US20040079090A1

US20040079090A1 - Hydrogen storage alloy unit, thermoelectric conversion apparatus, and cooling, heating and freezing apparatus

Info

Publication number: US20040079090A1
Application number: US10/448,210
Authority: US
Inventors: Nobuyoshi Tsuji
Original assignee: IP Trading Japan Co Ltd
Current assignee: IP Trading Japan Co Ltd
Priority date: 2001-02-26
Filing date: 2003-05-30
Publication date: 2004-04-29
Also published as: JPWO2002068882A1; WO2002068881A1; JPWO2002068881A1; CN1509399A

Abstract

The present invention provides a thermoelectric conversion apparatus having a thermoelectric conversion module and a temperature restoration module. The thermoelectric conversion module comprises hydrogen storage and release devices provided with circulating heating medium changeover valves and containers in which are formed inside a plate cassette laminate or a pipe aggregate provided with a hydrogen storage alloy in the form of a thin film on the outer surfaces of the plate cassettes or pipes, a pump device for an working liquid provided with a liquid piston, an electronic control device that controls the changeover valves, and an electric power generation device that converts the flowing force of the actuator liquid into electricity. Moreover, the temperature restoration module comprises temperature restoration devices that relatively provide the hydrogen storage alloy units, use waste heat of the thermoelectric conversion module and external heat as a heat source, reciprocally transfer hydrogen between the hydrogen storage and release devices by pump pressure or differential pressure of hydrogen dissociation pressure, and raise and restore the temperature of the waste heat of the thermoelectric conversion module, a circulation system of a generated heat receiving medium, and an electronic control device that controls changeover valves of the circulation system.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to thermoelectric conversion in which pumping action is generated by fluctuations in hydrogen pressure by imparting a temperature difference to a hydrogen storage alloy using the functions of hydrogen occlusion and hydrogen release of a hydrogen storage alloy followed by conversion to electricity by using its mechanical movement, as well as cooling, heating and freezing that uses the collection of heat by causing the generation of heat by a hydrogenation reaction and the absorption of heat by a hydrogen releasing reaction of a hydrogen storage alloy. In particular, the present invention relates to that which is able minimize the stroke time of a hydrogenation reaction and hydrogen releasing reaction of a hydrogen storage alloy, and apply the generated hydrogen pressure, cooling heat and warming heat to a thermoelectric conversion and cooling, heating and freezing apparatus.

2. Description of Related Art

Examples of related apparatuses of the prior art that use a hydrogen storage alloy include a thermoelectric conversion apparatus in the form of an electric power generation device that uses the heat of a high-temperature gas and normal temperature air as heat sources (JP-A No. 08-240106; Reference 1), and a water supply device, which although is not a device in the field of electric power generation based on its overall constitution, uses a heat source obtained by introducing electric power into a Peltier element (JP-A No. 09-256425; Reference 2).

As means for heating and cooling these hydrogen storage alloys, the constitution of a unit into which is packed a hydrogen storage alloy powder suitable for a gas heating medium is proposed in Reference 1, while the product of performing copper plating on a hydrogen storage alloy powder and then compressing to a solid is used in Reference 2.

However, neither of these propose technologies such as a method and unit mechanism for installing a hydrogen storage alloy that enable rapid heating and cooling of a hydrogen storage alloy by a liquid heating medium, a pumping mechanism that uses a liquid surface piston without the use of a bellows or piston, a mechanism for shortening the stroke time of occlusion and release, a mechanism for transferring hydrogen and generating cooling heat and warming heat by maximizing the hydrogen dissociation pressure difference between hydrogen storage alloy units, or a mechanism for lowering the heat absorption temperature.

In addition, with respect to apparatuses of the prior art such as a chemical pump that resembles cooling, heating and freezing using a hydrogen storage alloy, due to the slow propagation of heat due to the gaps between particles caused by the specifications of the filling unit for the hydrogen storage alloy powder, the stroke of the hydrogenation reaction and hydrogen releasing reaction is excessively long, and the amount of hydrogen storage alloy inevitably becomes large.

In consideration of the above factors, an object of the present invention is to provide a thermoelectric conversion apparatus as well as a cooling, heating and freezing apparatus capable of minimizing the amount of hydrogen storage alloy used, and maximally utilizing the function of the hydrogen storage alloy even if the temperature of the heat source is low, based on technologies that include shortening of the stroke time between the hydrogenation reaction and hydrogen releasing reaction of the hydrogen storage alloy, pumping action generated by a liquid surface piston, hydrogen transfer utilizing a pressure difference in hydrogen dissociation pressure, raising and restoring the temperature of the heat source, and lowering the heat absorption temperature.

SUMMARY OF THE INVENTION

The first aspect of the present invention is a hydrogen storage alloy unit that performs storage and release of hydrogen, has a metal plate or metal pipe in which a hydrogen hole is formed in a flat section, and a plurality of linear corrugated grooves are formed in parallel over the entire surface of the flat section, and a hydrogen storage alloy in the form of a thin film is provided on the outer surface of the plate or pipe.

The second aspect of the present invention is a thermoelectric conversion apparatus having a thermoelectric conversion module and a temperature restoration module, the thermoelectric conversion has hydrogen storage and release devices provided with circulating heating medium changeover valves and containers in which are formed inside a plate cassette laminate or a pipe aggregate provided with a hydrogen storage alloy in the form of a thin film on the outer surfaces of the plate cassettes or pipes, a pump device for an working liquid provided with a liquid piston, an electronic control device that controls the changeover valves, and an electric power generation device that converts the flowing force of the actuator liquid into electricity, and the temperature restoration module has temperature restoration devices that relatively provide the hydrogen storage alloy units, use waste heat of the thermoelectric conversion module and external heat as a heat source, reciprocally transfer hydrogen between the hydrogen storage and release devices by pump pressure or differential pressure of hydrogen dissociation pressure, and raise and restore the temperature of the waste heat of the thermoelectric conversion module, a circulation system of a generated heat receiving medium, and an electronic control device that controls changeover valves of the circulation system.

The third aspect of the present invention is a cooling, heating and freezing apparatus having a cooling, heating and freezing heat source module, the heat source module has hydrogen storage and release devices provided with circulating heating medium changeover valves and containers in which are formed inside a plate cassette laminate or a pipe aggregate provided with a hydrogen storage alloy in the form of a thin film on the outer surfaces of the plate cassettes or pipes, cooling heat and warming heat generation devices that generate cooling heat and warming heat by using external heat as a heat source and reciprocally transferring hydrogen by pump pressure or the differential pressure of hydrogen dissociation pressure between the hydrogen storage and release devices, a circulation system of a generated heat receiving medium including a heat exchanger, and an electronic control device for controlling changeover valves of the circulation system.

As a result of employing such a constitution, within the hydrogen storage alloy unit, volume changes accompanying expansion of the hydrogen storage alloy volume can be accommodated by depositing a thin film of hydrogen storage alloy, and the hydrogenation and hydrogen releasing reaction times of the hydrogen storage alloy can be increased as a result increasing the rate of heat propagation from the thin film by preventing the dispersion of fine particles of hydrogen storage alloy.

In addition, in the case of applying the hydrogen storage alloy unit to a thermoelectric converting thermoelectric conversion module, working liquid can also be circulated in one direction by a check valve without using a solid piston, by pressing on the liquid surface of a liquid piston within a cylinder with the pressure of hydrogen gas from a hydrogen releasing reaction when a heating medium heats the hydrogen storage alloy within the hydrogen storage alloy unit. At the same time, excess working liquid that is pushed out of the cylinder flows into a sub-tank provided in the circulation path of the working liquid, and the entire circulation path of the working liquid is pressurized as a result of the gas within the sub-tank being compressed.

On the other hand, when the hydrogen storage alloy in the hydrogen storage alloy unit is cooled by changing over to a cooling medium, the hydrogenation reaction of the hydrogen storage alloy is started. Hydrogen gas in the cylinder is occluded at a faster rate for the hydrogenation reaction time as compared with that at normal pressure due to pressurization of the circulation path of the working liquid. At the same time, it is possible that the cooling medium receives a generated heat, and when the pressure in the cylinder falls below the pressure of the circulation path of the working liquid, the working liquid circulates and flows in one direction into the cylinder by the check valve as well due to the pressure of the circulation path of the working liquid.

A generator performs electric power generation by causing the rotation of a rotating system linked with the generator due to the flowing force of the working liquid of the circulation path as a result of continuing this series of cycles.

In addition, in the case of applying the hydrogen storage alloy unit to a thermoelectric converting temperature restoration module, the temperature of the thermoelectric conversion module exhaust heat is raised and recovered by causing hydrogen to be reciprocally transferred between hydrogen storage alloy units by the pressure difference in pump pressure or hydrogen dissociation pressure using the exhaust heat of the thermoelectric conversion module and external heat as heat sources, after which the exhaust gas is re-supplied to the thermoelectric conversion module as a reheating source.

In addition, in the case of applying the hydrogen storage alloy unit to a heat source module for cooling, heating and freezing, cooling heat and warming heat are generated by causing hydrogen to be reciprocally transferred between hydrogen storage alloy units by a pressure difference in pump pressure or hydrogen dissociation pressure using external heat for the heat source, followed by collecting the heat by a generated heat receiving medium and utilizing the cooling heat and warming heat by means of a heat exchanger.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sketch drawing of one embodiment of the present invention, and in this embodiment, the hydrogen storage alloy unit is composed by laminating plate cassettes. [0018]
FIGS. 2 and 3 show the procedure for depositing a thin film of hydrogen storage alloy provided on the outer surface of a pipe or plate cassette in the hydrogen storage alloy unit of the present invention. [0019]
FIGS. 4 and 5 are development drawings of an embodiment of the present invention, and show the form of a plate cassette inside the hydrogen storage alloy unit. [0020]
FIG. 6 is an overall schematic diagram of a thermoelectric conversion module of the present invention, and this embodiment is composed so as to be able to generate hydroelectric power when necessary by directly generating power or pumping up water utilizing the flowing force of an working liquid from pumping action generated by the hydrogen pressure applied to the liquid surface of a liquid piston. [0021]
FIG. 7 is an overall schematic diagram of a temperature restoration module and heat source module of the present invention, in this embodiment, each module is composed by providing a hydrogen pipe between hydrogen storage alloy units via a pump, and enabling the warming heat generated by the hydrogen storage alloy and the cooling heat generated by absorption of heat to be collected by a generated heat receiving medium and absorbed heat receiving medium, respectively. [0022]
FIGS. 8, 9 and [0023] 10 are drawings for explaining the temperature restoration method and cooling heat and warming heat generation methods, and this embodiment indicates the circulation of a heating medium through a temperature restoration module and heat source module that use as a heat source a thermoelectric conversion module in which hydrogen is reciprocally transferred spontaneously without introducing external pressure by generating a pressure difference in the hydrogen dissociation pressure between hydrogen storage alloy units using a heat source of the same temperature.

DETAILED DESCRIPTION OF THE INVENTION

The following provides an explanation of the present invention using the embodiments shown in FIGS. 2 and 3. A hydrogen storage alloy used for the hydrogen storage alloy unit of the present invention is a paste-like alloy consisting of a mixture of a rubber agent or adhesive and a powder adjusted to a particle diameter of about 50 μm obtained by occluding hydrogen into a hydrogen storage alloy and going through an initial crushing step. [0024]
Conditions for depositing this hydrogen storage alloy include adaptation to changes in volume accompanying expansion, prevention of dispersion of fine particles and good heat conductivity. For example, silicon rubber is suitable for use as the rubber agent, while an organic polymer material is suitable for the adhesive. [0025]
In addition, examples of other deposition methods include covering the alloy with a filtering substance and high-temperature deposition by subjecting the powder to metal plating. [0026]
In the case of an aggregate consisting of pipes as shown in FIG. 2, fine wires or [0027] fins 96 that support the hydrogen storage alloy are provided by wrapping around the outer periphery of metal pipe 95 and brazing, and hydrogen storage alloy paste 92 is coated and hardened from the outer periphery of pipe 95 to the protruding ends of fine wires or fins 96.
Furthermore, a filtering [0028] pound material 93 may be wrapped onto the outer surface to prevent separation and serve as a reinforcing material of the hydrogen storage alloy.
In addition, in case of a laminate composed of plate cassettes as shown in FIG. 3, hydrogen [0029] storage alloy paste 92 is coated into corrugated grooves 6 on both sides of metal plate cassettes and then hardened after providing a concave groove 94 in the groove surfaces so as to accommodate changes in volume caused by expansion and facilitate the flow of hydrogen.
Moreover, after depositing the hydrogen storage alloy in [0030] corrugated grooves 6, a method may also be employed in which the hydrogen storage alloy is covered with a filtering or other film-like pound material.
In a hydrogen storage and release device, by using a thin film-like hydrogen storage alloy in this manner, since the hydrogen storage alloy is able to accommodate changes in volume caused by expansion, is prevented from being dispersed even when in the form of fine granules, and has a rapid heat propagation, the stroke time of the hydrogenation reaction and hydrogen releasing reaction can be shortened, thereby making it possible to minimize the amount of hydrogen storage alloy used. [0031]
The following provides an explanation of the present invention using the embodiments shown in FIGS. 1, 4 and [0032] 5. In the case of using a laminate 15 of plate cassettes for the hydrogen storage alloy unit, first a hydrogen hole 5 is opened in the center of a rectangular flat section 4, and metal plates 2 and 3 are produced having a hydrogen guide groove 11 and corrugated grooves 6, in which a plurality of linear grooves are provided in a plurality of parallel rows over the entire surface of the plate in the direction at a 45 degree angle to the hydrogen guide groove 11. In this case, plates 2 and 3 are produced by press forming using a metal mold so that both ends of the long sides of the plates are able to respectively form bent flat side section 10.
Next, a plate cassette is produced by interposing a thin film of a brazing material between [0033] plates 2 and 3 and brazing the portions where the surfaces of flat section 4, ridges and valleys of corrugated groove 6, and surfaces of side section 10 are respectively joined by high-temperature treatment in a vacuum furnace.
Subsequently, a thin film of a hydrogen storage alloy is applied to both side of the plate cassette using a hydrogen storage alloy paste, the required number of plates are laminated, the plate cassettes are joined together tightly, and the hydrogen storage alloy portion is sealed by welding the joining outer peripheral ends to produce [0034] plate cassette laminate 15.
In addition, in the case of using an organic polymer adhesive suitable for carbonization for the hydrogen storage alloy paste, by applying the hydrogen storage alloy in the form of a thin film on both sides of the plate cassette and interposing a thin film of a brazing material between the cassettes followed by high-temperature treatment in a vacuum furnace, simultaneous to brazing the junctions of the cassettes, the adhesive is carbonized causing hydrogen storage alloy powder to be trapped inside the carbide. [0035]
A [0036] hydrogen pipe 14 is attached to hydrogen hole 5 in the uppermost plate cassette, and covers provided with heating medium nozzles that are continuous with the inside are attached to both ends of plate cassette laminate 15 to produce a hydrogen storage alloy unit.
In addition, in the case of using a pipe aggregate, a pipe aggregate is formed by hardening or carbonizing the periphery of the pipes, passing both ends of the plurality of pipes having a thin film of a hydrogen storage alloy formed thereon to the outside of both plate materials of a cylindrical sealed container, and welding the gaps between the pipe periphery and the plate materials on both ends to form a sealed pipe aggregate. A hydrogen nozzle that is continuous with the inside is attached to the side of the sealed container, and a cover integrated into a single unit with [0037] cap 86 and provided with a heating medium nozzle that is continuous with the inside of the container is attached to both ends of the sealed container to produce a hydrogen storage alloy unit.
In this manner, as a result of composing the hydrogen storage alloy unit in the manner described above, since hydrogen can be pressurized at about 30 kg/cm[0038] ²by drawing a vacuum through the hydrogen nozzle while allowing heating medium at about 80° C. to pass through from a heating medium nozzle to degas the hydrogen storage alloy, followed by allowing heating medium at about 20° C. to pass through from a heating medium nozzle, the hydrogen storage alloy can be activated immediately after installing the device without using a special-purpose chamber.
The following provides an explanation of the present invention using the embodiment shown in FIG. 6. In this embodiment, a thermoelectric conversion module is composed of a hydrogen storage alloy unit containing heating medium changeover valves, a cylinder containing a check valve, a sub-tank containing an working liquid circulation system, and a generator containing a control valve. Thus, this thermoelectric conversion module is capable of thermoelectric power generation as necessary by directly generating electric power or pumping up water by using the flowing force of an working liquid from a pump action generated by increasing or decreasing the hydrogen pressure applied to the liquid surface of a liquid piston. [0039]
In sealed [0040] containers 18, 18A and 18B of the hydrogen storage alloy unit, heating medium changeover valves 38, 37, 38A, 37A, 38B and 37B are provided on heating medium inlet nozzle 12 and heating medium outlet nozzle 13, respectively, and a heating medium circulation path that passes through heat exchanger 40, thermoelectric element unit 55, a hydrogen storage alloy unit, pressurization tank 58 and pump 51, and a cooling medium circulation path that passes through heat exchanger 53, thermoelectric element unit 55, a hydrogen storage alloy unit, pressurization tank 59 and pump 52, are connected so as to allow circulation of each heating medium.
Although the liquid piston is a separated liquid layer that floats on the liquid surface of an working liquid inside [0041] cylinders 1, 1A and 1B, in the case of using silicon oil for said working liquid, alcohol is suitable for the separated liquid layer. In this case, as a result of the separated liquid layer covering the liquid surface of the working liquid, the silicon oil flows into the hydrogen storage alloy unit, enabling it to prevent impairment of function, thereby eliminating the need for a bellows, hollow rubber body or other hydrogen partition previously proposed.
The circulation path of the silicon oil used for the working liquid is connected so as to allow silicon oil that has flowed from inside [0042] cylinders 1, 1A and 1B to merge, pass through rotation system 47 linked to relief valves 68 and 69 and pump 49, pass through rotation system 45 linked with generator 46, and be able to circulate to the original cylinder via lines communicating with the inside of sub-tank 57 in which argon or other gas is sealed.
In addition, [0043] silicon oil valves 24, 25, 24A, 25A, 24B and 25B are provided respectively equipped with check valve in the lower sections of cylinders 1, 1A and 1B to prevent backflow of silicon oil.
In this manner, when an working liquid pump device composed of a check valve, cylinder and liquid piston pushes out the silicon oil of an working liquid from a cylinder with the hydrogen gas pressure generated by the release of hydrogen by a hydrogen storage alloy within the cylinder, a rotation system of a generator of a power generation device is rotated by that flowing force resulting in the generation of electric power. [0044]
At the same time, as a result of silicon oil pushed out of a cylinder by a hydrogenation reaction time shortening device composed of a relief valve and sub-tank flowing into a [0045] reserve tank 57 and compressing the gas inside, during the hydrogenation reaction of the hydrogen storage alloy, the hydrogen storage time is considerably reduced by that pressure, thereby enabling a heating medium to receive high-temperature heat generated by hydrogenation.
In addition, as a result of heaters and coolers for a heating medium and cooling medium being laminated inside [0046] thermoelectric element device 55 interposed with thermoelectric elements, one side of the thermoelectric elements is either heated or cooled, and electric power is generated by the Seebeck effect.
In addition, [0047] pressurization tanks 58 and 59 are provided while being pressurized inside to the required pressure with a gas, and as a result of this pressurization, for example, in the case of using water for the heating medium or in the case of using ultra-low-temperature silicon oil, a heat source having a broad temperature range can be used since boiling can be prevented.
The electronic control device electronically controls interruption of the power supplies of heating [0048] medium changeover valves 38, 37, 38A, 37A, 38B and 37B so as to enable the discharge stroke of the working liquid pump device to be sequentially continuous according to preset data and the data of each detection sensor for temperature, pressure and liquid level, and electronically controls the frequency of the motive power supply of pumps 51 and 52 so that the temperature of the heating medium remains constant.
With respect to the collection of heat of the heating source, [0049] heat exchanger 40 collects heat from the converging heat of sunlight, natural heat such as ground heat, combustion heat of fuel and incinerators and heat of chemical reactions and waste heat from manufacturing plants so that there is a temperature difference with the cooling source.
In addition, although [0050] heat exchanger 53 collects heat from the outside air or the heat of vaporization of water to function as an ordinary cooling heat source, in the case of using by collecting the heat of vaporization of low-temperature boiling point substances such as liquefied natural gas (LNG) for use as an ultra-low-temperature cooling heat source, an ultra-low-temperature hydrogen storage alloy is used since heat exchanger 40 collects heat using the outside air as a heating source.
In addition, in the thermoelectric conversion module, after raising the temperature of a heating medium that has cooled after going through a hydrogen release stroke of the hydrogen storage alloy unit of a first stroke by using in the hydrogenation stroke of the hydrogen storage alloy unit of a second stroke, the temperature of the heating medium is raised by heating with an external heat source and re-circulated, thereby enabling operation with an external heat source only even in the case in which it is difficult to secure an external cooling heat source. [0051]
In addition, in the case of using thermoelectric conversion modules corresponding to the final amount of electric power generated while leaving the required number unchanged, they are used by connecting nozzles of the heating medium inlet and outlet provided on each hydrogen storage alloy unit with pipes of heating and cooling [0052] medium circulation paths 34 and 35.
In addition, in the case of storing water for electric power generation, electric power is generated by pumping up water to the required height by a [0053] pump 49, pooling the pumped water and allowing the water to fall as necessary to rotate a rotating system 50 linked with a generator 48.
When explained using the embodiment of FIG. 7, this embodiment is composed so that, in the absence of a heating source, warming heat resulting from the generation of heat by a hydrogen storage alloy and cooling heat resulting from the absorption of heat are collected by a generated heat receiving medium and absorbed heat receiving medium, respectively, by providing hydrogen pipes via pumps between the hydrogen storage alloy units of hydrogen storage alloy units containing heating medium changeover valves in a cooling heat and warming heat generation device of a temperature restoration module and heat source module. [0054]
In addition, in the case a heating source is present, hydrogen is transferred between hydrogen storage alloy units while conserving the pump by increasing the hydrogen dissociation pressure difference through the use of a heat source of the same temperature using a hydrogen storage alloy having different hydrogen dissociation pressure characteristics for the relative device. [0055]
In the embodiment of FIG. 7, the hydrogen flow paths of sealed [0056] containers 18 and 18A of the hydrogen storage alloy unit provided as a relative unit are connected with hydrogen pipes via pumps 73 and 74 linked with motive power supplies 71 and 72, and the circulation path of the generated heat receiving medium that runs through heat exchanger 40, pump 51, a hydrogen storage alloy unit and pressurization tank 58, and the circulation path of the absorbed heat receiving medium that runs through heat exchanger 53, pump 52, a hydrogen storage alloy unit and pressurization tank 59, are connected so that heating medium is able to circulate through each path.
In addition, an electronic control device electronically controls interruption of the power supplies of heating [0057] medium changeover valves 38, 37, 38A and 37A and the frequency of the motive power supplies of pumps 73 and 74 so that the warming heat resulting of heat generation by the hydrogen storage alloy and cooling heat resulting from heat absorption by the hydrogen storage alloy are each able to be collected in a stable manner by the generated heat receiving medium and the absorbed heat receiving medium, according to preset data and each of the temperature and pressure sensor data.
The following provides an explanation of the embodiment shown in FIGS. 8, 9 and [0058] 10. These drawings are drawings for explaining a temperature restoration method in which hydrogen is transferred reciprocally due to a pressure difference in the hydrogen dissociation pressure using an external heat source, and a cooling heat and warming heat generation method. This embodiment indicates the circulation of a heating medium of a temperature restoration module and heat source module, which use as a heat source the waste heat of a thermoelectric conversion module in which hydrogen is reciprocally transferred spontaneously with the introduction of external force by generating a difference in hydrogen dissociation pressure between hydrogen storage alloy units by a heat source of the same temperature.
The temperature restoration module consists of a plurality of modules composed of hydrogen [0059] storage alloy units 18C, 18D, 18E and 18F, while the heat source module is composed of a primary side module composed of hydrogen storage alloy units 18G and 18H, and a secondary side module composed of hydrogen storage alloy units 18J and 18K, and within the hydrogen storage alloy units provided for the respective relative units, a thin film of a hydrogen storage alloy for which the temperature of the hydrogen dissociation pressure characteristics differs by 20-50° C. is used for each relative unit, and hydrogen is transferred spontaneously due to the pressure differences in the hydrogen dissociation pressure between the hydrogen storage alloy units.
With respect to the temperature restoration method of the temperature restoration module in the thermoelectric conversion shown in FIG. 8, although the hydrogen dissociation pressure of the hydrogen storage alloy is higher in hydrogen [0060] storage alloy units 18D and 18F, units having a low hydrogen dissociation pressure are used for hydrogen storage alloy units 18C and 18E, thereby resulting in continuous operation by making the strokes of the left and right modules relative.
The circulation of heating medium consists of, in the first stroke shown above the broken line, heating medium circulation in which heating medium that has received the waste heat of the thermoelectric conversion module circulates as a heating source of the thermoelectric conversion module by being sent to hydrogen [0061] storage alloy units 18C, 18D, 18E and 18F provided relative to the temperature restoration module and passing through hydrogen storage alloy units 18C and 18E on the hydrogenation side, and heating medium circulation in which the heating medium circulates as a cooling heat source of the thermoelectric conversion module by passing through hydrogen storage alloy units 18D and 18F on the hydrogen release side, and in the second stroke shown below the broken line, heating medium circulation in which heating medium that has received warming heat generated in hydrogen storage alloy unit 18E on the hydrogenation side in the first stoke or waste heat of the thermoelectric conversion module circulates by passing through hydrogen storage alloy units 18C and 18E n the hydrogen release side of the second stroke, and heating medium circulation in which the heating medium that has received an external cooling heat source equal to or lower than the outside temperature circulates by passing through hydrogen storage alloy units 18D and 18F on the hydrogenation side.
This circulation of heating medium performs temperature restoration of the waste heat of the thermoelectric conversion module by first, in the first stroke shown above the broken line, sending an equal temperature heat source, in which circulating heating medium of heating and cooling of the thermoelectric conversion module are mixed, to each hydrogen storage alloy unit, and raising the temperature of the heating medium that passes through from the heat absorption action for hydrogen [0062] storage alloy units 18D and 18F on the hydrogen release side for which the hydrogen pressure is high, and raising the temperature of the heating medium that flows through from the heat generation action for the other hydrogen storage alloy units 18C and 18E on the hydrogenation side having a low hydrogen pressure.
In this case, the heating medium which received the heat restored with hydrogen [0063] storage alloy unit 18C supplies and re-circulates the heat as the heating source of the thermoelectric conversion module, while the heating medium from the other hydrogen storage alloy unit 18E is heated with external heat by heat exchanger 40 and circulated after being accumulated as the heating source of the second stroke by the heat exchange section within heating medium tank 80.
In addition, heating medium that has dropped in temperature as a result of passing through hydrogen [0064] storage alloy units 18D and 18F circulates again as the cooling source of the thermoelectric conversion module.
Next, in the second stroke shown below the broken line, as a result of the accumulated heating medium of the heating source being sent to hydrogen [0065] storage alloy units 18C and 18E, and heating medium that has received heat at a temperature equal to or lower than the outside air temperature being sent from heat exchanger 53 within the other hydrogen storage alloy units 18D and 18F in the form of a cooling heat source, hydrogen transfer is performed between the hydrogen storage alloy units in the reverse direction of the first stroke, thereby completing one cycle of temperature restoration.
In addition, in the first stroke, heating medium that has dropped in temperature after going through the hydrogen release stroke of the hydrogen storage alloy units of the thermoelectric conversion module is sent to the hydrogen storage alloy units provided relative to the temperature restoration module, the temperature of the heating medium rises due to generation of heat by the hydrogen storage alloy units on the hydrogenation side, and the heating medium is then circulated to the thermoelectric conversion module as a heating source. In the second stroke, heating medium that has received heat generated by the hydrogenation reaction time shortening device of the thermoelectric conversion module can also be used as a heating source in the other hydrogen storage alloy units on the hydrogen release side. [0066]
This temperature restoration method employed by the temperature restoration module makes it possible to raise the temperature of the heat source in a stepwise manner using a plurality of temperature restoration modules, and for example, by using a heat source such as solar heat or ground heat having a heat source temperature of 60-70° C. for the heat source, and using the outside air temperature of heat of vaporization of water for the cooling heat source, this method can be applied to a hot water heater that creates a high-temperature heat source of 100° C. or higher without introducing pressurization from the outside. [0067]
FIG. 9 shows a method for generating cooling heat and warming heat in a heat source module used for cooling, heating and freezing. The primary heat source module on the left side depicts a cooling and heating heat source module performing heat generation at about 55° C. and heat absorption at about 0° C. using an external cooling heat source having an external heating source at about 85° C. and an indoor and outdoor temperature of about 32° C. [0068]
In addition, in a heat source module composed of a primary side on the left side and a secondary side on the right side, a heat source module is depicted that generates low-temperature cooling heat used in [0069] heat exchanger 84 of a freezer by accumulating absorbed heat at about −50° C. using the generated heat of generated heat and absorbed heat of the primary side heat source module for the heat source of heating and cooling by the secondary side heat source module via heat exchangers 82 and 83, with the first stroke being above the broken line and the second stroke being below the broken line.
In addition, if the primary side or secondary side heat source module is composed with a plurality of modules of cooling heat and warming heat generation devices in the same manner as the temperature restoration module, interruptions in the circulation of the heating medium can be eliminated. [0070]
In the case of a heat source module for cooling and heating, similar to the temperature restoration method of the temperature restoration module during thermoelectric conversion, a high hydrogen dissociation pressure is used for hydrogen [0071] storage alloy unit 18H, while a low hydrogen dissociation pressure is used for hydrogen storage alloy unit 18G.
In the first stroke shown above the broken line, the circulation of heating medium is composed of heating medium circulation in which heating medium that has passed through [0072] heat exchangers 82 and 83 of the indoor and outdoor devices within relatively provided hydrogen storage alloy units 18G and 18H is circulated by merging or heat exchange, heating medium circulation in which heating medium circulates by receiving an external heating source and passing through hydrogen storage alloy unit 18G on the hydrogen release side, and heating medium circulation in which heating medium circulates by exchanging heat with heat exchanger 83 of the outdoor device or indoor device, and passing through hydrogen storage alloy unit 18H on the hydrogenation side.
In the circulation of heating medium in this manner, first, in the first stroke, heating medium that has received heat from the outdoor and indoor temperature within hydrogen [0073] storage alloy units 18G and 18H merges or exchanges heat, and an intermediate temperature heating medium is set to each hydrogen storage alloy unit. As a result of hydrogen transfer taking place due to the pressure difference in the hydrogen dissociation pressure between the hydrogen storage alloy units, hydrogen storage alloy unit 18H on the hydrogen release side causes the temperature of the heating medium that passes through to fall due to the action of heat absorption, while hydrogen storage alloy unit 18G on the hydrogenation side causes the temperature of the heating medium that passes through to rise due to the action of heat generation. Thus, the generated cooling heat is released for cooling or into the atmosphere with heat exchanger 82, while warming heat is released for heating or into the atmosphere with heat exchanger 83 of the second stroke.
Next, in the second stroke shown below the broken line, external heat such as converging heat of sunlight, natural heat such as ground heat, combustion heat of fuel and incinerators and heat of chemical reactions and waste heat from manufacturing plants is collected as a heating source by [0074] heat exchanger 81 and then sent to hydrogen storage alloy unit 18G. As a result of then sending heating medium that has received the outdoor or indoor temperature with heat exchanger 83 as a cooling source, hydrogen transfer takes place between the hydrogen storage alloy units in the reverse direction of the first stroke, thereby completing one cycle of cooling heat and warming heat generation.
In the case of a heat source module for freezing, the hydrogen storage alloy of the secondary side heat source module uses a low-temperature hydrogen storage alloy for which the hydrogen dissociation pressure is further increased from that of the hydrogen dissociation pressure used in the primary side heat source module, and that having a high hydrogen dissociation pressure is used for hydrogen [0075] storage alloy unit 18K, while that having a low hydrogen dissociation pressure is used for hydrogen storage alloy unit 18J.
In the first stroke shown above the broken line, the circulation of heating medium is composed of heating medium circulation in which heating medium that has received cooling heat generated by the primary side heat source module is sent to relatively provided hydrogen [0076] storage alloy units 18J and 18K and circulates by passing through hydrogen storage alloy unit 18J on the hydrogenation side, and heating medium that passes through hydrogen storage alloy unit 18J on the hydrogenation side of the second stroke by passing through hydrogen storage alloy unit 18K on the hydrogenation side of the second stroke after having passed through heat exchanger 84 within a freezer by passing through the other hydrogen storage alloy unit 18K on the hydrogen release side, circulate by merging or heat exchange, and in the second stroke shown below the broken line, heating medium circulation in which heating medium that has received warm heat generated by the primary side heat source module circulates by passing through hydrogen storage alloy unit 18J on the hydrogen release side.
In the circulation of heating medium in this manner, first, in the first stroke, heating medium that has received absorbed heat of the primary side heat source module via [0077] heat exchanger 82 is sent to hydrogen storage alloy units 18J and 18K provided relative to heat sources of the same temperature as the heat source of the secondary side heat source module, and as a result of hydrogen transfer taking place between the hydrogen storage alloy units due to the difference in hydrogen dissociation pressures, hydrogen storage alloy unit 18K on the hydrogen release side causes a drop in the temperature of the heating medium that passes through due to the action of heat absorption, while the other hydrogen storage alloy unit 18J on the hydrogenation side causes a rise in the temperature of the heating medium that passes through due to the action of heat generation. After being supplied as a freezing heat source with heat exchanger 84 within the freezer, heating medium that has received the generated cooling heat passes through hydrogen storage alloy unit 18K of the second stroke, and then circulates to heat exchanger 82 by merging or heat exchanging with heating medium that passes through hydrogen storage alloy unit 18J.
Next, in the second stroke shown below the broken line, as a result of heating medium that has received the generated heat of the primary side heat source module via [0078] heat exchanger 83 being sent to hydrogen storage alloy unit 18J as a heating source, and heating medium that circulates from heat exchanger 84 being sent to the other hydrogen storage alloy unit 18K as a cooling heat source, hydrogen transfer takes place between the hydrogen storage alloy units in the reverse direction of the first stroke, thereby completing one cycle of low-temperature cooling heat generation.
FIG. 10 shows the case of generating low-temperature cooling heat using the primary side heat source module shown in FIG. 9, and the module on the left side is composed of an initial heating medium circulation system, while the module on the right side is composed of a subsequent heating medium circulation system. [0079]
In the first stroke of the initial heating medium circulation system shown above the broken line, the circulation of heating medium is composed of heating medium circulation in which heating medium that circulates by passing through hydrogen [0080] storage alloy unit 18G on the hydrogenation side of a relatively provided hydrogen storage alloy unit and receiving an external cooling heat source, and heating medium that circulates by passing through hydrogen storage alloy unit 18H on the hydrogen release side and exchanging heat with a heat storage tank 99, circulate by merging or exchanging heat, and in the first stroke of the subsequent heating medium circulation system shown above the broken line, the circulation of heating medium is composed of heating medium circulation in which heating medium that circulates by passing through heat exchanger 84 inside a freezer after passing through hydrogen storage alloy unit 18H on the hydrogen release side of a relatively provided hydrogen storage alloy unit, and heating medium that circulates by exchanging heat with heat storage tank 99 after passing through hydrogen storage alloy unit 18G on the hydrogenation side, circulate by merging or exchanging heat. In the second stroke of the initial heating medium circulation system and subsequent heating medium circulation system, the circulation of heating medium is composed of heating medium circulation in which heating medium circulates by receiving an external heating source and passing through hydrogen storage alloy unit 18G on the hydrogen release side, and heating medium circulation in which heating medium circulates by receiving an external cooling heat source and passing through hydrogen storage alloy unit 18H on the hydrogenation side of hydrogen storage alloy unit 18G on the hydrogen release side.
Circulation of heating medium in this manner accumulates cooling heat that has received absorbed heat of hydrogen [0081] storage alloy unit 18H on the hydrogen release side in heat storage tank 99 in a first stroke of the initial heating medium circulation system, and by using this stored cooling heat as a heat source in the first stroke of the subsequent heating medium circulation system, the absorbed heat temperature of hydrogen storage alloy unit 18H on the hydrogen release side is further lowered, and cooling heat collected at a low temperature is used as a freezing heat source with heat exchanger 84 inside the freezer.
In addition, in the second stroke of the initial heating medium circulation system and subsequent heating medium circulation system, heating medium that has received an external heating source in [0082] heat exchanger 81 is sent to hydrogen storage alloy unit 18G, and as a result of sending heating medium that has received an external cooling heat source in heat exchanger 83 in the other hydrogen storage alloy unit 18H, hydrogen transfer takes place between the hydrogen storage alloy units in the reverse direction of the first stroke.

Claims

What is claimed is:

1. A hydrogen storage alloy unit that performs storage and release of hydrogen, comprising:

a metal plate or metal pipe in which a hydrogen hole is formed in a flat section, and a plurality of linear corrugated grooves are formed in parallel over the entire surface of the flat section; and

a hydrogen storage alloy in the form of a thin film is provided on the outer surface of the plate or pipe.

2. A hydrogen storage alloy unit according to claim 1, comprising:

a laminate in which thin films of hydrogen storage alloy are laminated onto both sides of a plate cassette in which a plurality of the plates are layered and then brazed, followed by welding the periphery or brazing the joined sections between the plate cassettes; or

an aggregate of the pipes in which a plurality of the pipes are provided within containers, and both ends of the pipes penetrate to the outside of the plate materials on both ends.

3. A thermoelectric conversion apparatus having a thermoelectric conversion module and a temperature restoration module, the thermoelectric conversion module comprising:

hydrogen storage and release devices provided with circulating heating medium changeover valves and containers in which are formed inside a plate cassette laminate or a pipe aggregate provided with a hydrogen storage alloy in the form of a thin film on the outer surfaces of the plate cassettes or pipes;

a pump device for an working liquid provided with a liquid piston;

an electronic control device for controlling the changeover valves; and

an electric power generation device for converting the flowing force of the actuator liquid into electricity, and

the temperature restoration module comprising:

temperature restoration devices that provided relatively the hydrogen storage alloy units, use waste heat of the thermoelectric conversion module and external heat as a heat source, reciprocally transfer hydrogen between the hydrogen storage and release devices by pump pressure or differential pressure of hydrogen dissociation pressure, and raise and restore the temperature of the waste heat of the thermoelectric conversion module;

a circulation system of a generated heat receiving medium; and

an electronic control device for controlling changeover valves of the circulation system.

4. A thermoelectric conversion apparatus according to claim 3, wherein

in the case the working liquid is silicon oil,

the material of the separated liquid layer that composes the liquid piston is alcohol.

5. A thermoelectric conversion apparatus according to claim 3, wherein

the thermoelectric conversion module comprising

a hydrogenation reaction time shortening device provided with a reserve tank in the circulation path of the working liquid.

6. A thermoelectric conversion apparatus according to claim 3, wherein

the temperature restoration devices respectively use hydrogen storage alloys in the from of thin films having different hydrogen dissociation pressure characteristics within the hydrogen storage and release devices, and generates a differential pressure in the hydrogen pressure between the hydrogen storage and release devices by the heat source.

7. A thermoelectric conversion apparatus according to claim 3, wherein

the hydrogen storage and release devices and covers provided on both ends of a heating medium nozzle that links and opens the inside of the hydrogen storage and release devices, are respectively attached and sealed.

8. A thermoelectric conversion apparatus according to claim 3, wherein

the plate cassette laminate or pipe aggregate is the hydrogen storage alloy unit according to claim 1.

9. A cooling, heating and freezing apparatus having a cooling, heating and freezing heat source module, the heat source module comprising:

cooling heat and warming heat generation devices that generate cooling heat and warming heat by using external heat as a heat source and reciprocally transferring hydrogen by pump pressure or the differential pressure of hydrogen dissociation pressure between the hydrogen storage and release devices;

a circulation system of a generated heat receiving medium that includes a heat exchanger; and

10. A cooling, heating and freezing apparatus according to claim 9, wherein

the cooling heat and warming heat generation devices respectively use hydrogen storage alloys in the from of thin films having different hydrogen dissociation pressure characteristics within the hydrogen storage and release devices, and generates a differential pressure in the hydrogen pressure between the hydrogen storage and release devices by the heat source.

11. A cooling, heating and freezing apparatus according to claim 9, wherein

the hydrogen storage alloy units and covers provided on both ends of a heating medium nozzle that links and opens the inside of the hydrogen storage and release devices, are respectively attached and sealed.

12. The cooling, heating and freezing apparatus according to claim 9, wherein

13. A hydrogen storage alloy deposition method of a hydrogen alloy storage device, wherein

the hydrogen storage alloy unit is provided with a plate cassette in which a plurality of metal plates are formed by lamination,

the hydrogen storage alloy deposition method employs a hydrogen storage alloy paste in which a powder that has gone through an initial crushing step in which hydrogen storage alloy is made to absorb hydrogen, is mixed with a rubber agent or adhesive, and

the hydrogen storage alloy paste is coated and hardened in grooves formed in both sides of the plate cassette, and deposited in the form of a thin layer.

14. A hydrogen storage alloy deposition method of a hydrogen storage alloy device, wherein

the hydrogen storage alloy unit is provided with metal pipes,

the hydrogen storage alloy paste is coated and hardened in grooves formed in the outer periphery of the pipes, and deposited in the form of a thin layer.

15. A heating medium circulation method in the temperature restoration devices according to claim 3, comprising:

a first stroke having a heating medium circulation in which heating medium that has received waste heat of the thermoelectric conversion module as a heat source is sent to the relatively provided hydrogen storage and release devices of the temperature restoration module, passes through the hydrogen storage and release device on the hydrogenation side, and circulates as a cooling heat source of the thermoelectric conversion module, and

a heating medium circulation in which heating medium passes through the hydrogen storage and release device on the hydrogen release side and circulates as a cooling heat source of the thermoelectric conversion module; and

a second stroke having a heating medium circulation in which heating medium receives generated warming heat of the hydrogen storage and release device on the hydrogenation side in the first stroke or waste heat of the thermoelectric conversion module, and circulates by passing through the hydrogen storage and release device on the hydrogen release side of the second stroke, and

a heating medium circulation in which heating medium receives an external cooling heat source and circulates by passing through the hydrogen storage alloy unit on the hydrogenation side.

16. A heating medium circulation method in the cooling heat and warming heat generation devices according to claim 9, comprising:

a heating medium circulation in which the heating medium is circulated by passing through the hydrogen storage and release devices, after making heating medium that pass through heat exchangers of an outdoor device and indoor device the same temperature by merging or heat exchanging in the heat generation module on the primary side.

17. A heating medium circulation method according to claim 16, wherein the heat source module on the secondary side comprising:

a first stroke having a heating medium circulation in which,

heating medium that has received generated cooling heat of the primary side heat source module is sent to the hydrogen storage and release devices, and circulates by passing through the hydrogen storage and release device on the hydrogenation side, and

heating medium, which after passing through the hydrogen storage and release device on the hydrogen release side and passing through a heat exchanger inside a freezer, passes through a hydrogen storage and release device on the hydrogenation side of a second stroke, and then passes through the hydrogen storage and release device on the hydrogenation side of the first stroke,

are merged or heat exchanged; and,

a second stroke having a heating medium circulation in heating medium receives generated warming heat of the heat source module on the primary side, and circulates by passing through the hydrogen storage and release device on the hydrogen release side.

18. A heating medium circulation method according to claim 17, wherein the first stroke of the primary heat source module comprising:

an initial heating medium circulation system in which, heating medium that circulates by receiving an external cooling heat source after passing through the hydrogen storage and release device on the hydrogenation side, and heating medium that circulates by collecting heat after passing through the hydrogen storage and release device on the hydrogen release side, circulate by merging or heat exchange; and

a subsequent circulation system in which heating medium that circulates by passing through a heat exchanger in a freezer after passing through the hydrogen storage and release device on the hydrogen release side, and heating medium that circulates by receiving collected heat after passing through the hydrogen storage and release device on the hydrogenation side, circulate by merging or heat exchange.