JPS5835921B2 - Hydrogen supply system - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrogen supply system to a hydrogen-using device using a combination of a metal hydride hydrogen storage and a microporous hydrogen storage.

From an environmental point of view, hydrogen is clean to use, has great capacity for energy transport, and can be supplied reversibly in the form of water, making it suitable as a fuel in many different systems. The use of hydrogen is becoming extremely important.

Hydrogen can be used as a fuel in devices powered by combustion engines, in which case the hydrogen is oxidized and the energy obtained from this oxidation process is used to power the engine, with water being the only oxidation product.

Additionally, hydrogen can be used as a fuel for generating electrical energy, either by using the heat of combustion to drive a conventional steam turbine, or by using hydrogen directly in a combustion cell.

Water exists as a gas at any temperature except cryogenic temperature.

Currently, large amounts of hydrogen can be stored as a gas by compressing it and storing it in large tanks.

However, since the hydrogen is at high pressure, these tanks need to be very strong, thus requiring very thick walls and heavy tanks.

When hydrogen is stored as a liquid at cryogenic temperatures, as in the case of gaseous hydrogen, the low-temperature liquid hydrogen must also be placed in strong and heavy tanks, further consuming energy in the liquefaction process.

Besides the weight disadvantage of storing hydrogen in tanks as a liquid and gas, storage tanks must be designed and constructed from suitable materials to contain and control the permeability and reactivity of hydrogen with bulk metals. .

It has been proposed to store chemically bound hydrogen in a chemical medium such as methylcyclohexane that can be catalytically converted to toluene and hydrogen, with the hydrogen used as fuel and the toluene recycled to methylcyclohexane.

Two transport networks are required to use such a system.

One is for delivery of the methylcyclohexane to the service station where it will be delivered for consumption, and the other is for the toluene to be returned to the reconversion unit for hydrogenation to methylcyclohexane.

Systems of this type are still in a semi-future state, and many technologies have yet to be developed before such systems can be considered functional.

Systems currently being field tested for using hydrogen as a fuel to propel automobiles include the use of metal hydrides as carriers for the hydrogen fuel.

This system basically involves filling a storage tank with metals that reversibly form metal hydrides.

In the presence of hydrogen and the removal of heat, this metal absorbs hydrogen to form metal hydrides.

When heat is applied, the hydride dissociates into metal and hydrogen, and the hydrogen can be used as fuel.

The heat to dissociate the metal hydride is obtained from the hot exhaust gas from the engine.

Two metal hydride systems have recently been investigated for automotive applications.

One is a hydride of an iron-titanium alloy, and the second is a hydride of a magnesium alloy.

The disadvantage of all metal hydride systems is that they are heavy and expensive.

The issue of weight becomes a serious problem in transport applications such as cars and buses, as transporting additional weight reduces the fuel economy of the vehicle.

In stationary systems, such as those that use hydrogen to generate electricity, the weight of the system is not a critical factor, but these systems require large amounts of metal hydride and the economics of the system becomes a significant issue.

The next issue that must be considered in metal hydride transport systems, such as automotive applications, is the refueling of metal hydride vehicle storage tanks, ie, metal hydride regeneration.

During regeneration, the storage tank of the vehicle must be connected to a device that removes heat from the storage tank and regenerates the metal hydride.

This requires a complex combination of hydrogen supply pipes and cooling pipes.

Metal hydride regeneration would require longer fuel stops compared to the typical five minute stops currently required to receive gasoline.

As is evident from the above, there is a need for new and improved systems for supplying hydrogen to devices that use hydrogen as a fuel.

Accordingly, it is a broad object of the present invention to meet this need.

A further object of the invention is to provide a hydrogen supply system which is not as expensive as hydrogen systems consisting exclusively of metal hydrides.

It is further an object of the present invention to provide a system having a hydrogen capacity comparable to that of liquid hydrogen, but which does not involve the hazardous use of large amounts of liquid or gaseous hydrogen.

Further objects of the present invention include hydrogen supply systems that deliver hydrogen above atmospheric pressure to devices that use hydrogen, but do not require equilibrium storage pressures greater than about 50 to 60 atmospheres.

These and other objectives are met by providing the following hydrogen supply system.

That is, this system uses a metal hydride hydrogen supply component and a microporous hydrogen storage hydrogen supply component, both components supply hydrogen to devices that use hydrogen, and the micropore hydrogen storage hydrogen supply component is a metal hydride hydrogen supply component. supplying hydrogen to regenerate
The system includes a storage tank filled with a compound containing a metal capable of extracting a metal hydride and a heat exchanger capable of adjusting the temperature of the metal hydride to control the adsorption/desorption of hydrogen from the hydride. a hydrogen supply component; a microporous hydrogen storage hydrogen supply component having a microporous hydrogen reservoir and a reservoir having a heating element for heating the microporous hydrogen reservoir and releasing hydrogen from the microporous hydrogen reservoir; Controls for controlling the flow of hydrogen from both the metal hydride hydrogen supply component and the microporous hydrogen storage hydrogen supply component to the hydrogen use device and from the micropore hydrogen storage hydrogen supply component to the metal hydride hydrogen supply component Has a valve.

The invention herein employs the operational concepts or principles set forth and defined in the claims which form a part of this specification.

Those skilled in the art to which this invention pertains will recognize that these conceptual concepts or principles may be readily applied to differently expressed or differently described embodiments, and therefore the invention is not limited to the illustrated embodiments. It will be understood that the invention should not be construed as being limited to the embodiments disclosed herein, but should be construed in light of the scope of the claims.

FIG. 1 shows a generalized embodiment of the present invention, in which a hydrogen consumption device 10 is supplied with hydrogen using the hydrogen supply system of the present invention.

Device 10 can be an energy generating device such as a combustion engine or a fuel cell, or it can be a process plant that uses hydrogen as a chemical reactant.

Representatives of process plants include plants that produce organic chemicals or fertilizers and steel mills that use hydrogen as a reducing agent.

In any case, the hydrogen consumer 10 is supplied with hydrogen by a system comprising a micropore hydrogen storage hydrogen supply component 12 and a metal hydride storage hydrogen supply component 14 .

The metal hydride component 14 provides hydrogen for short term hydrogen usage demands such as peak loads or acceleration.

The microporous component 12 supplies an overall constant demand for hydrogen and is also used for regeneration or refueling of the metal hydride component 14.

To release hydrogen from components 12 and 14, heat is supplied to their respective components to generate hydrogen from both the microporous hydrogen supply and the metal hydride hydrogen supply.

In the case of energy generating devices such as fuel cells or combustion engines, a useful source of this heat is waste heat emitted from the engine or fuel cell.

Control of the rate of hydrogen release from components 12 and 14 is governed by controlling the calothermal rates of components 12 and 14, as described below.

To do this, components 12 and 14 are provided with a heat or temperature controller 1.
6 and 18 are provided.

The humidity controller 16 has a single function of controlling heat addition to the microporous component 12, while the temperature controller 18 controls the addition of heat to the hydride component 1.
This is a two-function control that controls both the addition of heat to and the removal of heat from the heat source.

Heat is supplied to temperature controllers 16 and 18 from a common heat source 20, which in the case of an energy generating device may be waste heat from the device.

Heat from the heat source 20 is routed through branches 24 to components 16 and 18, respectively.
and 26 through the heat supply line 22 to the humidity controller 1
6 and 18.

Heat from temperature controllers 16 and 18 is transferred to heat supply lines 28 and 30.
conducted from.

Line 28 supplies heat to heating element 32 in component 12;
Line 30 supplies heat to heat exchanger 34 in component 14 .

Heat is typically supplied to energy-using devices in the form of a heated fluid.

The supply lines, heating elements and heat exchangers therefore consist of hollow tubes through which this heated fluid flows.

The heat source 20 may be a source of electrical energy, since thermal energy can be supplied as electrical energy, both in energy-using devices and in other devices, and the heat supply line 22.2
4.26.28 and 30 may be electrical conduits.

Heating element 32 and heat exchanger 34 include resistive elements that can generate heat when current is passed through them.

If the heat is provided by a fluid, the heat source 32 and heat exchanger 34 are connected to discharge tubes 36 and 38 for discharging fluid from the heating element 32 and heat exchanger 34, respectively.

If the heat is provided as electrical energy, lines 36 and 38 represent electrical connections that form a complete circuit.

Heat exchanger 34 in component 14 is also connected to coolant supply 40 via lines 42 and 44.

A thermal controller 18 is located between lines 42 and 44 to control the heat in heat exchanger 34 and to control the flow of coolant in heat exchanger 34 .

The line 44 is connected to the heat exchanger 34 and the heat exchanger 34 is also provided with a coolant discharge line 46 for discharging the coolant discharged from the heat exchanger 34.

Alternatively, the discharged coolant is returned to the coolant source 40 through line 48, shown in FIG.

The hydrogen gas released from component 12 is transferred to component 14 and device 10.
The hydrogen released from component 14 is supplied to apparatus 10.

Both of these supply systems are completed by a series of conduits with flow control valves to control the flow of hydrogen.

Conduit 50 supplies hydrogen gas to conduits 52 and 54.

Conduit 52 leads to a flow control valve 56 from which hydrogen gas flows through conduits 58 and 60 to apparatus 10.

Further, the hydrogen gas is passed from the component 12 to the conduit 54 and the flow rate control valve 62.
and to component 14 via conduits 64 and 66.

Hydrogen gas from component 14 is supplied to apparatus 10 via conduit 66.6B, flow control valve 70, conduit 72, and conduit 60.

The micropore storage component 12 is excavated from a mass of micropores filled with hydrogen gas at pressures up to 10,000 psi.

The micropores are generally about 5 to about 500 microns in diameter.

The pore walls are generally about 0.01 to about 0.1 times the pore diameter.

Generally, micropores are microspheres.

However, the microspheres are sintered together to form a porous structure having both interconnected pores and closed microspheres.

Rapid hole making provides access to closed micropores throughout the sintered structure.

In the form of discrete microspheres, the filled microspheres may move like fine sand or be suspended in a transport gas or fluid with each operation.

However, porous structures have the advantage of being easier to handle.

For example, a porous canister of calcined microspheres can be filled and inserted into a tube provided with an outlet to release hydrogen.

The above-mentioned porous canister of fired microspheres is described, for example, in the US NASA report of July 1978, NASA
- CR-254 A, Tobi (Reference by 1st class) D
development of C1osed-Pore
It can be made according to the lnsulat-ing material guide.

This report describes the fabrication of microsphere composite materials by calcination.

Hollow microspheres can be made of plastic, carbon, or
It can be made from metal, glass or ceramics.

Generally, the above microspheres are Emerson-Cumming SI class (E
The microspheres are made from silicate glasses such as high silica microspheres (Merson-Cuming SI grade).

The above Emerson-Cumming SI grade silica microspheres were previously manufactured by Emerson-Cumming Corporation (Emerson-Cumming Corporation).
erson-Cuming Corporation
The microspheres are commercially available from ).

Recently, Emerson Corporation has acquired Grace Chemicals.
These microspheres were then merged into SI class Ecco spheres or Micro Bal 1oons.
It is currently commercially available under the trade name Dewey Almy Chemical Divi, Gerace Chemical Corporation, Canton, Massachusetts, USA.
sion).

Under high hydrogen pressure and elevated temperature, hydrogen diffuses into the micropores.

When stored at room temperature and atmospheric pressure, hydrogen remains under high pressure in the micropores.

Reheating the pores causes hydrogen to diffuse out of the pores and become available for use by device 10.

The permeability of the microsphere wall can be changed by coating the wall.

Typical coatings include plastic and metal.

Metallic coatings are particularly preferred and can be used to reduce dusting of hydrogen from the microspheres at storage temperatures, but at elevated temperatures during filling of the microspheres or dispensing hydrogen from the microspheres. does not impede the diffusion of hydrogen into and out of the microspheres.

Metallic coatings can be applied by electroless or electroplating, chemical vapor decomposition or centrifugal coating methods.

Representative metals suitable for coating silicate glass microspheres include aluminum, molybdenum, nickel, copper, and alloys thereof.

Metal hydride hydrogen storage component 14 uses a composition having at least one metal that forms a metal hydride when exposed to hydrogen.

Additionally, other metals can be alloyed with the primary metal to change the properties of the final metal hydride.

The base metal chosen and the additive metal to be alloyed with it will depend on the hydrogen supply device.

The criterion for determining which metal hydride to use is the heat of formation of the hydride.

When heating a metal hydride to generate hydrogen using the waste heat of the device 10, the metal hydride must be able to generate hydrogen within the heat range of the waste heat from the standpoint of energy conservation. No additional energy needs to be expended to heat the hydride.

As mentioned above, two hydride systems have recently been investigated for use in hydrogen fueled vehicles.

These systems are derived from iron titanium and magnesium alloys.

An alloy with equimolar amounts of iron and titanium has 5.5K per mole of hydrogen.
It has a heat of formation of cal.

Magnesium hydride has -17,8 Kc per mole of hydrogen
It has heat of formation of al.

The heat of formation can be reduced by alloying magnesium with nickel or copper.

A nickel alloy with a typical composition of M g 2 N t has -15.4 KcaJl per molecule! It has a heat of formation of

Hydrides with high decomposition pressures at low temperatures have relatively small values of the heat of formation.

Magnesium nickel hydride has a dissociation temperature of about 300°C.

By adding zinc to the alloy, the dissociation temperature can be lowered to provide a dissociation temperature of about 260°C.

Other metals with useful heats of formation that can be used to make metal hydrides include vanadium, niobium, palladium, and Mitsch metal alloys.

Also potassium, uranium, zirconium, calcium,
Lithium and cerium are known to form hydrides; however, the heat of formation of hydrides of these metals is very large.

Iron titanium hydride is heavier than magnesium nickel hydride; however, the heat of formation of iron titanium hydride is -5.5
It's just Kcal.

The dissociation temperature of iron-titanium hydride is only 25°C.

Device for generating hydrogen from metal hydride using waste heat 1
Iron titanium hydride is the preferred metal alloy for use in 0.0.

If this hydride is heated to an appropriate temperature, it will decompose and about 10
Hydrogen is supplied at a pressure of 0 to about 1000 psi.

The efficiency of metal hydrides also depends on the surface area of the metal.

Surface area can be greatly improved by cycling the metal through a series of hydride formation-hydrogen generation cycles.

Therefore, the efficiency of metal hydrides as hydrogen absorbers or hydrogen generators increases with use, but the hydride is initially prepared by subjecting it to several cycles of hydride formation-dissociation.

A useful property of metal hydrides is that they can contain more hydrogen by volume than cryogenic liquid hydrogen.

Microspheres can contain approximately the same volume of hydrogen as cryogenic hydrogen; however, microspheres can perform this hydrogen storage in smaller unit volumes when compared to metal hydrides.

In order to further illustrate the present invention below, (a) Hydrogen using device 1
(b) The microporous hydrogen storage component 12 is a microsphere and p (the CJ metal hydride storage component 14 is an iron titanium hydride).

Figure 2 shows an overall diagram of hydrogen utilization from manufacturing to power generation.

Hydrogen production plant 74 produces hydrogen by one of a variety of methods.

Water can be electrolyzed using conventional power systems such as solar, fossil fuel or nuclear generators.

Other methods such as radiochemical or thermochemical hydrogen generation methods may also be used in the future.

In any event, the water is converted to hydrogen and oxygen, and the waste heat from this conversion is used to encapsulate this hydrogen into microspheres in an encapsulation plant 76, which may preferably be located near the manufacturing plant.

There are various benefits to encapsulating hydrogen at or near a hydrogen production plant.

One is the potential economic gain from mass production.

;Secondly, waste heat from production is used to encapsulate hydrogen;
Part 3 simplifies the transport of hydrogen by contacting the hydrogen with microspheres, and safety benefits are achieved from this transport method as described below.

After the hydrogen is encapsulated, it can be stored in a long-term storage 78 until delivered to the consumer.

Because the hydrogen gas is contained within the microspheres, the pressure in the tank used to hold the microspheres is much lower than the pressure in the tank when hydrogen is stored as a liquid or gas.

This has the advantage of reducing hydrogen-induced embrittlement of storage tanks or storage pipes to negligible levels.

For long-term storage, the storage tank can be cooled to prevent hydrogen from escaping from the microspheres.

After storage, the microspheres are transported by transport hole 80 to a local service station dispensing device 82.

Transport of the microspheres can be carried out by transporting tanks of microspheres by truck, ship, rail tank car, etc., or the microspheres can be slurried in a transport fluid such as nitrogen or air and transported by fluid in a pipeline. .

At the receiving end of the pipeline, the microspheres are separated from the fluid using a cyclone separator or the like.

In the service station dispensing system 82, microspheres can be used in the hydride preparation operation shown at block 84 and described above.

However, the primary purpose of service station dispensing device 82 is to dispense hydrogen-containing microspheres to vehicles 86.

Car 86 will carry a microsphere storage tank 88 filled with microspheres.

The hydrogen contained in the microsphere storage tank is used in car engines9
0 as a fuel source and as a fill source for metal hydrides in storage tank 92.

The car's engine 90 burns hydrogen and uses the power obtained from the hydrogen to propel the car.

The waste product from this process is water; thus completing the ecological cycle.

Once the hydrogen in the microspheres is emptied, it could be recycled to the encapsulation plant for refilling.

As shown in FIG. 3, a vehicle 86 with an engine 90 is provided with a microsphere storage tank 88 and a metal hydride storage tank 92.

The storage tank 88 is filled with microspheres 94 and the storage tank 9
2 is filled with metal hydride composition 96.

The storage tank 88 has an inlet 9B with a cap that allows access to and from the tank to refill the tank with a fresh supply of microspheres 94.

Inside the tank 8B is a heating element 102.

Heating element 102 is a hollow tube through which hot gas passes.

Within tank 92 is a heat exchanger 104 having a hollow passage for hot gas and a second passage for cooling fluid.

Exhaust pipe 106 is connected to the exhaust manifold of engine 90 and guides hot gases from the engine.

The exhaust pipe 106 extends and connects to the branch pipe 10B.

There is a flow control valve 109 downstream of the branch pipe 108, and when this valve is closed, the exhaust gas in the exhaust pipe 109 is transferred to the branch pipe 1.
Divided into 08.

Branch pipe 108 connects to two temperature regulators, temperature controller 110 controlling hot gas flow to heating element 102 and temperature controller 112 controlling hot gas flow to heat exchanger 104. .

Heating element 102 extends to become exhaust pipe 114 and connects to exhaust pipe 106 downstream of diverter valve 109 .

Similarly, the exhaust pipe 116 is connected from the heat exchanger 104 to the exhaust pipe 106.
It grows to.

The car 86 has a radiator 11B for engine cooling.

A heat exchange pipe 120 is integrated into the radiator 118 and connects to a coolant supply pipe 122 and a coolant return pipe 124 .

Coolant flows through tube 122 to temperature controller 112 .

Coolant flows from temperature controller 112 through heat exchanger 104 to metal hydride tank 92 and then to return line 124.
and then returns to the heat exchanger pipe 120.

Metal hydride tank 92 has an opening 126 to which hydrogen conduit 12B is connected.

Conduit 12B connects to hydrogen flow valve 130.

There is a hydrogen conduit 132 on the outlet side of the hydrogen flow valve 130,
Connected to engine supply conduit 134.

Microsphere storage tank 88 has an opening 136 that connects to conduit 138 .

Conduit 13B extends into two branch conduits 140 and 142.

Branch pipe 140 connects to a flow control valve 144 with a conduit 146 on the outlet side of flow control valve 144 that connects to engine supply conduit 134 .

Branch pipe 142 connects to a flow control valve 148, the outlet of which connects to an additional conduit 150, which in turn connects to conduit 12B.

Conduit 138 includes conduit 1 having a two-way flow control valve 154.
It is connected to 52.

The flow rate control valve 154 is connected to a small hydrogen gas receiver 156.

The main controller 158 includes the engine 90, temperature controllers 110 and 112, flow rate control valves 130, 144, 148 and 154.
, are connected to the flow control valve 109 by suitable control lines, all collectively represented by the number 160.

Pressure sensitizers 162, 164 and 166 are connected to conduits 128, 1
38 and the gas receiver 156, respectively.

These pressure sensitizers are also connected to the master controller 158 by control lines, all designated collectively by the numeral 168.

In use, to start the engine, main controller 1
5B, the flow control valves 144 and 154 are opened to allow the residual hydrogen gas in the tank 88 and the hydrogen gas in the receiver 156 to flow into the engine and be used as fuel.

After a few minutes, engine 90 reaches its operating temperature and the exhaust gases exiting engine 90 become very hot.

Master controller 158 signals diverter control valve 109 to close and temperature controller 112 to open and allow hot exhaust gas to flow through heat exchanger 104 .

The heat exchanger heats the metal hydride in tank 92 to release hydrogen from the metal hydride.

The flow rate control valve 130 opens and hydrogen flows into the metal hydride tank 9.
2 to the engine 90.

The temperature controller is opened at the main controller 158 to allow heated gas to pass through the heating element 102 .

This heating element initiates the release of hydrogen from the microspheres 94.

As the flow of hydrogen being discharged from tank 88 increases, the flow of hydrogen from reservoir 156 is stopped and reservoir 156 is recompressed to a predetermined level sensed by pressure sensitizer 166 .

Valve 154 is then closed to trap a new amount of hydrogen in reservoir 156, which reservoir will be used for the next engine start.

In response to engine fuel demand, main controller 158 opens and closes temperature controllers 110 and 112 and flow control valve 109;
This controls the amount of heated gas passing through heating element 102 and heat exchanger 104, which in turn controls the release of hydrogen from tanks 88 and 92.

When the metal hydride in tank 92 is depleted of hydrogen, the pressure drop in tank 92 is signaled by pressure sensitizer 162 and master controller 158 sends a signal to temperature controller 112 to turn heat exchanger 104 on. Stop the heated gas flow passing through the heat exchanger 1
Begin cooling fluid flow through 04.

This causes heat to begin to be removed from tank 92 and flow valve 13
0 is closed and flow valve 148 is opened to allow hydrogen in tank 88 to pass to tank 92 for metal hydride regeneration.

An additional advantage of the present invention is that most of the hydrogen used in vehicle fuel is stored in microspheroidal hydrogen storage, which reduces safety factors.

It is known that explosive gas can be stored in microspheres because the balls effectively suppress the layer propagation necessary to sustain the explosion.

Even if the large amount of hydrogen encapsulated in the microspheres were to meet with an accident and destroy the microsphere storage tank, the hydrogen would not be released and would remain safely inside each microsphere.

In another embodiment, shown in FIG. 4, hydrogen is delivered to apparatus 170 using a metal hydride hydrogen storage hydrogen supply component 172 in series with a microspherical hydrogen storage hydrogen supply component 174.

Metal hydride component 172 is connected to microporous hydrogen component 174 via tube 176.

A control valve 178 is provided in the middle of the pipe 176 .

A second tube 180 connects the microporous hydrogen component 174 to the hydrogen usage device 170.

A second control valve 182 is provided in the middle of the pipe 180.

Component 172 is the same metal hydride 184 as the above hydride.
have.

Component 174 is hydrogen microporous storage 186 such as the above-mentioned globules.
have.

Component 172 has the same components as above and a heat exchanger 188 having the same heating section 190 and cooling section 192.

Component 174 includes a heater 194 as described above, and the heating element and heater 194 are supplied with heat from the same heat source 196 as described above.

The cooling component 192 again includes a coolant receiver 198 as described above.
Coolant is supplied from

By opening valve 182, micropore storage component 18
6 can directly supply hydrogen to the device 170.

Alternatively, valves 178 and 182 can be opened to supply hydrogen from metal hydride component 172 to device 170.

Metal hydride component 184 is recharged from microspheres 186 with valve 182 closed and valve 178 opened.

The system may also use suitable controllers similar to those described above to monitor and control hydrogen flow.

To start up the device 170, the microspheres can be filled with the microporous component 174 as the hydrogen supply component and the void spaces between the individual spheres serve as residual hydrogen storage.

Therefore, the microporous component 174 can have hydrogen at two different pressures.

That is, the first is high pressure hydrogen inside the micropores, and the second is low pressure hydrogen outside the micropores.

This type of hydrogen receiver can also be used in conjunction with the other embodiments described above.

Another embodiment of the invention uses only one storage tank.

Both the metal hydride and the microporous storage system are placed within this storage tank.

This specific example has the advantage that the metal hydride is located in the immediate vicinity of the micropores, and hydrogen can be directly exchanged from the micropores to the metal hydride, and when the metal hydride absorbs hydrogen, it is released from the metal hydride. Heat can be used to directly heat the microspheres and stimulate them to release more hydrogen.

Typical glass microspheres release hydrogen just below 175°C.

Therefore, in this system the metal hydride chosen will be one with a somewhat higher dissociation temperature.

Therefore, the energy released when hydrogen is absorbed will be at a temperature slightly higher than that required to release hydrogen from the micropores.

In systems of this type metal hydrides based on magnesium or one of its alloys are preferred.

Example 1 Filling and Ejection of Microspheres A sample of D-32-45003M microspheres obtained from 3M Corporation, St. Paul, Minn., USA, was used for testing purposes.

The above microspheres were placed in a sealed container at a hydrogen pressure of 472 atm.
Filling was carried out at 50° C. for 2 hours.

The filled microspheres were then placed in a container connected to a gas billet and a gas flow meter.

The test bed was continuously heated to higher temperatures while maintaining a minimum flow rate of 0.7 cc/bed volume CCl3+.

At the end of the test, a total of 0.055 g of hydrogen per gram of bed was obtained.

Of this, 58% of hydrogen was obtained at temperatures between room temperature and 200°C.

77% of the hydrogen was obtained between room temperature and 250°C.

91% of the hydrogen was obtained between room temperature and 300°C, and all gas beds were vented of hydrogen above 400°C.

At the completion of the test, more than 90 microspheres remained intact.

The above test flow rate of 0.7cc/Icc/min indicates that a vehicle with a fuel efficiency of 20 miles per gallon using gasoline and 20 gallons of fuel would be expected to travel for 66 hours. The hydrogen requirement was set based on the amount of hydrogen required to run a car at 60 miles per hour.

Actually, 0.77ccli less cc from the above microspheres
A hydrogen flow rate of /min removed hydrogen from the microsphere bed in 4 hours.

This indicates acceptable hydrogen pumping rates for vehicle use at highway speeds, allowable fuel capacity, and temperatures obtained using waste engine heat.

Example 2 Boarding test of microsphere-metal hydride storage combination 3.00
A passenger vehicle with an equipped weight of 0 pounds and a four passenger load of 700 pounds was considered.

For this passenger car, the front projected area is 20 ft2 and 1
A vehicle length of 1.7 ft resulted in a drag coefficient of 0.35.

This passenger vehicle was evaluated using a 67 horsepower engine with a combination engine, transmission, cooling, and exhaust system weighing 525 pounds.

For a projected test range of 150 miles at a maximum hydrogen usage of 2.76 p/d/hr, a total useful hydrogen storage capacity of 17 pounds of hydrogen was demonstrated.

Of the total hydrogen, 3.6 pounds of hydrogen was stored in a container weighing 53 pounds and having a capacity of 1.3 ft2;
Situated in a bed of 210 pounds of B 5 M n 6.15.

The remaining 13.4 pounds of hydrogen is placed in a bed of 268 pounds of microspheres stored in a 64 pound container with a capacity of 13.7 square feet.

The heat exchanger weight and compressor weight account for an additional 78 pounds and 16 pounds, respectively, for the total hydrogen supply weight of 689 pounds.

For the above device, approximately 20% of the hydrogen is initially stored in the metal hydride and the remainder of the hydrogen is stored in the microspheres.

The titanium-iron-manganese metal hydride used is currently commercially available.

The use of another metal hydride with a higher hydrogen capacity per bed weight to supply 20% of the hydrogen carried by the hydride would result in a lighter overall hydrogen storage device.

Matters related to this application are described below.

A hydrogen supply system to a combustion engine, which is provided with an air-hydrogen mixing means for supplying a combustion mixture of hydrogen and air to the combustion engine, comprising a first storage tank and exposed to hydrogen in said first storage tank. and a metal hydride hydrogen supply means having a large amount of a composition containing at least one metal capable of absorbing hydrogen to form a metal hydride, and capable of thermally decomposing the metal hydride to generate hydrogen; a second storage tank; microporous hydrogen storage hydrogen supply means having microporous means containing hydrogen encapsulated in the microporous means located in the second storage tank; a first conduit means for supplying hydrogen to the apparatus; a second conduit means for supplying hydrogen from the micropore hydrogen storage hydrogen supply means to the apparatus; from the micropore hydrogen storage hydrogen supply means to the metal hydride hydrogen storage means; third conduit means for supplying hydrogen; first control means for regulating the adsorption/desorption of hydrogen from the metal hydride hydrogen storage means by regulating the temperature of the composition in the metal hydride hydrogen supply means; second control means for regulating the release of hydrogen from said microporous hydrogen storage hydrogen supply means; first valve means for regulating hydrogen flow through said first conduit means; and first valve means for regulating hydrogen flow through said second conduit means. second valve means: third valve means for regulating the flow of hydrogen through said third conduit means; said microporous means comprising a number of microspheres containing hydrogen encapsulated within said microspheres; Application of heat to the microspheres can release hydrogen contained therein, and the second control means controls the second control means for heating the microspheres.
storage tank heating means, said heating means comprising at least one hollow tube within said second storage tank; said engine having hot exhaust gas discharge means; said hollow tube comprising at least one hollow tube within said second storage tank; The high temperature exhaust gas from the high temperature exhaust gas discharge means can pass through the hollow tube to heat the contents in the second storage tank, and the high temperature exhaust gas can pass through the hollow tube. high temperature gas flow rate control means for regulating the flow; the metal hydride is iron titanium hydride;
The control means includes a heat exchanger in the first storage tank, the heat exchanger causing the composition in the first storage tank to absorb or release heat, and the heat exchanger to cause the composition in the first storage tank to absorb or release heat; Both are made of one hollow tube, and the high temperature exhaust gas discharge means is connected to the hollow space, and the high temperature exhaust gas from the high temperature gas discharge means heats the contents in the first storage tank. the heat exchanger having at least one coolant inlet pipe means; a coolant supply means; the coolant supply means supplying coolant to the coolant inlet pipe means; second hot exhaust gas flow control means for removing heat from said first storage tank by a coolant flowing through said coolant introduction means and regulating hot exhaust gas passing through said heat exchanger; cooling through said heat exchanger; The hydrogen supply system described above, comprising: a coolant flow rate controller that adjusts the flow of the coolant.

[Brief explanation of drawings]

FIG. 1 is an explanatory schematic diagram showing each component of the present invention, FIG. 2 is a block diagram showing the steps between hydrogen production and hydrogen use, and FIG. 3 is a partially cutaway side elevational view showing the present invention. FIG. 4 is a partial schematic diagram showing another embodiment of the present invention. 10... Hydrogen consumption device, 12... Micropore hydrogen storage hydrogen supply component, 14... Metal hydride hydrogen storage hydrogen supply component, 16.18... Temperature regulator, 20... Heat source,
32... Heating element, 34... Heat exchanger, 40...
Coolant supply source, 56...Flow rate control valve, 70...Flow rate control valve, 78...Storage, 80...Transportation means, 82
...Service station distribution device, 86...Car,
88... Microsphere storage tank, 90... Car engine,
92... Storage tank, 94... Microsphere, 96...
Metal hydride composition, 102... heating element, 104.
・・Heat exchanger, 106° 114 ・・Discharge pipe, 11
0,112...Temperature controller, 11B...Radiator, 128,132...Hydrogen conduit, 134...Engine supply conduit, 154...Two-way valve, 156...Hydrogen receiver, 158 ... Main controller, 170 ... Device, 17
2... Metal hydride hydrogen storage hydrogen supply component, 174.
・・Micropore hydrogen storage hydrogen supply component, 178,182・・
- Control valve, iso, 194... Heater, 196... Heat source, 192... Cooling component, 198... Coolant receiver.

Claims (1)

[Scope of Claims] 1. A storage means for containing hydrogen; said storage means connected to said storage means for releasing said hydrogen from said storage means. an extraction conduit, a first chamber means, a second chamber means and a connection means connecting the first chamber means to the second chamber means, the microporous hydrogen storage means being located in the first chamber; Under pressure, the pore hydrogen storage means has a porous structure with a large number of micropores delimited by closed pores surrounded by hydrogen permeable walls, said micropores being encapsulated inside these walls. of hydrogen, the micropores being capable of releasing the compressed hydrogen encapsulated within them when heated; a large amount of composition capable of forming at least one metal hydride when exposed to hydrogen; is located in said second chamber means, and said metal hydride releases hydrogen when heated and absorbs hydrogen when cooled in the presence of hydrogen. heating the pores to diffuse the compressed hydrogen from the interior of the pores to the exterior of the pores through the permeable wall; hydrogen from the first chamber to the second chamber through the connecting means; supplying; adjusting the temperature of said composition in accordance with the pressure of said hydrogen in said second chamber means to maintain a substantially constant hydrogen pressure in said second chamber means; supplying said hydrogen from said hydrogen storage system; 2. A method according to claim 1, characterized in that the hydrogen is removed for external use through a removal conduit. 2. A method according to claim 1, wherein the microporous hydrogen storage means comprises a plurality of microspheres. 3. A method as claimed in claim 2 comprising salt glass microspheres.'□4 The microporous hydrogen storage means is defined by communicating holes and obturator pores, and wherein the communicating holes provide access to the obturator pores. 5. The method of claim 1, wherein the closed pores contain hydrogen under pressure and the hydrogen is released into the open pores. 5. The porous structure is sintered together to form a single piece. 6. The method of claim 4, wherein the composition comprises a large number of glass microspheres. 6. The method of claim 1, wherein the composition comprises iron titanium hydride. 7. The method of claim 1, wherein the composition comprises iron titanium hydride. The method according to claim 1, wherein the microporous material comprises a large number of microspheres. □8 In a hydrogen supply device for a hydrogen fuel device, the first
a storage tank, capable of absorbing hydrogen to form a metal hydride when exposed to hydrogen in the first storage tank;
A metal hydride hydrogen supply means, in which a quantity of a composition containing at least one metal capable of thermally decomposing the metal hydride to release hydrogen is located: a second storage tank; and a second storage tank located in the second storage tank. microporous hydrogen storage hydrogen supply means having microporous means containing hydrogen encapsulated within the microporous means; first conduit means for supplying hydrogen from said metal hydride hydrogen storage means to said device; said microporous means. A second conduit means for supplying hydrogen from the hydrogen storage hydrogen supply means to the device; a third conduit means for supplying hydrogen from the microporous hydrogen storage hydrogen supply means to the metal hydride hydrogen storage means; a third conduit means for supplying hydrogen to the metal hydride hydrogen storage device; a first control means for regulating the adsorption/desorption of hydrogen from the metal hydride hydrogen supply means by regulating the temperature of the composition within the means; regulating the release of hydrogen from the microporous hydrogen storage hydrogen supply means; second control means; first valve means for regulating hydrogen flow through said first conduit means; second valve means for regulating hydrogen flow through said second conduit means;
and a third valve means for regulating hydrogen flow through the third conduit means. 9 A patent in which said microporous means consists of a number of microspheres containing hydrogen encapsulated within said microspheres, said microspheres being able to release the hydrogen contained therein by application of heat to said microspheres. The hydrogen supply device according to claim 8. 10. The hydrogen supply device according to claim 9, wherein said second control means includes heating means for heating said microspheres in said second storage tank. 11 The above composition is iron titanium hydride, magnesium hydride, vanadium hydride, niobium hydride, magnesium nickel hydride, magnesium copper hydride,
9. The hydrogen supply device according to claim 8, which is selected from the group consisting of Mitsushi metal hydride and magnesium nickel zinc hydride. 12. The hydrogen supply device according to claim 11, wherein the composition is selected from the group consisting of iron titanium hydride, magnesium hydride, and magnesium nickel hydride. 13 The metal hydride is iron titanium hydride. A hydrogen supply device according to claim 12. 14. Claim 8, wherein said first control means includes a heat exchanger in said first storage tank, said heat exchanger absorbing or releasing heat to said composition in said first storage tank. The hydrogen supply device described. 15. The hydrogen supply device of claim 8, comprising a gaseous hydrogen receiver and fourth conduit means, said fourth conduit means supplying hydrogen from said receiver to said device. 16. The hydrogen supply system of claim 8, wherein said hydrogen fuel system is a combustion engine provided with air-hydrogen mixing means for supplying a combustible mixture of hydrogen and air to the combustion engine. 17. Said microporous means consists of a number of microspheres containing hydrogen encapsulated in said microspheres, said microspheres releasing the hydrogen contained therein by application of heat to said microspheres. A hydrogen supply device according to claim 16. 1B. The hydrogen supply device according to claim 17, wherein said second control means includes heating means in said second storage tank for heating said microspheres. 19. The hydrogen supply system according to claim 16, wherein said combustion engine has means for discharging hot exhaust gases. 20 The heating means comprises at least one hollow tube in the second storage tank; the engine has hot exhaust gas exhaust means; the hollow tube is connected to the hot exhaust gas exhaust means; 19. The hydrogen supply system of claim 18, wherein hot exhaust gas from the hot exhaust gas exhaust means passes through the hollow tube to heat the contents in the second storage tank. 21 Claim 20 further comprising hot exhaust gas flow rate regulating means for regulating the flow of hot exhaust gas through the hollow tube.
Hydrogen supply device described in section. 17. The hydrogen supply device according to claim 16, wherein the composition is selected from the group consisting of iron titanium hydride, magnesium nickel hydride, and magnesium hydride. The hydrogen supply device according to claim 22, wherein the metal hydride is an iron titanium hydride. 24. Claim 16, wherein said first control means includes a heat exchanger in said first storage tank, said heat exchanger causing said composition in said first storage tank to absorb or release heat. The hydrogen supply device described. b. said heat exchanger is connected to at least one of said first storage tanks;
25. The hydrogen supply device according to claim 24, which comprises a hollow tube. 26 The combustion engine has a hot exhaust gas exhaust means, the hot exhaust gas exhaust means is connected to the hollow tube, and the hot gas exhaust means passes through the hollow tube to the first
26. A hydrogen supply device according to claim 25, which heats the contents in a storage tank. 27 The heat exchanger has at least one coolant inlet pipe means; a coolant supply means, the coolant supply means supplying coolant to the coolant inlet pipe means from the first storage tank. 27. The hydrogen supply device according to claim 26, wherein the heat is extracted by the coolant flowing through the coolant introduction pipe means. 28 Claim 27 further comprising hot exhaust gas flow control means for regulating the flow of hot exhaust gas through said heat exchanger.
Hydrogen supply device described in section. (iv) A hydrogen supply device for a hydrogen fuel device, comprising a first storage tank, in which at least one metal capable of absorbing hydrogen and forming a metal hydride when exposed to hydrogen is contained in the first storage tank. a metal hydride hydrogen supply means in which a large amount of a composition containing a metal hydride can be thermally decomposed to release hydrogen; a second storage tank in the microporous means located within the second storage tank means; microporous hydrogen storage means having microporous means containing hydrogen encapsulated in a microporous hydrogen storage means; first conduit means connecting said microporous hydrogen storage and hydrogen supply means to said hydrogen fuel device; and said microporous hydrogen storage and hydrogen supply means. second conduit means for connecting said metal hydride hydrogen storage means to said first conduit means, first valve means for regulating hydrogen flow through said first conduit means, second valve means for regulating hydrogen flow through said second conduit, and more. The hydrogen supply device described above. - a first control means for controlling the adsorption/desorption of hydrogen from the metal hydride hydrogen supply means by adjusting the temperature of the composition in the metal hydride hydrogen supply means; the micropore hydrogen storage hydrogen supply; 30. A hydrogen supply system as claimed in claim 29, including second control means for regulating zero hydrogen release from the means.