• 专利附录
  • 专利说明
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  • 类似技术
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    • 专利摘要:
    Apparatus useful for generating a gas, comprising an enclosure defining an interior space for containing a liquid capable of generating the gas by contacting a catalyst, a catalytic system comprising first and second second pieces which together define a catalyst chamber for containing the catalyst, and which are movable relative to each other between a closed position in which the catalyst chamber is isolated from the internal space; An open position in which the catalyst chamber is in fluid communication with the interior space, so that when the liquid and the catalyst are contained respectively in the interior space and in the chamber of catalyzes, in the open position, the liquid penetrates into the catalysis chamber and the gas is generated by bringing the liquid into contact with the catalyst, an actuator connected to the catalytic system and configured to arranging the catalytic system in the open position and / or in the closed position, and a control unit for controlling the actuator.
    公开号:FR3072303A1
    申请号:FR1759786
    申请日:2017-10-18
    公开日:2019-04-19
    发明作者:Michael Bouvier；Philippe Capron；Jerome Delmas；Vincent MATHIEU；Isabelle Rougeaux
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    The present invention relates mainly to an apparatus for generating a gas, and in particular dihydrogen, by bringing a liquid into contact with a catalyst.
    A well-known method for generating dihydrogen consists in bringing an aqueous hydride solution, for example a sodium borohydride solution, into contact with a catalyst for the hydrolysis reaction of the hydride, formed for example of cobalt, platinum or ruthenium. On contact with the catalyst, a hydrolysis reaction of the aqueous solution occurs, generating dihydrogen.
    By way of illustration, WO 2012/003112 A1 and WO 2010/051557 A1 describe apparatuses for implementing such a catalyzed hydrolysis of hydride. The gas generation devices described in these documents comprise an enclosure containing, in operation, an aqueous hydride solution, and a catalytic system defining a catalysis chamber containing a catalyst for the hydrolysis of the aqueous hydride solution. The catalytic system has a body and a removable cover. In the closed position of the catalytic system, the cover and the body together isolate the catalyst from the aqueous hydride solution. There is then no generation of dihydrogen. In the open position of the catalytic system, the cover is arranged at a distance from the body. The aqueous hydride solution then comes into contact with the catalyst, thereby initiating the generation of dihydrogen. The dihydrogen thus generated is evacuated from the enclosure through an evacuation opening.
    To prevent the pressure of generated hydrogen from being too high inside the enclosure, the catalytic system described in WO 2012/003112 A1 and WO 2010/051557 A1 comprises an elastomeric membrane, in the form of a hollow cylindrical tube, fixed both on the body and on the cover. The body also comprises a drain opening out of the enclosure at one of its ends and into the interior space of the membrane at its opposite end, so that the pressure in the interior space of the membrane is equal to atmospheric pressure. Thus, when the hydrogen pressure in the enclosure is greater than a threshold pressure, the cover is pushed against the body under the effect of the pressure in the enclosure, contracting the elastomeric membrane by torsional effect, until the closed position of the catalytic system. When the pressure in the enclosure is lower than the threshold pressure, the elastomeric membrane, seeking to regain its equilibrium position, deploys and releases the cover in the open position of the catalytic system, so as to allow access to the aqueous catalyst hydride solution.
    The exposure of the catalyst to the aqueous hydride solution is controlled in WO 2012/003112 A1 and WO 2010/051557 A1 in a passive manner, that is to say that the opening and closing of the catalytic system s 'operates only according to the pressure of hydrogen in the enclosure. The catalytic system described in these two documents is therefore not very flexible to use.
    The catalytic system of WO 2012/003112 Al and WO 2010/051557 Al has other drawbacks.
    In order to ensure optimal contraction and deployment of the elastomeric membrane, it is necessary for the height of the membrane to be low, which limits access to the catalyst of the aqueous hydride solution.
    The threshold pressure for closing the catalytic system is determined by the rigidity of the elastomeric membrane which depends on the shape and the mechanical properties, in particular elastic properties, of the elastomeric membrane. The dimensioning of the membrane is therefore complex to ensure optimal operation of the device.
    Furthermore, it is not possible to control the opening and closing of the catalytic system independently of the pressure within the enclosure.
    There is therefore a need for an apparatus useful for generating a gas by bringing a liquid into contact with a catalyst overcoming the aforementioned drawbacks.
    This need is satisfied by means of a device useful for generating a gas, the device comprising
    an enclosure defining an interior space for containing a liquid capable of generating the gas by bringing it into contact with a catalyst,
    - a catalytic system comprising first and second parts which together define a catalysis chamber to contain the catalyst,
    the first and second parts being movable relative to each other, preferably in translation and / or in rotation, between a closed position in which the catalysis chamber is isolated from the interior space, and an open position in which the catalysis chamber is in fluid communication with the interior space, so that when the liquid and the catalyst are contained respectively in the interior space and in the catalysis chamber, in the open position, the liquid enters the catalysis chamber and the gas is generated by bringing the liquid into contact with the catalyst, and
    an actuator connected to the catalytic system and configured to place the catalytic system in the open position and / or in the closed position, and
    - a control unit to control the actuator.
    As will appear in more detail below, the yield of dihydrogen generated by the apparatus according to the invention is increased compared to that generated by an apparatus as described in WO 2012/003112 A1, for the same amounts of solution aqueous hydride and catalyst and under identical experimental conditions.
    The control unit is configured to issue a control signal so as to actuate the actuator directly or indirectly. As will appear later, the emission of the control signal may be independent of the pressure of the gas in the enclosure. In other words, according to the invention, the generation of gas can be stopped regardless of the value of the pressure of the gas in the enclosure. In particular, in the closed position, the catalysis chamber being isolated from the interior space, when the liquid and the catalyst are contained in the interior space and the catalysis chamber respectively, the liquid cannot enter the catalysis chamber, the tightness of the catalysis chamber to the liquid being ensured by the connection between the first and second parts. The apparatus according to the invention is thus reliable in operation.
    "Open position" means any position in which the catalysis chamber is in fluid communication with the interior space. The device can be arranged in several open positions, which differ from each other by the distance and / or the angle separating the first and second parts. In particular, the catalytic device can be arranged in first and second open positions different from each other, the volume of the chamber accessible to the liquid in the first open position being different from the volume of the chamber accessible to the liquid in the second position open. In this way, the kinetics of gas generation by means of the device can be modified by moving the catalytic device between two different open positions. In particular, the open position can be an extreme open position in which the actuator stroke is reached.
    The actuator is preferably fixed, for example rigidly, to the catalytic system.
    The actuator can be a cylinder, in particular a hydraulic cylinder or an electric cylinder or a pneumatic cylinder, or an electric motor.
    Preferably, the actuator is a cylinder. A cylinder has the advantage of ease of application between the open and closed positions. Such a jack conventionally comprises a cylindrical body in which is housed a piston able to move between a deployment position and a folded-up position, in a translational and / or rotational movement, in or around respectively a parallel direction, notably confused with the axis of the cylinder. Preferably, when the cylinder is hydraulic or pneumatic, the cylinder further comprises a return member configured to exert a force on the piston tending to return the piston to the folded-back position.
    Preferably, the cylindrical body of the jack is fixed to the first part and / or to the enclosure. The piston is preferably fixed on the second part.
    Preferably, the cylinder is pneumatic. A pneumatic cylinder has the advantage of not requiring an electrical power supply device to ensure its operation. It can in particular be supplied from a reserve of compressible fluid under pressure.
    Alternatively, the cylinder may be hydraulic. According to another variant, it can be electric.
    The actuator is not, however, limited to a cylinder. In a variant, the actuator can be a motor, in particular an electric motor, for example a stepping motor.
    Preferably, in at least one of the open and closed positions of the catalytic system, at least part of the cylinder is disposed in the catalysis chamber. Thus, the encroachment of the jack on the volume of the enclosure accessible to the liquid is limited.
    Furthermore, the first and second parts can be movable in translation with respect to one another between the open and closed positions, the direction of translation being parallel to the longitudinal axis of the jack.
    The apparatus may include a control valve connected to the control unit and the actuator, the control valve being configured to receive a control signal from the control unit and to deliver an amount of pressurized fluid to the cylinder and / or to purge the cylinder of said fluid, following the reception of said control signal.
    In particular, in order to supply the actuator, the device may include a member for supplying pressurized fluid connected to the control valve.
    In a variant, the fluid is pneumatic, in particular gaseous, and the fluid supply member can be a cartridge having a reservoir in which the pneumatic fluid is stored under pressure. Preferably, the cartridge is removably connected to the control valve.
    In another variant, the fluid supply member may be an assembly formed by a reservoir comprising the fluid, for example at atmospheric pressure, connected to a compressor in the case where the fluid is gaseous, or to a pump in the case where the fluid is liquid, for example an oil, to compress the fluid coming from the reservoir to a pressure higher than atmospheric pressure. The compressor or the pump, if necessary, can be in fluid communication, for example via a pipe, with the control valve, to convey the pressurized fluid through the control valve to the actuator.
    In a variant, in particular when the fluid supply member is the assembly as described in the previous paragraph, the fluid supply member, the actuator and the control valve define a closed circuit for the fluid. In other words, the flow of the fluid takes place only from the fluid supply member towards the jack through the control valve during the supply of the pressurized fluid in the cylinder of the jack, and in the opposite direction during purge the cylinder.
    By fluid, in particular gaseous, "under pressure" is meant that the pressure of the fluid is greater than atmospheric pressure. Preferably, the pressure of the fluid is greater than 1.1 bar, preferably greater than 1.5 bar, or even greater than 2 bar. The "pressure" is defined with reference to the zero vacuum pressure reference. The fluid can be a gas chosen from air, carbon dioxide, argon, dinitrogen or isobutane. Isobutane is preferred because it liquefies at 20 ° C at a pressure of 1.6 bar. Isobutane can be introduced under pressure into the tank, so that at least part of the tank is filled with isobutane in liquid form. Isobutane in liquid form can go into the gas phase when subjected to atmospheric pressure. As a variant, the fluid can be a fluid, and in particular an oil.
    Furthermore, the device may include a power supply unit, for example a battery. Preferably, the power supply unit is configured to deliver electrical power supply to the control unit. In addition, in particular depending on the type of actuator, the power supply unit can be configured to provide power supply power to other units and organs of the device.
    In particular, in the variant where the actuator is a pneumatic or hydraulic cylinder, the electrical supply unit can be configured to deliver supply power to the control valve and / or to the control unit to set implement the opening and closing of the control valve and thus supply or bleed the cylinder respectively. If necessary, it can be connected to the compressor or to the pump to supply them electrically.
    In the variant where the actuator is an electric jack or an electric motor, the electric power unit can be electrically connected to the actuator to operate the displacement of the piston of the electric jack or the rotation of the motor.
    As for the control unit, it is configured to emit a control signal, so as to control the actuator directly or indirectly so that the actuator has the catalytic system in the open position or in the closed position.
    The control unit can directly control the actuator. For example, the actuator is an electric motor and the control unit is electrically connected directly to the electric motor.
    Alternatively, the control unit can control the actuator indirectly. For example, the actuator is a cylinder, and the control unit can send a control signal to the control valve, so that opening or closing the control valve causes movement of the cylinder.
    Preferably, the control signal is an electrical signal.
    The control unit can be configured to control the actuator according to at least one control mode configured by means of at least one control parameter.
    The control mode can be a regulation control mode, as will be described below, or a specific control mode, different from the regulation control mode.
    The control unit preferably comprises a processor suitable for the execution of a computer program, called the control program, for the implementation of at least one control mode. The computer program may include instructions for reading and interpreting the control parameters.
    The device may include a storage module, for example a computer hard disk or a flash memory, in which said control program and / or the control parameters can be stored.
    As a variant, the device may include a reading module configured to read a storage medium, for example a USB key or an S SD card, and the control program and / or the parameters of the control program can be stored in said storage media. According to another variant, the reading module can include an input unit, for example a keyboard or a touch screen, suitable for entering the control parameters. In particular, the input unit can comprise a member for adjusting at least one control parameter, for example in the form of a rotary button, the angular position of the rotary button defining the value to which the control parameter is fixed. .
    The input unit can be configured so that the control parameter can be set before and changed during gas generation. Thus, when the control parameters are for example the minimum and maximum regulation pressures as will be described below, it is possible to modify said minimum and maximum regulation pressures, in order to adapt the flow generated as a function of gas needs. of the application for which the gas is generated by the appliance.
    The preferred control mode is a regulation control mode.
    In particular, depending on the regulation mode, the control parameter (s) preferably comprise at least one, preferably at least two regulation parameters.
    Preferably, the control unit is configured to carry out a comparison of at least one quantity to be regulated with the at least one regulation parameter, called regulation comparison, and is configured to send a control signal as a function of the result of the regulatory comparison.
    Preferably, the regulation mode is parameterized by means of control parameters comprising first and second regulation parameters, and the control unit is configured to receive a quantity to be regulated and to control the actuator so as to arrange the system. catalytic in a first position and in a second position, when the quantity to be regulated is less than the first regulation parameter and respectively greater than the second regulation parameter. The first and second positions can be open positions, preferably different from each other. According to a preferred variant, the first position is an open position and the second position is the closed position.
    The quantity to be regulated can be chosen from the gas pressure in the interior space, the gas pressure in a machine, preferably a fuel cell, with which the device is in fluid communication, the flow of gas generated and a temperature, for example the temperature of the liquid or the temperature of the catalyst or the temperature of the environment of the device.
    Preferably, the quantity to be regulated is the gas pressure in the interior space, and the first and second regulation parameters are minimum regulation pressure and maximum regulation pressure respectively.
    Preferably, the control unit is configured to send a control signal to the control valve, in order to arrange the catalytic system in a first position, respectively in a second position, when the gas pressure in the interior space is less than or equal to the minimum control pressure, respectively greater than or equal to the maximum control pressure. The first and second positions can be open positions. Preferably, the first and second positions are respectively an open position and a closed position.
    The minimum control pressure and / or the maximum control pressure can be set by the user of the device. In particular, they can be determined according to the application for which the generation of gas is intended. Advantageously, by modifying the minimum and / or maximum regulation pressures, the device can ensure a generation of gas at a constant reference flow rate and at a pressure adapted to the application for which the gas is intended.
    As described above, the control unit can be configured to execute at least one specific control mode different from the regulation mode.
    In particular, according to at least one specific control mode, the control unit can be configured to maintain the catalytic system in the open position and / or in the closed position for a holding period. The holding time is a control parameter of the specific control mode and is preferably independent of at least one, and in particular of all the regulation parameters of the regulation mode.
    For example, according to a variant, the specific piloting mode is a cold piloting mode, according to which the control unit is configured for:
    optionally placing the catalytic system in the open position for a first holding time, then placing the catalytic system in the closed position for a second holding time.
    The first hold time can be at least 10 times shorter than the second hold time. For example, the first hold time is 1 second, then the second hold time is 60 seconds.
    Furthermore, preferably, the device includes a control unit configured for:
    - receive at least one quantity to be checked,
    - analyze the quantity to be checked, in particular by comparing the quantity to be checked with at least one control parameter, and as a function of the result of the analysis,
    - generate a control signal according to the regulation mode or a specific control mode different from the regulation mode, and
    - send the piloting signal to the control unit which is configured to receive said piloting signal and execute the piloting mode corresponding to the piloting signal.
    Preferably, the quantity to be controlled depends on the control mode to be executed by the control unit. In particular, the quantity to be checked may be different for two different control modes. For example, depending on the regulation mode, the quantity to be checked can be the flow rate of gas generated and / or the temperature in the chamber and, depending on the cold control mode, the quantity to be checked can be the pressure of gas generated.
    The quantity to be controlled can be chosen from the gas pressure in the interior space, the gas pressure in a machine with which the apparatus, preferably a fuel cell, is in fluid communication, the flow of gas generated and a temperature, for example the temperature of the liquid or the temperature of the catalyst or the temperature of the environment of the device.
    Preferably, according to the regulation mode in which the quantity to be regulated is the gas pressure in the interior space, the control unit is configured to analyze, in particular jointly, the flow of gas generated, the temperature of the liquid, the temperature of the catalyst and the temperature of the environment of the apparatus, preferably the flow rate and the temperature of the catalyst.
    Depending on the regulation mode, the quantity to be checked is preferably different from the quantity to be regulated.
    Furthermore, the control unit preferably comprises a processor suitable for executing a computer program, called an analysis program, for analyzing the quantity to be checked with the at least one control parameter.
    The analysis program and / or the analysis parameters can be stored in the storage module or read by the reading module as described above and the analysis program can include instructions for reading and interpreting the control parameters .
    Preferably, the analysis of the quantity to be compared depends on the control mode executed by the control unit. In particular, the analysis program may include series of instructions specific to at least one control mode.
    In particular, the control unit can be configured to receive over a duration of analysis, for example less than 2 seconds, in particular less than 1 second, a plurality of values of the quantity to be checked, and formulate a result of the analysis following the comparison of each of the values of the quantity to be checked with a control parameter. In particular, if the result of the control is that each value of the plurality is less than the control parameter, the control unit can send and send a control signal according to a specific mode or according to the regulation mode, intended for the control unit.
    For example, according to an example of the regulation mode, the control unit is configured to receive and analyze two quantities to be controlled being the flow of gas generated and the temperature of the catalyst, the analysis being carried out by comparison of each of said quantities with control with a respective control parameter, respectively a set flow and a set temperature, throughout the analysis time. Thus, if during the analysis time, the flow of gas generated is lower than the set flow and / or the temperature of the catalyst is lower than the set temperature, the control unit is configured to send to the control unit a piloting signal in cold piloting mode.
    Preferably, the control unit is configured to analyze, in particular jointly, at least two different control quantities from one another, for example the flow of gas generated and at least one temperature, for example the temperature of the catalyst. .
    In the variant where the control mode is the regulation mode, the quantities to be controlled can be the temperature of the liquid and the pressure of gas contained in the interior space and the control parameters can be a maximum temperature of the liquid and a pressure gas maximum.
    In the variant where the control mode is the cold control mode, the quantities to be controlled can be the temperature of the catalyst and the gas pressure in the interior space and the control parameters can be a set temperature of the catalyst and minimum and maximum set pressures, for example equal respectively to the minimum regulation pressure and to the maximum regulation pressure. The control unit can be configured to emit a control signal, for example in regulation mode, as soon as the temperature of the catalyst is higher than the set temperature of the catalyst and as soon as the pressure of the gas in the enclosure is higher at the set pressure.
    As described above, the control unit and the control unit are configured to receive respectively at least one quantity to be regulated and at least one quantity to be controlled.
    Preferably, the device comprises at least one unit of measurement of a quantity chosen from the pressure of gas in the interior space, the pressure of gas in a machine, preferably a fuel cell, with which the device is in fluid communication, the flow of gas generated and a temperature, for example the temperature of the liquid or the temperature of the catalyst or the temperature of the environment of the device. The measurement unit is further configured to send said measured quantity to the control unit and / or to the control unit. The measurement unit can be electrically connected to the control unit and / or the control unit and can be configured to send the measured value of the quantity in the form of an electrical signal.
    In one embodiment, the measurement unit is arranged in the interior space.
    Preferably, the device comprises at least two measurement units, which are preferably each configured to measure different quantities. In particular, the apparatus may include a unit for measuring the gas pressure in the interior space, a unit for measuring the flow of gas generated, and at least one unit for measuring a temperature.
    Depending on the control mode to be implemented by the control unit, the measured quantity can be a quantity to be checked and / or a quantity to be regulated.
    Furthermore, the device may include an interrupt unit comprising a switch, for example an electrical switch, capable of being arranged in a configuration turned on or off by a user of the device. The interrupt unit is configured to generate an interrupt signal and send said interrupt signal to the control unit, which is configured to receive it, in order to control the closing, respectively the opening of the catalytic system. , when the switch is placed in the off configuration, respectively in the on configuration.
    The device may include the control unit and the interrupt unit. Preferably, the control unit is configured to process only the interrupt signal, when the control unit and the control unit each send jointly a control signal and an interrupt signal towards the unit. control.
    In addition, the device may include an alarm unit, configured to emit a signal, for example an audible or light signal.
    Preferably, the enclosure has a gas discharge opening. The apparatus preferably includes a pressure measurement unit configured to measure the pressure of the gas. The pressure measurement unit preferably includes a pressure sensor which can be disposed in the discharge opening. Alternatively, the gas discharge opening may be closed, or respectively open, for example by means of a valve, preferably flow regulator, so as to prevent, respectively allow the evacuation of gas from the enclosure, when the gas pressure in the enclosure is lower, respectively greater than or equal to an exhaust pressure. For example, the discharge pressure can be higher than 4 bar. The control unit can be configured to control the opening and closing of the valve. Alternatively, the valve may be formed from an elastic deformable material configured to prevent, respectively allow the evacuation of the fluid from the enclosure when the fluid pressure is lower, respectively greater than or equal to the evacuation pressure.
    Preferably, the catalytic system is arranged in the interior space of the enclosure. The fluid communication of the catalytic system with the interior space of the enclosure is thus facilitated in the open position of the catalytic system.
    Preferably, the catalytic system is completely immersed in the liquid. The generation of gas in the device can be stopped in such a configuration, for example following the sending of a closing control signal to the control valve, in particular when the pressure of the gas in the enclosure does not result in no compression force on the catalytic system.
    In one embodiment, the apparatus includes the catalyst. Preferably, the catalyst is a metal, preferably adapted to catalyze the hydrolysis of a hydride-based solution. A particularly preferred catalyst is chosen from cobalt, nickel, platinum, ruthenium and their alloys.
    Furthermore, the device may contain the liquid contained in the interior space of the enclosure. Preferably, the liquid is an aqueous solution comprising a hydride as described below.
    Preferably, at least a portion of the catalyst is fixed to the first part and / or to the second part. In an exemplary embodiment, the catalyst is fixed only on the first part or only on the second part.
    The catalyst can be arranged so as to be mobile or to be fixed relative to the enclosure when passing from the open position to the closed position.
    Furthermore, the device is shaped so that, in the open position of the catalytic system, when the enclosure contains the liquid, more than 50%, preferably more than 80%, preferably more than 90%, or even in particular any the surface of the catalyst free from contact with the first part and / or with the second part is in contact with the liquid. This advantageously improves the kinetics of the reaction for generating the gas by bringing the liquid into contact with the catalyst.
    Preferably, to facilitate access of the liquid to the catalyst, the stroke of the cylinder piston is equal to or greater than the thickness of the catalyst, said thickness being measured in a direction parallel to the axis along which the piston deploys.
    The catalyst can be in various forms, in particular in the form of a coating, for example deposited by chemical vapor deposition or physical vapor deposition, disposed on one face of a wall of the first part and / or on a face of a wall of the second part which at least partially define the catalysis chamber. Preferably, the coating has a thickness of less than 1 mm. In the form of a coating, the ratio of the surface area accessible to the liquid to the volume of catalyst is optimal. Furthermore, such a form of the catalyst promotes the manufacture of a compact catalytic system, which when it is arranged in the interior space of the enclosure, hardly encroaches on the volume accessible to the liquid.
    Alternatively, the catalyst may be in the form of a block, having a thickness greater than 1 mm. For example, the block may have the shape of a pellet, or of a hollow cylindrical tube of revolution.
    Preferably, the first part is fixed relative to the enclosure and the second part is movable relative to the enclosure between the open and closed positions. Preferably, the catalytic system, preferably the second part, is fixed, in particular rigidly, to the actuator. In particular in the variant where the actuator is a jack, the second part is fixed, preferably rigidly, to the piston of the jack, preferably at the end of the piston arranged in the open position outside the cylindrical body of the jack.
    The first and second pieces can be of various shapes. The first part can have a container shape to contain the catalyst. In particular, in the variant where the apparatus comprises the catalyst, the catalyst is for example placed in the interior space of the container or for example covers at least one, or even all the faces of the walls of the container which at least partially define the chamber of catalysis. Preferably, the container has at least one opening, and the second part has the shape of a cover, for example a form of a plate, suitable for closing the opening of the container in the closed position.
    In a variant, the first part has the shape of a plate. In particular, the plate can be covered with a coating formed by the catalyst. Preferably then, the second part preferably has the shape of a bell, so that in the closed position, the second part rests on the first part and isolates the catalysis chamber from the interior space.
    Preferably, whatever the shape of the first and second parts, to ensure the tightness of the catalysis chamber to the liquid in the closed position, the first part and / or the second part may include a seal, which in position closed is sandwiched and compressed between the first and second pieces. Alternatively, the second part can be covered with a flexible material, or be made of a flexible material, in order to ensure the seal in the closed position.
    As regards the catalysis chamber defined by the catalytic system, its volume is preferably greater than 1 ml.
    In a particular embodiment of the invention, a wall of the first part, respectively of the second part, may comprise at least one window passing through said wall in its thickness, the window of the first part, respectively of the second part, being entirely closed by the second part, respectively by the first part in the closed position of the catalytic system, and the windows of the first and second parts defining a path for access to the liquid through the walls of the first and second parts towards the catalysis chamber in the open position of the catalytic system. Thus, access to the liquid in the catalysis chamber is facilitated and an optimal exchange by convection of the liquid with the catalyst can take place. According to a variant, said walls of the first and second parts can extend transversely to the axis of deployment of the piston. According to another variant, the first and second parts are movable in rotation relative to one another between the open and closed positions. The first and second parts may comprise hollow tubular and cylindrical portions of revolution of axis coincident with the axis around which the rotation takes place, and the wall of the first part, respectively of the second part, comprising said pluralities of windows. is the side wall of the respective cylindrical portion.
    The apparatus according to the invention may also include a liquid-tight and fluid-permeable membrane, and arranged in the enclosure so as to separate the interior space into a space containing the liquid and a space containing the gas generated. In addition, the device may include a filter, for example mounted on the exhaust opening, configured to purify the generated gas.
    Furthermore, the invention relates to a method for generating a gas in which there is an apparatus according to the invention, the interior space of the enclosure containing a liquid capable of generating the gas by contact with a catalyst, the catalysis chamber of the catalytic system containing said catalyst, the method being implemented according to a control mode parameterized by means of first and second regulation parameters, called regulation mode, the method comprising the steps consisting in measuring a quantity to be regulated and controlling the actuator to place the catalytic system in the open position, respectively in the closed position, when the quantity to be regulated is less, respectively greater than the first regulation parameter, respectively to the second regulation parameter.
    In a particularly preferred way:
    - the gas is dihydrogen,
    the liquid is an aqueous solution comprising a hydride, preferably chosen from sodium borohydride, potassium borohydride, magnesium borohydride, calcium borohydride, lithium borohydride, lithium aluminum hydride, hydride magnesium, sodium aluminum hydride and mixtures thereof, and
    - The catalyst is suitable for catalyzing the hydrolysis reaction of the aqueous solution, and is preferably chosen from platinum, ruthenium, nickel, cobalt and their mixtures.
    Furthermore, the liquid may comprise an alkaline agent, preferably chosen from NaOH, KOH and their mixtures. This limits the spontaneous decomposition of the hydride. When the catalytic system is in the closed position, this limits the rise in gas pressure in the enclosure. When the catalytic system is in the open position, this ensures that the decomposition of the hydride results mainly from its catalyzed hydrolysis.
    Furthermore, the method according to the invention is such that the quantity to be regulated can be chosen from the pressure of gas in the interior space, the pressure of gas in a machine with which the apparatus, preferably a fuel cell, is in fluid communication, the flow of gas generated and a temperature, for example the temperature of the liquid or the temperature of the catalyst or the temperature of the environment of the apparatus, and the first and second regulation parameters are respectively minimum values and maximum of the quantity to be regulated.
    Preferably, the quantity to be regulated is the gas pressure in the interior space or the gas pressure in a machine with which the apparatus, preferably a fuel cell, is in fluid communication, and the first and second parameters of regulation are minimum regulation pressure and maximum regulation pressure.
    Preferably, depending on the regulation mode, the number of cycles, each consisting of the arrangement of the catalytic system in a first position then in a second position, preferably each consisting of an opening and a closing of the catalytic system, can be between 1 and 10000. The duration of a cycle can be between 1 second and 10 hours.
    In particular, the method comprises a plurality of cycles and the minimum regulation pressure and / or the maximum regulation pressure can be modified between two successive or even consecutive cycles.
    For example, the minimum regulation pressure defined for a second successive cycle, or even consecutive, to a first cycle can be lower than the regulation pressure defined for the first cycle, and / or the maximum regulation pressure defined for said second successive cycle may be higher than the regulation pressure defined for the first cycle.
    As a variant, the minimum regulation pressure defined for a second successive cycle, or even consecutive, to a first cycle may be greater than the regulation pressure defined for the first cycle, and / or the maximum regulation pressure defined for said second successive cycle may be lower than the regulation pressure defined for the first cycle.
    In particular, the minimum and maximum regulation pressures defined for a second successive or even consecutive cycle to a first cycle can be modified so that the arithmetic mean of said minimum and maximum regulation pressures on said second cycle is equal to the arithmetic mean of said minimum and maximum regulation pressures on said first cycle.
    In a variant, the minimum and maximum regulation pressures defined for a second successive cycle, or even consecutive, to a first cycle, may be such that the difference between the maximum regulation pressure and the minimum regulation pressure in said second cycle is equal to the difference between the maximum regulating pressure and the minimum regulating pressure in said first cycle, and preferably, the arithmetic mean of said minimum and maximum regulating pressures in said second cycle is different, in particular higher or lower, from the arithmetic mean of said minimum pressures and maximum regulation during the first cycle.
    Furthermore, according to a preferred mode of implementation:
    - at least one, preferably several, quantity to be checked is measured,
    - the quantity to be controlled is analyzed, in particular by comparing it with at least one control parameter, and as a function of the result of the analysis,
    - we stop controlling the process according to the regulation mode and then we control the process according to a specific control mode different from the regulation mode.
    Preferably:
    the quantities to be controlled are the temperature of the liquid and / or the temperature of the environment of the apparatus and / or the temperature of the catalyst, and the control parameters are respectively a minimum control temperature of the liquid and / or a temperature minimum environmental control and / or minimum control temperature of the catalyst,
    - the analysis is carried out which consists in checking whether during a period of analysis, preferably between 0.1 and 2 seconds, the temperature of the liquid and / or the temperature of the environment of the device and / or the catalyst temperature are respectively lower than the minimum control temperature of the liquid and / or a minimum environment control temperature and / or the minimum control temperature of the catalyst, and if this is the case,
    - the process is ceased to be controlled according to the regulation mode, then the process is controlled according to a cold control mode in which:
    i) optionally, the actuator is controlled so as to have the catalytic system in the open position, preferably for a period of between 1 and 10 seconds, then ii) the actuator is controlled so as to arrange and maintain the catalytic system in closed position as long as the gas pressure in the enclosure is lower than a maximum set pressure which is preferably greater than or equal to the maximum regulation pressure, iii) the actuator is controlled so as to arrange and maintain the catalytic system in position open and the enclosure is opened so that the generated gas is evacuated from the enclosure, and if during step iii) the measured gas pressure becomes lower then higher than a minimum set pressure, which is preferably less than or equal to the minimum regulation pressure, the process is no longer controlled according to the cold control mode and, preferably, the process is controlled die according to the control mode,
    - otherwise steps i) and ii) are carried out.
    Preferably, the minimum control temperature of the liquid and / or the minimum environmental control temperature and / or the minimum control temperature of the catalyst are equal to -10 ° C., or even equal to -20 ° C.
    In this way, by placing the liquid in the catalysis chamber and then the catalytic system in the closed position in step ii), the generation of gas is favored by the effect of confining the liquid and the catalyst in the catalysis chamber isolated from the 'pregnant. The gas generation reaction being exothermic, the temperature of the catalyst increases, which makes the catalyst more reactive for the gas generation reaction during the subsequent successive opening-closing cycles in regulation mode, which makes it possible to reach faster a set flow. The catalytic system being arranged in a closed configuration in step ii) of the cold piloting mode, the liquid located in the enclosure cannot enter the catalysis chamber and the generation of gas stops when the reactants of the liquid previously trapped in the catalysis chamber are consumed.
    In one embodiment, the method comprises a step of transporting the gas generated by the device outside the enclosure, and preferably within an anode chamber of a fuel cell. The gas pressure can then be measured in said anode chamber. Thus, the amount of gas generated by the device is adapted to the operating conditions of the fuel cell.
    Finally, the invention relates to a device for producing electrical energy, the device comprising
    - a fuel cell configured to generate an electric current by oxidation of a gas,
    - a gas generation device according to the invention, in fluid communication with the fuel cell and configured to supply the fuel cell with said gas.
    The fuel cell preferably comprises an oxidation unit comprising a stack formed in succession of an anode, an electrolytic membrane and a cathode, the oxidation unit being configured to generate an electric current by oxidation of the gas. The fuel cell preferably defines an anode chamber for supplying gas to the anode.
    The device preferably includes a dispensing member connecting the device and the fuel cell in fluid communication. Preferably, the dispensing member is fixed to the discharge opening of the device and opens into the anode chamber of the fuel cell.
    In one embodiment, the measurement unit can be adapted to measure the pressure of the gas in the anode chamber. Preferably, the measurement unit is arranged in the anode chamber. Thus, the opening and closing of the catalytic system are easily controlled so as to optimize safe operation of the fuel cell.
    Furthermore, the control unit can be configured to send a start-up signal and / or an extinction signal to the fuel cell which is configured to receive the start-up signal and / or the signal. respectively, and to be placed in energy generation mode and / or inactive mode.
    Other characteristics, variants and advantages of the invention will emerge more clearly on reading the detailed description and examples which follow, given by way of illustration and not limitation, and on examining the appended drawing, in which:
    FIGS. 1 to 3 schematically represent an apparatus according to different embodiments of the invention, FIGS. 4 to 6 represent enclosures and catalytic systems of apparatus according to different embodiments of the invention seen in longitudinal section, the Figures 7 and 8 on the one hand and 9 and 10 on the other hand represent enclosures and catalytic systems of devices according to different embodiments of the invention seen in longitudinal section in the closed position, respectively open, Figures 11 and 12 represent the catalytic system of FIGS. 9 and 10 respectively, seen in perspective, FIG. 13 represents a device according to an exemplary embodiment of the invention, FIG. 14 is a graph representing the variation of pressure of the gas within the enclosure during an example of implementation of the method according to the invention, FIG. 15 is a graph representing the variation in pressure at the neck rs of time during an implementation of the method according to the invention and of a method of the prior art, and FIGS. 16 and 17 illustrate the variations of pressure in the enclosure, of the flow of gas generated, of the temperature of the catalyst and the temperature of the environment during an example of implementation of the process.
    In the figures, the scales and proportions of the various organs and units making up the apparatus and the device are not necessarily observed. Furthermore, for the sake of clarity, organs can be represented as not being in contact with each other when they are in practice. Different references can designate the same body.
    FIG. 1 represents a first embodiment of the apparatus according to the invention.
    The device 5 comprises:
    - An enclosure 10 defining an interior volume 15 in which are arranged a catalytic system 20 and a pressure measurement unit 25, temperature measurement units 26, 27 and 28, and a measurement unit of the flow of gas generated 29;
    - An actuator in the form of a pneumatic cylinder 30 fixed on the enclosure and on the catalytic system;
    a control valve 35 in fluid communication on the one hand with the jack, for delivering pressurized fluid to the jack, and on the other hand with a fluid supply member 40,
    - a control unit 45 electrically connected to the control valve and to the pressure measurement unit,
    a control unit 46 electrically connected to the control unit, and
    - a reading module 50 electrically connected to the control unit and to the control unit.
    The apparatus further comprises a battery 55 for electrically supplying the control unit, the control unit, the reading module and the control valve.
    Furthermore, the control unit may include a switch 60, so that when the switch is placed in the off position, the control unit is not supplied with electricity. Preferably then, the catalytic system is disposed in the closed position. When the switch is placed in the ignition position, the control unit is electrically powered.
    The enclosure has a side wall 65 which extends in a longitudinal direction X, a bottom wall 70 defining a bottom of the enclosure when the longitudinal direction is parallel to the direction of gravity, and an upper wall, having an opening gas outlet. Alternatively, the discharge opening may be surmounted by a valve, preferably a flow regulator. Furthermore, the discharge opening can be surmounted by a pressure relief valve, not shown, for discharging the gas when the pressure of the gas in the interior space is greater than a threshold pressure.
    The interior space 15 can contain an aqueous hydride solution 80. Other liquids suitable for forming a gas by contacting with a catalyst can be contained in the interior space.
    The pressure measurement unit 25 is arranged in the interior space of the enclosure. In the example of Figure 1, it is arranged near a discharge opening 85 formed in the upper wall of the enclosure. Other arrangements are however possible.
    The catalytic system 20 comprises a container 90 arranged, preferably rigidly fixed, on the bottom wall of the container and a cover 95.
    The container and the lid together define a catalysis chamber 100 in which is housed a catalyst 105 for the hydrolysis of the aqueous hydride solution.
    In the example of FIG. 1, the lid is closed on the container and has a liquid seal 110, so that the catalysis chamber is isolated from the interior space 15 of the container. Thus, in the closed position of the device of FIG. 1, the liquid contained in the interior space cannot enter the catalysis chamber.
    Catalyst 105 is attached to the cover and is in the form of a hollow tube. As will be detailed later, other arrangements of the catalyst in the catalytic system and other forms are possible.
    Furthermore, holes 115, 120 are provided respectively in the bottom wall of the container of the catalytic system and in the bottom wall of the enclosure. They pass right through the respective thicknesses of said walls and are fixed opposite one another. Preferably, said holes 115 and 120 have identical shapes.
    The cylinder 30 is disposed in said holes and rigidly fixed relative to the enclosure. The jack comprises a cylindrical body 125 and a piston 130 housed in the cylindrical body and movable relative to the cylindrical body. In the example of FIG. 1, the hole 115 formed in the lower wall of the enclosure is tapped and the cylindrical body is fixed to the enclosure by screwing the cylindrical body into the tapped hole 115. The jack also comprises a return member 135 in the form of a helical spring fixed at its opposite ends to the body and to the piston, which provides a return function. In a variant, the actuator can be of the "double effect" type, provided with two chambers each supplied with compressible fluid, one of the chambers ensuring the return function. In the closed position of the device illustrated in Figure 1, the spring is in an equilibrium position, in which it does not exert a return force on the piston.
    The cylinder defines a cylinder chamber 140 to contain a fluid under pressure so as to move the piston between the closed position illustrated in FIG. 1 and an open position illustrated in FIG. 2. The end 145 of the piston opposite to that opposite of the cylinder chamber is fixed to the cover. Thus, the cover is movable in translation relative to the enclosure and to the container between the open and closed positions.
    As regards the control valve 35, it has an inlet 150 connected to the fluid supply member, which in the example of FIG. 1 is a cartridge 155 of pneumatic fluid under pressure, by means of a inlet pipe 160. The control valve has a supply outlet 165 connected to the cylinder chamber by means of a pipe 170. It further comprises a purge outlet 175, leading to the environment 180 outside of device where the pressure is lower than the pressure in the cartridge, preferably where the pressure is atmospheric. The valve is electrically connected via a cable to the control unit configured to send an electrical control signal Sc to the control valve, and the control valve is configured to receive said signal.
    The control signal can be a command to open the control valve. When the control valve receives such an opening control signal, it is disposed in a configuration where the purge outlet 175 is closed, and the pressurized fluid cartridge is placed in fluid communication with the cylinder chamber. The fluid can then flow from the cartridge through the inlet 150 and feed outlet 165 of the control valve to the cylinder chamber, as illustrated by the arrows A g . Thus, the piston 130 can be moved from the closed position to the open position, or kept in the open position, as illustrated in FIG. 2.
    The control signal can be a close control signal. When the control valve receives a closing control signal, it is arranged in a configuration where the inlet 150 of the control valve is closed and where the purge outlet 175 and the supply outlet 165 are open and turned on. fluid communication. The fluid in the cylinder chamber flows through the supply hose to the outside of the device through the purge outlet. The pressure decreasing in the cylinder chamber, the piston then moves, under the effect of the spring return force or against pressure in the variant where the cylinder is of the "double effect" type, so that place the catalytic system in the closed position.
    Preferably, the control valve comprises an electric actuating member, not shown, for placing the valve in any of the configurations described in the two preceding paragraphs, as a function of the electrical signal received. The electric actuator is electrically connected to the battery.
    The electrical signal sent by the control unit to the control valve is a function of the result, obtained by the control unit, of the comparison between the minimum control pressure and / or the maximum control pressure on the one hand and the gas pressure measured by the pressure measurement unit on the other hand.
    In the example of FIG. 1, the pressure measurement unit 25 includes a pressure sensor 185 for measuring the gas pressure in the enclosure. According to a regulation control mode implemented by the control unit, the pressure measurement unit sends the pressure of the gas it measures to the control unit which receives it and compares it with the minimum regulation pressures. and maximum. When the gas pressure is lower than the minimum regulation pressure, the control unit sends an opening control signal to the control valve so as to open the regulation system. As illustrated in Figure 2 according to arrow P, the liquid can then enter the catalysis chamber and comes into contact with the catalyst, so that by reaction between the liquid and the catalyst, the gas is generated. The gas then flows under the effect of Archimedes' thrust through the liquid in the enclosure and is evacuated through the gas discharge opening 85, as indicated by the arrows E, for example towards the anode chamber of a fuel cell 355 as illustrated in FIG. 13.
    The generation of gas within the enclosure results in an increase in the pressure of the gas in the enclosure if said gas is not completely consumed, for example by a fuel cell as illustrated in FIG. 13. When the gas pressure is higher than the maximum regulation pressure, the control unit sends a closing control signal to the control valve, so as to have the catalytic system in the closed position. The generation of gas is then stopped. The gas remaining in the enclosure after putting the device in the closed position is evacuated from the enclosure if it is consumed, by a fuel cell for example, so that the gas pressure in the enclosure decreases, until it becomes lower than the minimum regulation pressure. According to the regulation mode, a new gas generation cycle comprising the opening of the catalytic system as described above can then be carried out.
    Furthermore, the reading module 50 makes it possible to adjust the minimum pressure and / or the maximum regulation pressure, which are for example stored in the form of a file in a storage medium. The reading module links and sends the value of the minimum regulating pressure and / or the value of the maximum regulating pressure to the control unit which receives it for comparison with the pressure measured by the pressure measuring unit. gas, before sending a control signal to the control valve.
    Regarding the control unit 46, although this is not shown for the sake of clarity, it is electrically connected to the temperature measurement units 26, 27 and 28, to the measurement unit of the gas flow generated 29, and electrically powered by the battery 55. The temperature measurement unit 26 is arranged in the interior space so as to measure the temperature of the liquid 80. The temperature measurement unit 27 is arranged in the catalysis chamber in contact with the catalyst 105 to measure the temperature.
    The temperature measurement unit 28 is arranged outside the device for measuring the temperature of the environment of the device. The generated gas flow measurement unit 29 is arranged on the discharge opening 85.
    In the example of FIGS. 1 and 2, each of the measurement units 26 to 28 is configured to send the temperature value that it measures to the control unit which is configured to receive and control it. Depending on the regulation mode, the control unit checks whether the liquid temperature, the catalyst temperature and the temperature of the environment of the device are below respective minimum control temperatures, during a period of analysis by example of 5 seconds. If this is the case, it sends a piloting signal Sp to the control unit so that the control unit executes a cold piloting mode.
    The apparatus represented in FIG. 3 differs from that illustrated in FIGS. 1 and 2 in that it comprises, in place of the fluid cartridge, a fluid supply member 40 comprising a reservoir 190 for containing the fluid and an electric compressor 195, powered by the battery 55, for compressing the fluid coming from the reservoir and delivering said fluid to the control valve. In the example in Figure 3, the fluid is a gas and the cylinder is pneumatic. Alternatively, the fluid is a liquid, for example an oil and the cylinder is hydraulic. The compressor 195 is then replaced by a pump.
    Furthermore, the tank has an inlet opening 200 in fluid communication with the purge outlet of the control valve. Thus, when the actuator is purged of the fluid following the reception of a closing control signal, the purged fluid is introduced into the reservoir. Thus, the fluid supply member, the control valve and the actuator form a closed circuit for the fluid.
    As already stated, the catalytic system comprises first 205 and second 210 parts which together define a catalysis chamber to contain the catalyst. FIGS. 4 to 6 illustrate different examples of catalytic systems, as well as of arrangements of the catalyst within the catalytic system.
    The catalytic system of FIG. 4 differs from that illustrated in FIG. 1 in that the inner face 212 of the side wall is covered with a coating 215 made up of the catalyst. Such a catalytic system makes it possible to limit the quantity of catalyst while having an exchange surface between the catalyst and the liquid to efficiently generate the gas.
    The catalytic system of FIG. 5 differs from the catalytic system of FIG. In that the first part 205 has the shape of a plate and the second part 210 has the shape of a bell. The face of the first part opposite the second part is covered with a coating 220 formed of the catalyst. The second part has an upper wall 225 fixed to the piston of the jack and a side wall 230 extending in the longitudinal direction of the jack. Alternatively, the side wall may be oriented obliquely to the longitudinal direction of the cylinder. The edge of the longitudinal wall of the second part is surmounted by a seal 110 which bears against the edge of the first part in the closed position to isolate the liquid from the catalyst. The catalytic system of FIG. 5 is easy to manufacture. In particular, the coating can easily be formed on the plate forming the first part at a lower cost. Furthermore, by limiting the height of the walls of the second part, a compact catalytic system can thus be manufactured.
    The catalytic system of FIG. 6 differs from the catalytic system of FIG. In that the side wall 230 is of height h greater. Thus, the catalysis chamber 100 of the catalytic system of FIG. 6 is of volume greater than that illustrated in FIG. 5. Such a system is more suitable than that of FIG. 5 in the case where a large volume of catalyst is necessary for implement gas generation.
    Figures 7 and 8 illustrate another variant of the catalytic system of an apparatus according to the invention in the closed and open position respectively.
    The catalytic system 20 illustrated in FIGS. 7 and 8 differs from the catalytic system in FIG. 1 in that the lower wall 250 of the first part 205 is disposed at a distance from the container 10. Furthermore, the second part 210 has an upper wall 255 in the form of a plate to close the upper opening 260 of the first part. A tubular portion 265 projects from the upper wall of the second part, in which the piston 130 of the jack is partially housed. Preferably, as illustrated, the piston and the tubular portion are of complementary shapes. At its end opposite to that closed by the cover, the second part has a lower wall 270 extending transversely to the longitudinal direction Y of the jack.
    The lower walls 250, 270 of the first and second parts are each pierced with at least one, preferably with several windows passing through each of said walls in its thickness. The windows 275, 280 of the lower walls of the first and second parts are arranged so that in the closed position, as illustrated in FIG. 7, said lower walls of the first and second parts form a liquid-tight assembly, insulating the catalysis chamber of the enclosure, and in the open position, as illustrated in FIG. 8, define a fluidic access path, represented by the arrow Ci, between the interior space 15 of the enclosure and the catalysis chamber 100 through the said lower walls of the first and second parts. Thus, in the open position, the catalytic system defines a fluid access path between the upper wall of the second part and the side wall of the first part, illustrated by arrow C2 and at least one access path between the lower walls first and second parts, illustrated by the arrow Ci. The convection of the liquid within the catalysis chamber is thus improved, which optimizes the yield of the gas generation reaction. In the example of Figures 7 and 8, the transition from the open position to the closed position is effected by translation of the second part relative to the first part.
    Figures 9 to 11 illustrate another variant of apparatus according to the invention in which the first 205 and second 210 parts are movable in rotation relative to each other between the open and closed positions around a Y axis .
    The first part has a general shape of portion 290 tubular cylindrical of revolution and hollow and having opposite ends closed respectively by a lower wall 295 and by an upper wall 300 extending in transverse directions to the axis of revolution of the portion tubular. The axis of revolution of the cylindrical tubular portion is parallel to the Y axis.
    Preferably, the upper wall 300 is removable, and fixed, in particular by screwing, to the tubular portion 290.
    The lower wall 295 of the first part has a recess 305 passing through the lower wall in its thickness and from which protrudes a spacer 310. The spacer maintains the tubular portion 290 of the first part at a distance from the enclosure
    10. The spacer has a shape of a hollow, cylindrical tube, preferably of revolution, coaxial with the tubular portion of the first part.
    Furthermore, the lower, upper and lateral walls of the first part comprise at least one, preferably a plurality of windows 275 passing through each of said walls in their thickness. In a variant, at least one of said walls of the first part can be free of windows.
    The second part 210 has a general form of hollow cylindrical tube of revolution 320 surmounted at its opposite ends by a lower wall 325 and an upper wall 330, preferably removable. The second part thus defines a catalysis chamber 100 for the catalyst.
    In addition, the lower, upper and lateral walls of the second part comprise at least one, preferably a plurality of windows 280 passing through each of said walls in its thickness. In a variant, at least one of said walls of the second part can be free of windows.
    The second part is at least partially, or even entirely received, in the interior space of the tubular portion of the first part as illustrated in FIG. 9. The first and second parts are of complementary shapes and are coaxial.
    The windows of the lower, side and upper walls of the first and second parts are arranged respectively so that in the closed position, as illustrated in FIGS. 9 and 11, said lower walls of the first and second parts obstruct the windows of the second and first parts respectively and form a liquid-tight assembly, isolating the catalysis chamber 100 from the interior space 15 of the enclosure, and in the open position, as illustrated in FIGS. 10 and 12, define a fluid path, illustrated by the arrow Ci between the catalysis chamber and the interior space of the enclosure through said lower, lateral and upper walls of the first and second parts. In FIG. 11, the windows of the second room are shown in dotted lines, to indicate their angular position relative to the windows of the first room.
    The transition from the closed position to the open position is effected by rotation of an angle a of the second part with respect to the first part about the Y axis. To this end, the second part is fixed on a shaft d '' a 350 stepper motor, engaged in the spacer. The stepper motor has a stator and a rotor movable in rotation relative to each other about the Y axis. The stepper motor is electrically powered by the battery and connected to the control unit. It is configured to drive the second part relative to the first part in the open position or in the closed position upon reception of a signal from the control unit.
    FIG. 13 illustrates a device 350 according to the invention, comprising a fuel cell 355 supplied with dihydrogen by an apparatus 5 according to the invention.
    The fuel cell includes an oxidation unit 360 including a stack formed by an anode 370, an electrolytic membrane 375 and a cathode 380. It also defines an anode chamber 385 for distributing the dihydrogen to the anode , and a cathode chamber 390, for distributing oxygen to the cathode.
    The anode chamber also has an inlet port 400 for the supply of hydrogen, connected to the outlet opening 85 of the apparatus by means of a hollow transport tube 410.
    The apparatus illustrated in FIG. 13 is identical to that described in FIG. 1, except that the pressure measurement unit 25 is arranged in the anode chamber 385 of the fuel cell. In another variant not shown, the pressure measurement unit 25 can be arranged in the hollow tube 410.
    Thus, in operation, the generation of dihydrogen by the device is adapted according to the dihydrogen requirement of the fuel cell.
    As regards the method according to the invention, it comprises at least one, preferably several cycles formed from steps a) to c).
    FIG. 14 illustrates the evolution of the pressure of the gas P g within an enclosure of an apparatus according to the invention, as notably described in FIGS. 1 and 2, as a function of the time t of implementation of the process. As can be observed, the gas pressure changes between minimum P g min and maximum P g max values, which correspond to the minimum and maximum regulation pressures respectively. For example, during the first period 400 of implementing the process (between t = 0 and t = 4), the minimum regulation pressure is equal to 1.3 bar and the maximum regulation pressure is equal to 1, 5 bar. From t = 4, in a second period 405 of implementing the method, the user modifies the maximum regulation pressure by means of the adjustment unit to a value of 1.6 bar. From t = 9, in a third period 410 of implementing the process, the maximum and minimum regulation pressures are modified simultaneously, respectively increased to 1.7 bar and lowered to 1.1 bar. Thus, the average pressure during the first 400 and third 405 periods is identical, equal to 1.4 bar. For example, for an identical average pressure, an increase in the maximum regulation pressure and a decrease in the minimum regulation pressure results in a reduction in the number of opening / closing cycles of the catalytic system, which reduces the fluid consumption. compressible and in energy to generate the gas. A reduction in the amplitude around the average pressure, by decreasing the maximum regulating pressure and increasing the minimum regulating pressure makes it possible to better adapt to the operating requirements of a fuel cell. It also allows the gas generation device to respond more quickly and easily to peak flow rates imposed by a fuel cell to which the device is connected. The adjustment of the minimum and maximum regulation pressures thus allows the user of the device to adapt the generation of gas to the specifics of the application for which the gas is intended.
    Examples
    The invention is illustrated by means of the following nonlimiting examples.
    Example 1
    A gas generation is carried out by means of an apparatus as illustrated in FIG. 1. To this end, the catalytic system includes, within the catalysis chamber, 1 gram of cobalt and the interior space of the container, with a capacity of 0.6 1, contains 0.5 1 of a solution of sodium borohydride. The initial temperatures of the catalyst and of the liquid solution are both equal to 25 ° C.
    The device is connected to a fuel cell which it supplies with generated hydrogen.
    The minimum regulating pressure is fixed at 1.4 bar, and the maximum regulating pressure is fixed at 1.5 bar.
    FIG. 15 illustrates the evolution of the gas pressure P g in the enclosure as a function of the time t of implementation of the method.
    At time to = O, the catalytic system is placed in the open position. The generation of gas begins and the set flow rate of generated gas is reached (value of 1000 ml / min) from the first cycle of implementation of the process. As observed in FIG. 15, the gas pressure Pg in the enclosure is, in the first moments of the generation of dihydrogen, greater than 2 bars while the maximum regulation pressure is 1.5 bar. This phenomenon is explained by the inventors, as resulting from a volume of the non-optimized catalytic chamber, too large compared to the volume of the catalyst. Over time, the hydride content of the solution decreases, so that the volume of solution trapped in the catalysis chamber during each closure leads to an increasingly low generation of gas. As the gas consumption by the fuel cell is constant, the gas pressure in the enclosure thus less and less often exceeds the maximum regulation pressure imposed. The generation of gas continues in this way until the instantaneous quantity of gas generated is less than the instantaneous quantity of gas consumed by the fuel cell to which the appliance is connected (instant ti = 220 min), as is observed in Figure 15.
    Thus, the mass yield of hydrogen, defined as the ratio between the mass of hydrogen generated and the total mass of solution of the process according to the invention is 3.6%.
    Comparative example
    A generation of gas is carried out by means of the enclosure of the device of the apparatus illustrated in FIG. 1. The catalytic system, in the form of a buoy described in WO 2012/003112 A1 is used in place of the catalytic system according to the invention. The same amounts of cobalt and of sodium borohydride solution as in Example 1 are used.
    FIG. 15 illustrates the evolution of the gas pressure p g com P in the enclosure as a function of the time t of implementation of the method.
    At time to = O, the catalytic system is placed in the open position. The gas generation begins and the set flow rate of the generated gas is immediately reached (value of 1000 ml / min).
    The generation of gas at the set flow rate thus continues until the pressure in the enclosure reaches 1 bar at t2 = l 10 min. From this moment, the pressure in the enclosure becomes equal to atmospheric pressure. The apparatus of the prior art can no longer produce gas in an amount sufficient to ensure the set flow rate, the concentration of reactants being too low vis-à-vis the accessibility of the catalyst.
    Thus, the mass yield of the process of the prior art is 1.8%.
    Example 3
    There is a device as described in FIG. 13, except that the pressure measuring unit 25 is arranged to measure the pressure of gas in the interior space as illustrated in FIG. 1. The method is set implemented under the following conditions.
    The desired target flow rate, regulated by a flow control valve fixed to the outlet opening of the device (not shown), is fixed at 160 ml / min. This flow control valve simulates the gas consumption of a fuel cell. The device is placed in a climatic chamber whose temperature is -8 ° C. Before opening the catalytic system, the temperature of the hydride solution is -1 ° C and the temperature of the catalyst is 0 ° C.
    The evolution of the temperatures of the catalyst T c , of the aqueous hydride solution Tsoi contained in the enclosure, of the environment external to the apparatus T ext , as well as of the flow of dihydrogen Mm and the pressure of dihydrogen P g in the enclosure as a function of the time for implementing the method are shown in FIGS. 16 and 17.
    At to = O, the device is controlled so that the control unit executes a control mode in regulation as described above. The catalytic system is opened following the sending of a command to open the piston to the control valve, the gas pressure being initially lower than the minimum regulation pressure. The temperature of the catalyst and of the aqueous hydride solution being both below 5 ° C., the catalyzed hydrolysis reaction exhibits slow kinetics, so that the flow rate of dihydrogen generated is approximately 100 ml / min, lower at the set flow rate, throughout a first period 430, up to t = 1.4 min.
    During the period 430, the control unit analyzes, as control quantities, the flow rate of dihydrogen generated Mm and the temperature of the catalyst Tc.
    At = 1.4 min, the control unit emits as a result of the analysis that the flow rate is lower than a set flow rate set at 160 ml / min, and that the temperature of the liquid is lower than a set temperature set at 0 ° C. It then sends a piloting signal to the control unit for the implementation of a cold piloting mode. Following reception of the piloting signal, the control unit executes the cold piloting mode by first sending a closing command signal to the control valve to place the catalytic system in the closed position. Optionally, it can send a signal to the flow control valve to close the discharge opening to prevent the evacuation of the hydrogen from the enclosure. Alternatively, a signal can be sent to the fuel cell so that the fuel cell is paused during the execution of the cold piloting mode. The closing control signal is maintained throughout the periods referenced 435 and 440. A volume of aqueous hydride solution is thus contained in the catalysis chamber, isolated from the interior space of the enclosure. This volume of aqueous hydride solution reacts on contact with the catalyst, which generates a generation of dihydrogen which is evacuated from the catalytic chamber in the interior. The pressure of dihydrogen increases in the enclosure. The hydrolysis of the aqueous hydride solution being exothermic, the temperature of the catalyst consequently increases during the periods 435 and 440 up to approximately 16 ° C. During periods 435 and 440, depending on the cold piloting mode, the control unit receives and analyzes the gas pressure generated and, optionally the temperature of the catalyst, as quantities to be controlled. At the end of period 440, the gas pressure generated is greater than a control parameter being the maximum regulation pressure of the regulation mode, fixed at 1.5 bar. The control unit then sends a control signal to open the enclosure, at the start of period 445 so that the dihydrogen is evacuated therefrom and is, for example, consumed by a PAC fuel cell, thereby reducing the pressure of hydrogen in the enclosure. The control unit can send, at the end of period 445, a control signal to place the catalytic system in the open position, as detailed below. For example, the emission of the command to open the enclosure may result from the reception of a signal from the fuel cell. During period 445, the gas pressure decreases, the flow control valve being open allowing the gas to escape from the enclosure. The control unit then analyzes the gas pressure and compares it to a second control parameter which is for example lower than the minimum pressure of the regulation mode. For example, the second control parameter is atmospheric pressure. In the event that the gas pressure in the enclosure becomes lower than the second control parameter, the control unit sends a closing control signal which is maintained as during periods 435 and 440, so as to reheat a new times the catalyst. Otherwise, if the pressure increases after reaching the minimum regulation value, following the decomposition of the hydrides of the solution in contact with the catalyst, the control unit emits a piloting signal in regulation mode. The control unit stops executing the cold piloting mode, as observed during period 450.
    When the hydrogen pressure in the enclosure falls below the minimum regulation pressure, from t = 2.75 min, during period 450, the control unit sends an opening control signal to the control valve. The temperature of the catalyst having increased compared to the first period, the target flow is reached immediately and several cycles of opening / closing of the catalytic system according to the regulation control mode are then implemented.
    As is clear from the present description, the generation of gas, in particular of dihydrogen, by means of the apparatus according to the invention can easily be adapted according to the application for which the generated gas is intended. In particular, it makes it possible to initiate a generation of dihydrogen in an efficient and reliable manner in an environment where the temperature is below 0 ° C., and makes it possible to adapt the pressure profile of the gas generated to the application.
    Of course, the invention is not limited to the embodiments of the apparatus and the device according to the invention as well as to the embodiments of the method described and shown.
    权利要求:
    Claims (19)
    [1" id="c-fr-0001]
    1. Device (5) useful for generating a gas, the device comprising:
    - an enclosure (10) defining an interior space (15) for containing a liquid (80) capable of generating the gas by contacting with a catalyst (105),
    - A catalytic system (20) comprising first (205) and second (210) parts which together define a catalysis chamber (100) to contain the catalyst, the first and second parts being movable Tune relative to each other, preferably in translation and / or in rotation, between a closed position in which the catalysis chamber is isolated from the interior space, and an open position in which the catalysis chamber is in fluid communication with the interior space, so that when the liquid and the catalyst are contained respectively in the interior space and in the catalysis chamber, in the open position, the liquid enters the catalysis chamber and the gas is generated by bringing the liquid into contact with the catalyst,
    an actuator connected to the catalytic system and configured to place the catalytic system in the open position and / or in the closed position, and
    - a control unit for controlling T actuator.
    [2" id="c-fr-0002]
    2. Apparatus according to claim 1, wherein the actuator is a hydraulic cylinder or an electric cylinder or a pneumatic cylinder or an electric motor.
    [3" id="c-fr-0003]
    3. Apparatus according to claim 2, wherein, in at least one of the open and closed positions of the catalytic system, at least part of the cylinder is disposed in the housing and / or the catalytic system is disposed in the interior space of the 'pregnant.
    [4" id="c-fr-0004]
    4. Apparatus according to any one of claims 2 and 3, wherein the cylinder is hydraulic or preferably pneumatic, the apparatus comprising a control valve (35) connected to the control unit and the cylinder, the control valve being configured to receive a control signal from the control unit and to deliver an amount of pressurized fluid to the cylinder and / or to purge the cylinder of said fluid, upon receipt of said control signal.
    [5" id="c-fr-0005]
    5. Apparatus according to claim 4, comprising a supply member (40) for pressurized fluid in fluid communication with the control valve, preferably chosen from a cartridge (155) comprising the pneumatic pressurized fluid, the cartridge being of preferably removably connected to the control valve, and an assembly formed by a reservoir (190) comprising the pneumatic fluid linked to a compressor (195) or to a pump for compressing the fluid.
    [6" id="c-fr-0006]
    6. Apparatus according to any one of the preceding claims, wherein the control unit is configured to control the actuator according to at least one control mode parameterized by means of at least one control parameter.
    [7" id="c-fr-0007]
    7. Apparatus according to the preceding claim, in which the piloting mode is a regulation mode parameterized by means of piloting parameters comprising first and second regulation parameters, and the control unit is configured to receive a quantity to be regulated, preferably the gas pressure, and to control the actuator so as to arrange the catalytic system in a first position and a second position, for example in an open position and a closed position respectively, when the quantity to be regulated is less than the first regulation parameter, preferably at a minimum regulation pressure, and respectively higher than the second regulation parameter, preferably at a maximum regulation pressure.
    [8" id="c-fr-0008]
    8. Apparatus according to any one of claims 6 and 7, comprising a control unit configured for:
    receive at least one quantity to be checked, analyze the quantity to be checked, in particular by comparing the quantity to be checked with at least one control parameter, and according to the result of the analysis:
    generate a control signal according to the regulation mode or a specific control mode different from the regulation mode, and send the control signal to the control unit which is configured to receive said control signal and control the actuator according to the piloting mode corresponding to the piloting signal.
    [9" id="c-fr-0009]
    9. Apparatus according to any one of the preceding claims, comprising a unit for measuring a quantity chosen from the pressure of gas in the interior space, the pressure of gas in a machine, preferably a fuel cell, with which the device is in fluid communication, the gas flow generated and a temperature, for example the temperature of the liquid or the temperature of the catalyst or the temperature of the environment of the device, the measurement unit being configured to send the quantity measured at the control unit and / or at the control unit.
    [10" id="c-fr-0010]
    10. Apparatus according to the preceding claim, wherein depending on the control mode to be implemented by the control unit, the quantity measured by the measurement unit is a quantity to be regulated and / or a quantity to be controlled.
    [11" id="c-fr-0011]
    11. Apparatus according to any one of the preceding claims, comprising the catalyst, at least a portion of the catalyst being fixed on the first part and / or on the second part, and / or the interior space contains the liquid.
    [12" id="c-fr-0012]
    12. Apparatus according to any one of the preceding claims, in which a wall (250; 270) of the first part, respectively of the second part, comprises at least one window (275; 280) passing through said wall in its thickness, the window of the first part, respectively of the second part, being completely closed by the second part, respectively by the first part in the closed position of the catalytic system, and the windows of the first and second parts define a path for the liquid to through the walls of the first and second parts to the catalysis chamber in the open position of the catalytic system.
    [13" id="c-fr-0013]
    13. A method of generating a gas, preferably dihydrogen, in which there is an apparatus (5) according to any one of the preceding claims, the interior space (15) of the enclosure (10) containing a liquid (80), preferably an aqueous hydride solution, capable of generating the gas by contact with a catalyst (105) and the catalysis chamber (100) of the catalytic system containing said catalyst, preferably chosen from platinum, cobalt, ruthenium, nickel and their alloys, the method being implemented according to a control mode parameterized by means of first and second regulation parameters, called regulation mode, the method comprising the steps consisting in measuring a quantity to be regulated and controlling the actuator to arrange the catalytic system in first and second positions, preferably in open and closed positions respectively, when the quantity to be regulated is t lower, respectively greater than the first regulation parameter, respectively the second regulation parameter.
    [14" id="c-fr-0014]
    14. Method according to the preceding claim, in which the quantity to be regulated is chosen from the pressure of gas in the interior space, the pressure of gas in a machine with which the apparatus, preferably a fuel cell, is in communication fluid flow, the gas flow generated and a temperature, for example the temperature of the liquid or the temperature of the catalyst or the temperature of the environment of the device, and the first and second regulation parameters are respectively minimum and maximum values of the quantity to be regulated.
    [15" id="c-fr-0015]
    15. Method according to the preceding claim, wherein the quantity to be regulated is the gas pressure in the interior space, and the first and second regulation parameters are minimum regulation pressures and maximum regulation pressure respectively.
    [16" id="c-fr-0016]
    16. Method according to one of claims 13 to 15, in which:
    we measure at least one, preferably several quantities to be checked, we analyze the quantity to be checked, in particular by comparing it with at least one control parameter, and depending on the result of the analysis, we stop controlling the process according to the regulation mode then the process is piloted according to a specific control mode different from the regulation mode.
    [17" id="c-fr-0017]
    17. Method according to the preceding claim, in which:
    the quantities to be controlled are the temperature of the liquid and / or the temperature of the environment of the apparatus and / or the temperature of the catalyst, and the control parameters are respectively a minimum control temperature of the liquid and / or a temperature of minimum control of the environment and / or a minimum control temperature of the catalyst, the analysis is carried out consisting in checking whether during a duration of analysis, preferably between 0.1 and 10 seconds, the temperature of the liquid and / or the temperature of the environment of the device and / or the temperature of the catalyst are respectively lower than the minimum control temperature of the liquid and / or a minimum environment control temperature and / or the minimum control temperature of the catalyst, and if this is the case, the process is ceased to be controlled according to the regulation mode and then the process is controlled according to a cold control mode in s which the quantity to be checked is the pressure of the gas in the enclosure, and:
    i) optionally, the actuator is controlled so as to have the catalytic system in the open position, preferably for a period of between 1 seconds and 10 seconds, then ii) the actuator is controlled so as to arrange and maintain the catalytic system in the closed position as long as the gas pressure in the enclosure is less than a maximum set pressure which is preferably greater than or equal to the maximum regulation pressure, iii) the actuator is controlled so as to arrange and maintain the system catalytic in the open position and the enclosure is opened so that the gas generated is evacuated from the enclosure, and if during step iii) the measured gas pressure becomes lower then greater than a minimum set pressure, which is preferably less than or equal to the minimum regulation pressure, the process is no longer controlled according to the cold control mode and, preferably, pil ote the process according to the regulation mode, otherwise steps i) and ii) are carried out.
    [18" id="c-fr-0018]
    18. Method according to the preceding claim, wherein the minimum control temperature of the liquid and / or the minimum control temperature of the environment and / or the minimum control temperature of the catalyst are equal to 5 ° C, or even equal to 0 ° vs.
    [19" id="c-fr-0019]
    19. Device (350) for producing electrical energy, the device comprising
    - a fuel cell (355) configured to generate an electric current by oxidation of a gas, and
    - an apparatus (5) for generating gas according to any one of claims 1 to 12, in fluid communication with the fuel cell and configured to supply the fuel cell with said gas.
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    同族专利:
    公开号 | 公开日
    CN111491888A|2020-08-04|
    JP2021500297A|2021-01-07|
    EP3697728A1|2020-08-26|
    KR102243868B1|2021-04-22|
    JP6903231B2|2021-07-14|
    FR3072303B1|2019-11-01|
    EP3697728B1|2021-11-10|
    WO2019077023A1|2019-04-25|
    KR20200044976A|2020-04-29|
    US20200290002A1|2020-09-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20040067195A1|2002-10-03|2004-04-08|Michael Strizki|Self-regulating hydrogen generator|
    US20060225350A1|2005-01-28|2006-10-12|John Spallone|Systems and methods for controlling hydrogen generation|
    US20080014479A1|2006-06-20|2008-01-17|Lynntech, Inc.|Microcartridge hydrogen generator|
    WO2010051557A1|2008-11-03|2010-05-06|Societe Bic|Hydrogen-generating fuel cell cartridges|WO2021023637A1|2019-08-07|2021-02-11|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Reusable dihydrogen generator|
    WO2021023636A1|2019-08-07|2021-02-11|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Reusable dihydrogen generator|
    WO2021037939A1|2019-08-30|2021-03-04|Safran Electronics & Defense|Device for generating a gas|CN1071142A|1991-09-30|1993-04-21|纳幕尔杜邦公司|Produce the method and the device of hydrogen peroxide by hydrogen and oxygen|
    US7316718B2|2001-07-11|2008-01-08|Millennium Cell, Inc.|Differential pressure-driven borohydride based generator|
    US8986404B2|2009-11-03|2015-03-24|Societe Bic|Gas generator with starter mechanism and catalyst shield|
    CN102530858B|2011-04-29|2015-01-07|中国科学技术大学|Method for preparing hydrogen by alcohol|
    CN104327902B|2014-11-11|2016-04-20|王号德|A kind of device of brine electrolysis coal slurry desulfurization hydrogen manufacturing|
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    法律状态:
    2018-10-30| PLFP| Fee payment|Year of fee payment: 2 |
    2019-04-19| PLSC| Publication of the preliminary search report|Effective date: 20190419 |
    2019-10-31| PLFP| Fee payment|Year of fee payment: 3 |
    2020-10-30| PLFP| Fee payment|Year of fee payment: 4 |
    2021-10-29| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1759786|2017-10-18|
    FR1759786A|FR3072303B1|2017-10-18|2017-10-18|APPARATUS FOR GENERATING A GAS|FR1759786A| FR3072303B1|2017-10-18|2017-10-18|APPARATUS FOR GENERATING A GAS|
    EP18785664.6A| EP3697728B1|2017-10-18|2018-10-18|Apparatus for generating a gas|
    CN201880068436.0A| CN111491888A|2017-10-18|2018-10-18|Apparatus for generating gas|
    PCT/EP2018/078513| WO2019077023A1|2017-10-18|2018-10-18|Apparatus for generating a gas|
    JP2020522047A| JP6903231B2|2017-10-18|2018-10-18|Device to generate gas|
    US16/753,163| US20200290002A1|2017-10-18|2018-10-18|Apparatus for generating a gas|
    KR1020207010830A| KR102243868B1|2017-10-18|2018-10-18|Device for generating gas|
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