2 type} ,

the first material is suitable for forming a hydride, preferably a metal hydride, for example alane, for example at least one alane phase, for example alane alpha, for example alane alpha prime and / or borazane and / or 1,2-di-amineborane, and / or lithium hydride and / or lithium aluminum hydride,

the second reservoir is, for example, configured to supply, at ambient temperature, the second flow of hydrogen so as to allow operation of the utilization unit,

the hydrogen outlet from the first reservoir to the second reservoir and / or the hydrogen utilization unit is provided with a non-return valve,

the hydrogen utilization unit comprises a fuel cell and / or an exhaust gas treatment system and / or a hydrogen engine,

for each second reservoir, the system comprises a hydrogen outlet from the second reservoir to the hydrogen utilization unit and a hydrogen inlet from the second reservoir, the inlet being at least partially distinct from the outlet,

control means (170) configured to implement the method as described below.

The invention further relates to a method of supplying hydrogen to a hydrogen consumption unit, the method being implemented by the system according to the invention. These characteristics are advantageously supplemented by the following characteristics, taken alone or in any of their technically possible combinations:

- temperature rise of the first material until an operating temperature is reached,

before and / or during the rise in temperature, supplying the second reservoir of the second stream of hydrogen to the utilization unit instead of the first flow,

- Once the operating temperature reached by the first material, supplying the first reservoir of the first flow of hydrogen, and preferably stopping the supply of the second flow,

- supply by the first reservoir of the first flow of hydrogen to the unit of use,

- supply by the second reservoir of the second hydrogen stream to the use unit in addition to the first flow,

reloading hydrogen of the second reservoir by the first reservoir,

at the end of at least one step of supplying the second reservoir of the second hydrogen stream, the second reservoir has a sufficient loading to implement a new step of supplying the second hydrogen stream.

Brief description of the figures

Other features and advantages of the invention will become apparent in the following description of an embodiment. In the accompanying drawings:

FIG. 1 represents an exemplary system according to an exemplary embodiment of the invention, FIG. 2 represents an exemplary behavior of the system during the implementation of an exemplary method according to an exemplary embodiment of the invention, and

FIG. 3 represents an example of differences in behavior between a reversible storage material and a metastable storage material.

Detailed description of the invention

Hydrogen storage and / or supply system

General presentation With reference to Figure 1, there is described a system 100 for storing and / or supplying hydrogen.

The system 100 is for example a hydrogen storage and / or supply system, for example at least one hydrogen utilization unit 130. The system 100 is for example a storage and / or supply system for hydrogen. hydrogen for a device.

The system 100 is for example a system for storing and / or supplying hydrogen for a vehicle. The vehicle is for example a motor vehicle. The motor vehicle is for example a vehicle with an electric motor, for example powered by a fuel cell. The motor vehicle is for example a vehicle with a heat engine.

The system 100 is for example a system for storing and / or supplying hydrogen for a stationary device. The stationary device is for example an electricity supply unit, for example a generator, for example a backup and / or emergency electricity supply unit, for example a lighting unit, for example lighting a construction. The electricity supply unit is for example portable.

The system 100 comprises for example at least one first hydrogen storage tank 1 10, for example a plurality of first tanks 1 10. The first tank 1 10 comprises for example a first material 1 1 1 for storing hydrogen.

Unless otherwise stated, the terms first, second and other ordinals are used simply to list elements and do not prejudge an order between them.

The first material 11 may be a solid material or in the form of a gel. The first material 11 may be a storage material by adsorption and / or absorption. The first material 11 may be a storage material by hydriding and / or dehydriding. The first material 1 1 1 is a metastable storage material of hydrogen, for example by sorption.

By metastable is meant a material which, in usual pressure domains (i.e., less than 200 bar), will still be in the hydrogen desorption regime.

FIG. 3 thus illustrates the difference between a metastable material, for example alane, and a reversible material (non-metastable), for example of TiMn2 type. In this figure are shown absorption equilibrium or adsorption or desorption curves, that is to say curves representing the equilibrium pressure absorption, adsorption or desorption, in this case the natural logarithm of this pressure, as a function of the hydrogen concentration in the material, for example expressed as a mass percentage, for example at a given temperature, for example at 80 ° C. Above the curve, the material is in the charging zone and therefore captures hydrogen. Below the curve, the material is in the discharge zone and thus releases hydrogen. It should be noted that this figure is schematic and that in reality, the curves absorption or adsorption and the desorption curves are not necessarily confused but keep a similar profile and orders of magnitude.

The equilibrium curve of the reversible storage material typically depends on the temperature: the higher the temperature, the higher the equilibrium pressure and the larger the discharge zone. The curve has a first increasing low pressure section, a second substantially stable or slightly increasing average pressure section, and a third increasing high pressure section. The second section is typically well below 200 bar.

The equilibrium curve of the metastable storage material has a first increasing low pressure section, a second substantially stable or a lower increasing average pressure section, and a third increasing high pressure section. The second section is typically much greater than that of a reversible storage material, for example much greater than 200 bar, for example of the order of several thousand bars. Thus, under operating or usual conditions, the metastable storage material is typically still desorbing hydrogen and not capturing it.

The system 100 comprises for example at least one second tank 120 for storing hydrogen. The second tank 120 comprises for example a second material 121 for storing hydrogen. The second material 121 is, for example, a reversible storage material for hydrogen, for example by sorption.

Sorption is the process by which a substance is adsorbed or absorbed on or in another substance. Absorption refers to the ability of a material to retain molecules in its volume. By adsorption is meant the ability of a material to retain molecules on its surface.

The second material 121 may be a solid material or in the form of a gel. The second material 121 may be a storage material by adsorption and / or absorption. The second material 121 may be a storage material by hydriding and / or dehydriding.

By reversible means that a material initially loaded and which has been at least partially discharged may be at least partially recharged in the medium in which the material is placed, for example a medium consisting of gaseous dihydrogen.

It can conventionally be defined the partial reloading as being a reloading at a pressure less than or equal to 200 bar, in a temperature range suitable for reloading the material, for example at an optimum temperature for reloading the material at the pressure in question, for example so as to achieve a given load rate, for example 50%, for example so as to increase the load ratio by a given percentage for example by at least 10%.

The system comprises for example a hydrogen outlet 101 of the first reservoir to the second reservoir and / or the hydrogen utilization unit, the system comprises, for example, a hydrogen outlet 1201 from the second reservoir to the unit. utilizing hydrogen, for example to allow the first reservoir to provide a first flow of hydrogen to the utilization unit, and the second reservoir to provide a second flow of hydrogen to the unit of use, the second stream to complete and / or replace the first stream.

For example, the system is configured and / or the first tank and the second tank are arranged and / or the first material and the second material are arranged to allow, for example in a first operating position, the first tank 1 10 to supply the first hydrogen stream to the utilization unit 130, for example when the system is in operation. For example, the system is configured and / or the first tank and the second tank are arranged and / or the first material and the second material are arranged to allow, for example in the first operating position, the second tank 120 of supplying the second stream of hydrogen to the utilization unit 130, the second stream for example completing and / or replacing the first stream, for example when the system is in operation.

It is thus possible to achieve a secure and compact system with the first tank, which can check pressure limit criteria and have a large hydrogen storage capacity while being compact using a metastable storage material, while presenting with the second tank a more responsive unit that comes to solve the problems associated with the use of a metastable storage material. This unit can for example allow the system to start to reach a temperature sufficient for the first tank. In particular, the second tank 120 is for example adapted to supply the second stream of hydrogen so as to allow the operation of the unit of use, for example in addition to the first stream of hydrogen, for example in the absence the first stream of hydrogen, for example at room temperature, for example at a room temperature of less than or equal to 15 ° C, for example less than or equal to 10 ° C, for example less than or equal to 0 ° C, for example lower or equal to -10 ° C, for example less than or equal to -20 ° C, for example to allow the start and / or operation of the use unit, for example until the first tank 1 10 be able to provide a first flow sufficient to operate alone the unit of use of hydrogen. It is thus possible to quickly start the system at all temperatures possible for the chosen application, for example despite low temperatures, for example not suitable for the first tank, for example while heating the first tank. It is thus possible to implement a system which is rapidly effective at startup while using as storage material, for example as main storage, a material requiring high operating temperatures, for example greater than or equal to 90 ° C. that a material forming alane.

Alternatively in addition, such a unit makes it possible to rapidly supply a surplus of hydrogen when the demand increases sharply, for example when the unit of use of hydrogen is strongly stressed or during a purge. In particular, the device is configured so that, in particular the first material and the second material are for example adapted so that the pressure decrease related to a hydrogen demand of the first reservoir causes the production of hydrogen by the second tank.

It is thus possible to obtain a system operating efficiently at lower pressures, which makes it possible to reduce the thickness of the walls of the tank and to improve its density and / or its gravimetric storage density.

In particular, it is thus possible to obtain a sufficient equilibrium pressure in the second reservoir which ensures the supply of hydrogen at a high pressure and / or a high flow rate and / or a high availability of hydrogen within the second reservoir. material.

Alternatively or in addition, such a unit can provide a flow of hydrogen during the crossing of a cold zone or in case of weakness of the heating of the first reservoir which causes a cooling of the first material and therefore a reduction at least temporarily of the production of hydrogen by the first tank. It is also possible to dispense with the preheating device of the first reservoir, or to limit the dimensions of the device preheating, or limit its use. This is particularly advantageous since electric batteries that would operate at low temperatures can occupy a large space and / or have a large mass to heat a metastable storage material. This also simplifies the system because preheating constraints are lower, especially for the first tank which contains a metastable storage material, especially in that it is no longer necessary for heating to have to allow sudden overproduction. by the same tank, and all the more vis-à-vis cases where the heating and preheating of the first tank are in different natures. This still allows to have quickly, or even immediately, a significant power unlike the limited powers during preheating. This further limits the energy losses associated with electric heating, especially at low temperatures. This further simplifies the control of the system.

It is thus possible to obtain an efficient and responsive system. Such a system is particularly advantageous compared to a large tank which has less efficiency, high inertia and therefore low reactivity in case of sudden demand as well as a low reactivity to return to a state of lower hydrogen production . Because of its efficiency, such a system can cause energy consumption, for example fuel, less.

It is also possible to dispense with overpressure release valve in the first tank, which is subjected to low pressure, or to reduce the leakage associated with the valve. It is also possible to do without valve or pressure relief valve in the second tank, which is smaller in size, can be designed with increased resistance, or reduce the leakage associated with the valve. It is thus possible to reduce the hydrogen losses associated with such valves and / or the safety risks associated with the release of hydrogen, for example if an element from the tank blocks the valve and / or limit this procedure to an emergency situation.

It is thus possible not to be subject to minimum and / or maximum temperature limitations for the system without this entailing operational or safety problems.

It is also possible to modify the tank design with respect to very stable tanks sized to be very resistant to high pressures. This then makes it possible to increase the volumetric and / or gravimetric storage capacity, and / or the efficiency and heat transfer because there is less material to heat, and / or a reduction in the weight of the tank and / or other elements associated with the reservoir such as connecting means which no longer have to withstand high pressures.

The system 100 is for example configured so as to reload the second tank 120 with the first tank 1 10, when the system is in operation. The system is for example configured so as to allow, for example in a second operating position, the first tank 1 10 to provide the first flow to the second tank 120 in order to recharge the second tank 120 hydrogen. This allows for example to operate the system until complete shutdown without loss or risk associated with a surplus of hydrogen production since the hydrogen produced to the end can be captured by the second tank. The system is for example configured so that the second tank can absorb all the hydrogen produced by the first tank during shutdown.

The system is therefore safer in that it requires less control, whether by automatic means or by an operator in operation. It also does not require the evacuation of hydrogen produced under conditions where it is not used by the unit for using hydrogen, for example during shutdown. It is thus possible alternatively to use the second tank 120 when the first tank 1 1 0 is not able or not enough to ensure the hydrogen demand, then to recharge the second tank 120 during stationary phases or quieter , in anticipation of a new use of the second tank 120.

The second tank 120 is for example configured to provide the second flow of hydrogen and / or to be reloaded passively depending on the pressure within the second tank and / or the pressure of the system. The second tank 120 is for example configured to provide the second flow of hydrogen and / or to be reloaded passively depending on the pressure difference between on the one hand the pressure within the second tank and / or the pressure of the system, and secondly the equilibrium pressure of the second material, for example the desorption and / or sorption equilibrium pressure, for example as a function of the temperature, for example as a function of the charge rate. The second reservoir 120 forms for example a compensation unit of the first reservoir 1 10 with respect to the hydrogen demand.

By desorption equilibrium pressure of a material at a given temperature and at a given charge rate is meant the minimum gas pressure exerted on the material for which there is no release of hydrogen. At an infinitesimally lower pressure, hydrogen is released.

By equilibrium pressure of absorption or adsorption of a material at a given temperature and at a given charge rate, is meant the maximum gas pressure exerted on the material for which there is no pressure. absorption or adsorption of hydrogen. At an infinitesimally higher pressure, hydrogen is absorbed or adsorbed.

The charge rate is for example expressed as a percentage.

The charge rate can be defined as the ratio of the mass of hydrogen introduced into the system to the maximum mass of hydrogen that the system can hold, at the given temperature. By convention, it can be defined that the maximum mass, and therefore the charge rate, is calculated at a reference pressure, for example 200 bar. Unit of use of hydrogen

The system 100 comprises for example at least one hydrogen utilization unit 130, for example a plurality of hydrogen utilization units.

The at least one hydrogen utilization unit 130 is or includes, for example, a hydrogen consumption unit.

The at least one hydrogen utilization unit 130 is or comprises, for example, a system for treating gases from an engine, for example at an exhaust line.

The at least one hydrogen utilization unit 130 is or includes, for example, a fuel cell, for example a proton exchange membrane fuel cell.

The at least one hydrogen utilization unit 130 may comprise the fuel cell and / or an electric motor adapted to be powered by the fuel cell. The at least one unit for using hydrogen is or comprises, for example, a hydrogen engine, for example a heat engine adapted to be supplied with hydrogen, for example an internal combustion engine and / or a mixed engine.

The system is for example configured so that the first tank 1 10 and / or the second tank 120 can supply the hydrogen utilization unit with hydrogen. The unit for using hydrogen has, for example, an inlet pressure greater than or equal to 1.5 bar, for example 2.5 bar, for example 5 bar, for example 10 bar.

Fluid connections The first tank 1 10 and / or the second tank 120 and / or the hydrogen utilization unit 130 are for example connected fluidically, for example as illustrated in FIG.

By "fluidic connection between two elements" means any means of fluid communication adapted to put in fluid communication the two elements. The fluidic communication means may for example comprise one or more pipes and / or one or more valves.

For example, the first tank 1 10 and the second tank 120 are fluidly connected, for example so that the fluid connection can be selectively blocked. For example, the second tank 120 and the hydrogen utilization unit 130 are fluidly connected, for example so that the fluid connection can be selectively blocked.

The second tank 120 is for example disposed between the first tank 1 10 and the hydrogen utilization unit 130, the first tank 1 10 and the hydrogen utilization unit 130 being connected fluidically via the second tank 120 .

The system 100 comprises, for example, the hydrogen outlet 1101 from the first tank 1 10 to the second tank 120 and / or the hydrogen utilization unit 130, for example towards the hydrogen utilization unit 130 via the second tank 120. The output 1 101 is for example provided with output blocking means 1 102, which comprise for example a valve, for example a solenoid valve, are for example movable at least between an open position and a closed position. In the open position, the outlet 1 101 allows the flow of hydrogen from the first tank 1 10. In the closed position, the outlet 1 101 does not allow the flow of hydrogen from the first tank 1 10. Alternatively the output 101 is for example devoid of blocking means. The output 1 101 comprises for example one or more pipes and / or one or more walls. Exit 1 101 can be provided a non-return valve, for example to prevent any return of hydrogen from the second tank 120 and / or the hydrogen utilization unit 130. The outlet 101 forms a fluid connection between the first tank 10 and the second reservoir 120, for example a direct fluid connection, for example, when the blocking means 1 101 are in the open position or when the outlet 1 101 has no blocking means, the pressure within the first tank 1 10 is substantially equal to the pressure within the second tank 120.

The system 100 comprises, for example, a hydrogen outlet 1201 from the second tank 120 to the hydrogen utilization unit 130. The outlet 1201 forms, for example, a hydrogen inlet of the second tank 120 from the first tank 1 10. It is then for example the pressure which determines whether the behavior of the output is that of an output or an input. Alternatively or in addition, the hydrogen inlet of the second tank 120 from the first tank 1 10 may be at least partially separate from the outlet 1201. The output 1201 is for example provided with output blocking means 1202, which comprise for example a valve, for example a solenoid valve, are for example movable at least between an open position and a closed position. In the open position, the outlet 1201 allows the flow of hydrogen from the second tank 120 to the utilization unit 130. In the closed position, the outlet 1201 does not allow the flow of hydrogen from the second tank 120. The output 1201 comprises for example one or more pipes and / or one or more walls. The output 1201 comprises for example a pressure sensor 1203, for example disposed between the second reservoir 120 and the locking means 1202.

The system 1 10 comprises for example a hydrogen inlet 1301 of the hydrogen utilization unit 130 from the first tank 1 10 and / or the second tank 120. The inlet 1301 forms for example the outlet 1201. The input 1301 is for example provided with locking means 1302 input, which include for example a valve, by For example, a solenoid valve can be moved at least between an open position and a closed position. The locking means 1302 form for example the blocking means 1202. In the open position, the inlet 1301 allows the flow of hydrogen to the consumption unit 130. In the closed position, the inlet 1301 does not allow the flow of hydrogen to the consumption unit 130. The inlet 1301 may be provided with dosing means, the input blocking means 1302 forming the dosing means or the dosing means being distinct from the blocking means input 1302. The input 1301 comprises for example one or more pipes and / or one or more walls. The inlet 1301 may be provided with a non-return valve, for example to prevent any return of hydrogen from the hydrogen utilization unit 130.

The second tank 120 comprises for example hydrogen recharging means separate from the first tank 1 10. The separate hydrogen charging means comprise for example a dedicated input, comprising for example one or more pipes and / or one or more walls. The dedicated input is for example provided with dedicated blocking means, which comprise for example a valve, for example a solenoid valve, are for example movable at least between an open position and a closed position.

The first reservoir 1 10, the second reservoir 120 and the hydrogen utilization unit 130 are for example fluidly connected so that, in at least one operating position, the first reservoir 1 10, the second reservoir 120 and the Hydrogen utilization unit 130 is maintained in fluid communication. The system is thus arranged so that the same pressure is the same within the first tank 1 10 and the second tank 120, the pressure of the hydrogen utilization unit 130 influencing the pressure within the first tank 1 10 and the second tank 120. Reservability of tank

The first tank 1 10 is for example removable.

The second tank 120 is for example irremovable. Removable means what can be replaced without disassembling the rest of the system that would make it non-functional. By irremovable means that can not be replaced without disassembling the rest of the system that would make it non-functional. Alternatively the second tank 120 is for example removable so as to allow easy replacement.

The fluid connection between the first and second tanks 1 10 and 120 therefore allows for example to recharge the second tank 120 without stopping the operation of the device, for example the vehicle, or in the case where the second tank 120 is irremovable.

It is possible to dimension separately the first tank of the second tank, which allows a simplification of the sizing of the system and compactness improve for the first tank, which is particularly interesting if it is removable. Plurality of second tanks

The system may comprise a plurality of second reservoirs 120. The first reservoir 1 10 and / or the second reservoirs 120 and / or the hydrogen utilization unit 130 are for example fluidly connected.

tanks

The first tank 1 10 comprises for example a first chamber 1 12, the first material January 1 being for example disposed within the first chamber 1 12. The second reservoir 120 comprises, for example, a second enclosure 122, the second material 121 being for example disposed within the second enclosure 122. The second enclosure 122 has, for example, a higher pressure resistance than the first enclosure 1 12.

hydride

The first material 11 comprises or is a hydrogen storage material, for example to form a hydride, preferably a metal hydride, for example alane, for example at least one alane phase, for example alane alpha, for example alane alpha prime, and / or borazane (ΒΗΘΝ) and / or 1,2-di-amineborane (also called EDAB, BH3NH2CH2CH2NH2BH3), and / or lithium hydride (LiH) and / or lithium aluminum hydride (LiAlH ₄ ).

The first material 11 comprises, for example, a powder.

The second material 121 comprises or is a hydrogen storage material, for example adapted to form a hydride, for example a metal hydride.

The second material 121 comprises or is for example a metal alloy adapted to form a hydride, for example at room temperature.

The second material 121 comprises for example a powder. The second material 121 may comprise or consist of a metal alloy, for example an intermetallic compound, of type A _n B _m , where A and B are metallic chemical elements, and n and m of natural numbers greater than or equal to 1 , for example of type AB _m , for example AB2 or AB5, for example of type A _n B, for example A2B, for example AB.

The second material 121 may comprise or consist of a metal alloy, for example comprising iron and / or vanadium and / or titanium and / or zirconium and / or magnesium. The second material 121 may comprise or consist of at least one alloy of LaNis and / or FeTi and / or TiCr and / or TiV and / or TiZr and / or TiMn2 type, and / or the corresponding hydride (s). (s). The second material 121 may also comprise or consist of at least one hydride of NaAIH ₄ and / or LiNh and / or LiBH _{4 type} , or the corresponding dehydrogenated form (s). The second material 121 may comprise or be made of a Ti type alloy (i _-y) Zry (MnVFe) 2 with y greater than or equal to 0 and y less than or equal to 1.

In particular, the second material 121 may comprise or consist of such an alloy, the second material 121 having a zirconium mass fraction of between 1% and 15%, for example between 1% and 10%, for example substantially equal to 3 %. The use of such mass fractions is particularly suitable for applications related to fuel cells for a vehicle.

Heating means

The system 100 comprises for example first heating means 1 13 of the first material 1 1 1 dedicated, for example a heater, for example a resistor, for example a heat exchanger. It is thus possible to heat the first reservoir while the second reservoir provides the necessary hydrogen, and then to use the first reservoir as the main or sole source of hydrogen for the hydrogen utilization unit and / or for recharge the second tank.

The first heating means 1 13 are for example adapted to receive all or part of the energy or heat necessary for their operation of the hydrogen utilization unit 130. The heat is for example directly supplied by means of a heat exchanger from the hydrogen utilization unit 130 to the first tank 1 10. The heat comprises or consists of, for example, heat from the reduction occurring within the hydrogen utilization unit 130 when the latter is a fuel cell. The heat comprises or consists of, for example, heat, for example heat from the gas exhaust line and / or from a heat engine, for example a hydrogen engine. The heat comprises or consists of, for example, heat resulting from a selective catalytic reduction reaction and / or the operation of an engine, for example a hydrogen engine. Alternatively or in addition to the energy is for example the electrical energy produced by the hydrogen utilization unit 130, the heating means 1 13 comprising at least one resistance.

In particular, the system can be configured so that, at a given environment temperature, the second tank 120 can supply hydrogen in sufficient quantity and / or flow and / or duration, to the unit use of hydrogen 130 to allow heating of the first tank 1 10 by the first heating means 1 13, in particular from an environmental temperature, in particular up to an operating temperature allowing the desorption of hydrogen from the first tank 1 10, in particular so as to allow the operation of the hydrogen utilization unit 130 without the supply of hydrogen by the second tank 120. The system can in particular be configured so that at a given environment temperature, the second reservoir makes it possible to supply hydrogen in an amount of at least 20%, for example at least 40%, for example at least 100%, for example, less than 300%, such energy and / or power and / or flow rate required. It is thus possible to provide a sufficient margin for several successive uses.

The operating temperature of the first chamber is for example a temperature at which the hydrogen release rate of the first material 1 1 1 is sufficient to provide the hydrogen utilization unit 130. The inlet pressure of the first chamber unit for using hydrogen 130 is, for example, less than or equal to 10 bar, for example less than or equal to 6 bars, for example less than or equal to 5 bars. The nominal operating temperature of the first material 1 1 1 is for example between 60 ° C and 300 ° C, for example between 80 ° C and 200 ° C, for example about 150 ° C. The starting temperature is for example between -40 ° C and 80 ° C, for example between -30 ° C and 50 ° C, for example approximately from -20 ° C.

The system 100 may for example comprise second heating means 123 of the second material 121 dedicated, for example a heater, for example a resistor, for example a heat exchanger. It is thus possible to provide even more rapidly a large amount of hydrogen, for example so as to boost the operation of the hydrogen utilization unit 130.

The second heating means 123 are for example adapted to receive all or part of the energy or heat necessary for their operation of the hydrogen utilization unit 130, for example when starting the system. The heat is for example directly supplied by means of a heat exchanger from the hydrogen utilization unit 130 to the second tank 120. The heat comprises or consists of, for example, heat resulting from the reduction taking place in the hydrogen utilization unit 130 when the latter is a fuel cell. The heat comprises or consists of, for example, heat, for example heat from the gas exhaust line and / or from a heat engine, for example a hydrogen engine. The heat comprises or consists of, for example, heat resulting from a selective catalytic reduction reaction and / or the operation of an engine, for example a hydrogen engine. Alternatively or in addition the energy is for example electric energy produced by the hydrogen utilization unit 130, the heating means 123 comprising at least one resistance. The second heating means 123 comprise, for example, a fan adapted to supply the second tank 120 with ambient heat. Cooling means

The system 100 comprises for example second cooling means 125 of the second material 121 dedicated, for example a cooling unit. The second heating means 123 form for example the second cooling means 125. The cooling is for example carried out by circulating a cooling fluid, for example air and / or Peltier effect.

The second tank 120 has for example a hydrogen storage capacity lower than that of the first tank 1 10. The second tank 120 has for example a hydrogen storage capacity less than or equal to 50%, for example less than or equal to 30% for example less than or equal to 20% of that of the first tank 1 10. The second tank 120 has for example a hydrogen storage capacity greater than or equal to 10% of that of the first tank 1 10.

The second tank 120 has for example a smaller volume than the first tank 1 10. The second material 121 has for example a smaller volume than the first material 1 1 1. Indeed, the second tank serving only for limited periods, its capacity, and therefore its size, can be limited. It also makes it possible to dimension it effectively by limiting the risks that it can present in terms of security. Thus, it is not necessary to resort to the use of a valve that involves a loss of hydrogen, or in any case it is possible to limit the use of this valve to specific cases. Moreover, it is thus possible to limit energy losses compared to a battery which would involve significant losses as time passes, and during temperature changes.

Working conditions

The second material 121 is for example adapted to supply hydrogen, for example according to a request from the unit of use, for example from control means as described below, at a temperature T _m in lower or equal to 0 ° C, for example less than or equal to -10 ° C, for example less than or equal to -20 ° C, for example at a pressure between 1 and 15 bar, for example between 1 and 10 bar for a battery with fuel, for example between 5 and 15 bar for an internal combustion engine or heat engine, for example between 1 and 2 bar for a gas treatment application, for example at ambient pressure, for example of the order of 1 bar for example to allow operation of the use unit 130.

The first tank 1 10, for example the first chamber 1 12, is for example adapted to withstand an internal pressure having a value between 1 and 100 bar, for example between 1 and 50 bar, for example between 1 and 25 bar, the pressure being a relative and / or absolute pressure.

The first tank 1 10, for example the first chamber 1 12, is for example adapted to withstand a temperature having a value between 60 ° C and 300 ° C, for example between 80 ° C and 200 ° C, for example about 150 ° C.

The system 100 is for example adapted so that the first tank 1 10 and / or the first chamber 1 12 is subjected only to pressures less than or equal to 100 bar, for example less than or equal to 50 bar, for example lower or equal to 25 bars. The second tank 120 has for example a mass strictly smaller than that of the first tank 1 10. The second material 121 has for example a mass strictly lower than that of the first material 1 1 1.

The level of filling of the second material 121 in the second chamber 122 is for example greater than or equal to 5%, for example 25%, for example 50% of the volume of the second chamber 122.

The second reservoir has for example an operating temperature, for example of nominal operation, greater than or equal to 10 ° C, for example less than or equal to 15 ° C, for example less than or equal to 20 ° C.

The second tank 120, for example the second chamber 122, is for example adapted to withstand an internal pressure having a value of between 20 and 130 bar, for example between 50 and 110 bar, for example between 70 and 90 bar, example of about 80 bar, the pressure being a relative pressure and / or absolute.

The second tank 120, for example the second chamber 122, is for example adapted to withstand a temperature having a value of between 40 ° C. and 120 ° C., for example between 50 ° C. and 90 ° C., for example between 60 ° C. C and 85 ° C.

Filtration means

The first tank 1 10 and / or the second tank 120 may comprise inlet and / or outlet gas particulate filtration means, for example one or more filters.

Heat transfer The first tank 1 10 and / or second tank 120 has for example an internal architecture for rapid heat transfer. Means of command

The system may comprise control means 170, for example a control unit. The control means may comprise at least one processor and / or a random access memory and / or a read-only memory and / or display means, for example a terminal.

The control means 170 may comprise one or more sensors adapted to measure and provide one or more measurements of the system state, for example in real time. The control means 170 may comprise a first temperature sensor 1 14 of the first reservoir, and / or a second temperature sensor 124 of the second reservoir, and / or a third temperature sensor 134 of the hydrogen utilization unit. and / or the pressure sensor 1203. The control means 170 may comprise a first pressure sensor 1 14 of the first reservoir, and / or a second pressure sensor 124 of the second reservoir, and / or a third pressure sensor 134 of the unit of use of hydrogen. The control means 170 may comprise a first hydrogen concentration sensor 1 14 of the first tank, and / or a second hydrogen concentration sensor 124 of the second tank.

The control means 170 are for example configured to control the state of hydrogen charge of the first tank 1 10 and / or the second tank 120 by controlling the pressure within the first tank 1 10 and / or the second tank 1 20, for example by controlling the supply of heat to the first tank 1 10 and / or the second tank 120.

The control means 170 may for example control the first tank 1 10, for example the first heating means 1 13. The control means 170 may for example control the second tank 120, for example the second heating means 123. The control means 170 may, for example, control the cooling means 125. The control means 170 may, for example, control the hydrogen utilization unit 130. The control means 170 may, for example, control the blocking means. 1 102. The control means 170 may for example control the locking means 1202. The control means 170 may for example control the locking means 1302.

The control means are for example configured to implement a method as described below.

Alternatively or in addition, the system is configured so that the evolution of the quantity of hydrogen stored by the second material can be controlled passively according to the hydrogen requirement of the hydrogen utilization unit 130. Thus, by the choice of materials, in particular the second material, a system can be obtained which only requires pressure management to be controlled.

In particular, the control means are for example configured to control the system so as to place or maintain it so that, as previously described, the first tank 1 10, the second tank 120 and the unit of use hydrogen are maintained in fluid communication, and to provide the first tank with a fixed flow control of hydrogen, for example via the first heating means 1 13. In such a position, if the hydrogen requirements of the unit the use of hydrogen 130 will vary, the hydrogen utilization unit 130 will cause pressure variations in the system, and the hydrogen production or hydrogen uptake by the second tank 120 will vary as a result of makes the transmission of the variation of pressure within the first tank 120, to adjust the production of hydrogen and restore a predetermined pressure depending on the temperature of the second material 12 1, the charge rate of the second material 121 and the flow rate provided by the first tank 1 10. For example, because of the unit of use of hydrogen 130 a pressure decrease, for example due to a purge of the hydrogen utilization unit 130, will cause the supply of a surplus of hydrogen by the second tank 120 while the flow rate of the first tank 1 10 remains substantially constant.

Fuel cell

Referring to Figure 1, there is described system 100 in which the hydrogen utilization unit 130 comprises or is a fuel cell. The system 100 is thus a system for storing and supplying hydrogen to a fuel cell, for example for a device, for example for a vehicle or a stationary device. There is also disclosed a fuel cell system including system 100.

The fuel cell is for example a fuel cell membrane proton exchange. The fuel cell is for example adapted to provide at output a nominal electric power sufficient for a given application. Exhaust line

The hydrogen utilization unit 130 may comprise or be an exhaust line or an exhaust gas treatment device by selective catalytic reduction. The system 100 is thus a system for storing and supplying hydrogen to an exhaust line and / or a catalyst for a device, for example for a vehicle or a stationary device. There is also described a system for treating the exhaust gases of a device, for example a vehicle or a stationary device, comprising the system 100.

Thermal motor The hydrogen utilization unit 130 may comprise or be a heat engine. It is thus possible to supply the heat engine directly with hydrogen. The system 100 is thus a system for storing and supplying hydrogen to a heat engine, for example for a vehicle or a stationary device. There is also described a system for supplying energy by a heat engine, for example a vehicle or a stationary device, comprising the system 100.

With reference to FIG. 2, there is described a method of supplying hydrogen to a hydrogen consumption unit, for example such as that described above. The method is for example adapted to be implemented by the system 100 described above or implemented by the system 100 described above.

Each of the described steps may be repeated one or more times or combined with one or more of the described steps if this combination is technically possible.

The method is or includes, for example, a method of starting the system and / or a method of using the system, for example during operation.

The method comprises for example a step of receiving a hydrogen demand for the utilization unit 130, and / or of calculating a hydrogen demand for the utilization unit 130, by the control means 170. .

The steps described below are for example implemented on command of the control means 170 and / or depending on the hydrogen demand. The hydrogen demand is for example updated, for example at regular intervals, for example in real time. The method comprises, for example, a step 800 of increasing the temperature of the first material January 1, for example until reaching the operating temperature.

The method comprises for example a step 802, for example carried out during step 800 and / or during a temperature rise of the first material 1 1 1. Step 802 includes, for example, supplying the second tank 120 with the second stream of hydrogen to the use unit instead of the first stream.

The rise in temperature is for example carried out by the first heating means 1 13. The first heating means 1 13 receive for example all or part of the energy or heat necessary for their operation of the utilization unit 130 , the heat being for example partially or completely resulting from the thermal discharges of the use unit 130.

The method can thus comprise, for example at the same time as at least a part of the step 800 and / or 802, a step 8001 of absence of supply of the first flow and / or blocking by the first blocking means 1 102 from exit 1 101.

The method can thus comprise, for example at the same time as at least a part of the step 800 and / or 802, for example after the step 8001, a step 8002 of supplying the first flow, for example of increasing the first flow and / or decrease of the second flow, for example the first flow remaining below a predetermined nominal flow and / or the temperature of the first material being lower than a nominal temperature, and / or the unlocking by the first locking means 1 102 from exit 1 101.

The method may comprise, for example once the nominal operating temperature reached by the first material, a step 804 for supplying the first tank 1 10 of the first hydrogen stream to the unit of use 130. The method may comprise a stop step 806 from supplying the second stream to the utilization unit 130, for example performed at the same time or after step 804 has started.

It is thus possible to start or operate the system while the first tank is not yet in a state to meet the hydrogen demand necessary for the operation of the unit of use, for example when starting the system. .

The method thus comprises, for example, a step of starting the system, the starting step comprising step 800 and / or 802 and / or 8001 and / or 8002.

At the end of the starting step, the second tank 120 may have a loading less than or equal to 50%, for example less than or equal to 40%, preferably less than or equal to 30%, of the maximum hydrogen capacity. the second reservoir 120, considered for example at a given temperature, for example at room temperature, for example at 20 ° C. The second material is thus able to absorb hydrogen possibly released by the first material, for example while this hydrogen is not intended to be used by the unit of use, for example during shutdown. of the system.

Maximum capacity means the capacity corresponding to a 100% charge rate at a given temperature.

The method may furthermore comprise a step 810 for recharging the second tank 120 with hydrogen by the first tank 1 10. It is thus possible to recharge the second tank which has already been used in a previous stage with hydrogen.

Step 810 takes place, for example, at the same time as a step of supplying the first reservoir 1 10 of the first stream of hydrogen to the utilization unit 130. It is thus possible to maintain the normal operation of the unit of use 130 while preparing the eventuality of new specific commands requiring the use of the second tank 120. Step 810 is then implemented for example up to a level of predetermined loading of the second tank 120, for example so as to allow to find the level of hydrogen in the second tank 120 equivalent to that prior to the last implementation of a step 808 as described below, for example less than or equal to 50%, preferably 40%, preferably 30%, preferably greater than or equal to 10%, for example greater than or equal to 15%, for example greater than or equal to 25%, of the maximum capacity hydrogen of the second tank 120 at a given temperature, for example at 50 ° C, for example at 20 ° C.

The method may comprise a step 808 of supplying the first reservoir of the first hydrogen stream to the unit of use and supply by the second reservoir of the second hydrogen stream to the use unit in addition to the first flux. Step 808 is for example implemented in the event of excessively high demand for the first reservoir 1 10, that is to say for example a demand that the first reservoir can not satisfy in terms of flows or beyond the nominal flow. It is thus possible to simultaneously combine the two streams to meet a particularly high demand and / or abrupt hydrogen, for example during a purge. Step 808 is for example implemented as a result of one or more of the steps previously described and / or described below. Step 808 is for example followed by a step of stopping the second stream. At the end of at least one step of supplying the second tank of the second hydrogen stream, for example step 800, for example 8001 and / or 8002, and / or 810, the second tank may have a charge. sufficient to implement a new stage of supply of the second hydrogen stream. It is thus possible to use the second tank 120 several times in succession, even if the tank has not been recharged or only partially recharged in the meantime. The loading is for example greater than or equal to 50%, for example greater than or equal to 30%, of the maximum loading of the second tank 120 considered for example at a given temperature, for example at room temperature. Alternatively, the second reservoir may not have sufficient loading to implement a new step of supplying the second hydrogen stream, the process relying on recharging by the first reservoir.

The method may furthermore comprise a step 812 for recharging the second tank 120 with hydrogen by the first tank 1 10. It is thus possible to recharge the second tank which has already been used in a previous stage with hydrogen.

Step 812 for example takes place at the same time as an absence and / or a reduction of supply by the first tank 1 10 of the first hydrogen stream to the unit of use 130, for example in the absence of a command to use the utilization unit 130 and / or in the absence of use of the utilization unit 130.

It is thus possible to prepare the possibility of new specific orders requiring the use of the second tank 120 when the unit of use no longer requires hydrogen input.

The method may comprise a step of stopping the supply of hydrogen, for example by the first reservoir 1 10, for example to the utilization unit 130, the stopping step comprising, for example, step 812. It is thus possible to take advantage of the inevitable production of hydrogen by the first tank at the end of the supply stage.

The method may include a step of stopping the utilization unit 130, the stopping step including for example step 812.

The method may include a system shutdown step, the shutdown step comprising for example step 812. It is thus possible to implement a shutdown step of the system, for example by preparing the possibility of new specific commands requiring the use of the second tank 120, for example during a next start.

The method may comprise a step of automatically controlling the quantity of hydrogen stored by the second reservoir 120, so as to maintain and / or bring the level of hydrogen stored by the second reservoir below a certain threshold, by example to maintain and / or bring the level of hydrogen stored by the second reservoir above a certain threshold, for example so as to maintain and / or direct the level of hydrogen stored by the second reservoir to a predetermined value. The control is for example carried out only in the operating phase, the operating phase being that between the start step and the stop step. It is thus possible, for example without start-up, shutdown and / or significant demand, to constitute a limited reserve of hydrogen with a view to a significant demand, while maintaining the level sufficiently low to absorb the hydrogen emitted during the stop.

The control may include limiting the use of the second tank 120 during the operating phase, for example a limitation to the implementation of one or more steps 808.

The control step aims for example to maintain or to bring the quantity of hydrogen stored by the second tank 120 preferably between 10 and 90%, for example between 15 and 85%, between 20 and 80% of the maximum capacity of hydrogen of the second tank 120, considered for example at a given temperature, for example at room temperature, for example at 20 ° C, this control being for example carried out during the start-up stage and / or the operating phase and / or the stop step.

The control step is intended, for example, to maintain or bring the quantity of hydrogen stored by the second reservoir 120 to a level low enough to absorb hydrogen from the first flow emitted by the first reservoir 1 10 when stopping the system, preferably at a level less than or equal to 50%, preferably 40%, preferably 30%, preferably at a level greater than or equal to 10%, for example at 15%, for example at 25% of the maximum hydrogen capacity of the second tank 120. This control is for example carried out during the operating phase.

The method may comprise a step of automatically controlling the temperature in the second tank 120, for example so as to maintain and / or bring the temperature below a certain threshold and / or above a certain threshold , for example so as to maintain and / or direct the level of hydrogen stored by the second reservoir to a predetermined value, for example with a tolerance less than or equal to 20 ° C, for example less than or equal to 15 ° C, by example less than or equal to 10 ° C.

The control step aims for example to maintain or bring the temperature within the second tank 120 for example between 10 and 50 ° C, preferably between 15 and 50 ° C, preferably between 20 and 50 ° C. The automatic control step comprises, for example, a step of passive control of the quantity of hydrogen stored by the second material 121 as a function of the hydrogen demand of the hydrogen utilization unit. The passive control step, for example, takes place in the operating position where the first reservoir, the second reservoir and the hydrogen utilization unit are maintained in fluid communication.

The passive control step comprises for example the movement of the system in this operating position or the maintenance of the system in this operating position.

The passive control step comprises, for example, an active command for supply of constant flow by the first tank 1 10, by the first heating means. The passive control step comprises, for example, an active control for supplying constant heat to the second tank 120 and / or heating at a constant temperature of the second tank 120 by the second heating means.

The passive control step comprises, for example, the passive control of the supply or the collection of hydrogen by the second tank 120 as a function of the pressure variations due to the hydrogen utilization unit 130.

The passive control step may thus comprise the implementation of steps 804 and / or 806 and / or 808 and / or 810 and / or 812. This implementation is particularly easy since it is sufficient to simply control, for example by a fixed control, the first tank, and to provide a simple heating control also to the second tank for the system to operate and regulate itself according to the needs of the unit of use of hydrogen.

With reference to FIG. 2, an example of the behavior of the system during the implementation of the method is described.

On a first graph 31, there is shown the flow of hydrogen 31 1 from the first reservoir 1 10 and the stream of hydrogen 312 from the second reservoir 120, and the hydrogen demand 313. The flow is represented as a percentage, 100 % corresponding to the nominal flow that the system is configured to supply via the first tank 1 10 or the second tank 120 taken separately.

On a second graph 32, the pressure 321 is represented, in bar, which is for example in the second tank 120 and / or common to the hydrogen utilization unit 130 and / or for example common to the two tanks 1 10 and 120 and / or the unit for using hydrogen 130.

On a third graph 33, it is represented, in degrees Celsius, the temperature 331 within the first tank 1 10 and the temperature 332 within the second tank 120. On a fourth graph 34, there is shown, in percentage, the level of hydrogen 341 in the first tank 1 10 and the hydrogen charge rate 342 in the second tank 120.

The graphs 31 to 34 represent for example a first phase 8001 followed by a step 8002, followed by an implementation phase of the steps 804, 806 and 810, followed by a step of implementing the step 808 , followed phase of implementation of steps 804, 806 and 810, followed by a step 812 stop.

Claims

claims

1. A system for storing and supplying hydrogen to a hydrogen utilization unit (130), comprising:

a first hydrogen storage tank (1 10) comprising a first material (1 1 1) for metastable storage of hydrogen by sorption, and

a second hydrogen storage tank (120) comprising second material (121) for the reversible storage of hydrogen by sorption; - an outlet (1 101) of hydrogen from the first tank to the second tank and / or the unit use of hydrogen,

a hydrogen outlet (1201) from the second reservoir to the hydrogen utilization unit,

so as to allow the first reservoir to provide a first flow of hydrogen to the utilization unit, and the second reservoir to provide a second flow of hydrogen to the utilization unit, the second flow completing and / or replace the first stream.

The system of claim 1, wherein the system is configured to allow the first reservoir to provide the first flow to the second reservoir to recharge the second reservoir with hydrogen.

3. System according to any one of the preceding claims, the system being configured so that, in at least one operating position, the first reservoir (1 10), the second reservoir (120) and the utilization unit hydrogen (130) are maintained in fluid communication and where evolution of the amount of hydrogen stored by the second material is passively controlled according to the hydrogen demand of the hydrogen utilization unit (130).

4. System according to any one of the preceding claims, wherein the second material (121) is adapted to form a hydride, preferably a metal hydride, preferably of LaNis, FeTi, TiCr, TiV, TiZr and / or TiMn type. ₂ .

5. System according to any one of the preceding claims, wherein the first material (1 1 1) is adapted to form a hydride, preferably a metal hydride, for example alane, for example at least one phase of alane, for example alane alpha, for example alane alpha prime and / or borazane and / or 1,2-di-amineborane, and / or lithium hydride and / or aluminum hydride and lithium.

The system of any of the preceding claims, wherein the second reservoir (120) is configured to provide, at ambient temperature, the second hydrogen stream so as to allow operation of the utilization unit.

7. System according to any one of the preceding claims, wherein the hydrogen outlet of the first reservoir to the second reservoir and / or the hydrogen utilization unit is provided with a non-return valve.

8. System according to any one of the preceding claims, wherein the hydrogen utilization unit comprises a fuel cell and / or an exhaust gas treatment system and / or a hydrogen engine.

9. A method of supplying hydrogen to a hydrogen consumption unit, the method being implemented by a system according to any one of the preceding claims.

Method according to the preceding claim, comprising steps

- Once the operating temperature reached by the first material, providing the first reservoir of the first hydrogen stream, and preferably stopping the supply of the second stream.

1 1. The method of any of claims 9 and 10, comprising steps of:

- Supply by the second reservoir of the second hydrogen stream to the use unit in addition to the first flow.

12. Method according to any one of claims 9 to 1 1, further comprising a hydrogen refueling step of the second tank by the first tank.

13. A method according to any one of claims 9 to 12, wherein, at the end of at least one step of supplying the second reservoir of the second stream of hydrogen, the second tank has a sufficient load to implement a new step of supplying the second hydrogen stream.

The system of any one of claims 1 to 8, further comprising control means (170) configured to implement the method according to any one of claims 9 to