WO1990008101A1

WO1990008101A1 - Recyclable hydrogen cartridge

Info

Publication number: WO1990008101A1
Application number: PCT/AT1990/000007
Authority: WO
Inventors: Peter Schütz
Original assignee: Elin Energieversorgung Gesellschaft M.B.H.
Priority date: 1989-01-16
Filing date: 1990-01-16
Publication date: 1990-07-26
Also published as: CS22290A3; AT396013B; DD291610A5; ATA7189A

Abstract

Recyclable, disposable hydrogen cartridge consisting of a container, such as a spray can, gas cartridge, soda water cartridge or cigarette-lighter gas refill container, and containing a hydrogen-binding material charged with hydrogen.

Description

RECYCLABLE HYDROGEN CARTRIDGE

The present invention relates to a recyclable disposable hydrogen cartridge which, in a practical manner, ensures that small consumers are supplied with hydrogen. -

Hydrogen is often referred to as the energy source of the future. The market launch has so far failed due to the high price and poor manageability.

Hydrogen is currently available in the following three storage forms:

1. In high-pressure accumulators, in which the gas is stored under high pressure, usually around 150 bar. This form of storage, e.g. Gas bottles are very common, but their use is limited by the high empty weight of the bottles, a certain minimum size of the same and various safety regulations.

2. Hydrogen can be liquefied at very low temperatures (-253 ° C) and stored and transported in this form. This form of storage takes place with very large units, e.g. Tankers use, but is out of the question for economic and technical reasons if small consumers are considered.

3. The safest and most modern form of storage is with the help of hydrogen-binding materials. Here the hydrogen gas is stored, for example under pressure, in the metal grid of special alloys and can be removed from the storage medium again under reduced pressure and by supplying heat. When using metal alloys to bind the hydrogen, hydride stores are referred to. However, other substances can also be used to bind the hydrogen, such as zeolites, ceramic substances, activated carbon or special plastics, which are able to bind the hydrogen adsorptively and are therefore suitable as a storage medium. One advantage of this form of storage is that medium-quality hydrogen is converted into a highly pure form by the gettering effect of the metal alloy.

The containers used for this are very similar to the high-pressure bottles. The hydrogen-binding material is filled as granules into special pressure bottles, which have heat exchangers inside and outside, in order to be able to dissipate or supply the heat released during loading and the required heat during unloading.

When loading the accumulator, charging pressures of 40 bar are required, although the equilibrium pressure and discharge pressure are usually only in the range of 1 bar. Conventional hydrogen tanks based on hydrogen-binding materials are therefore characterized by a solid design, pressure resistance, heat exchange devices, cyclability, long service life and therefore a relatively high price. The handling is quite cumbersome due to the large weight and volume of the containers.

The storage volumes of the previously known hydride stores

3 are designed for hydrogen quantities from 1 to 5 m.

From what has been said so far, it is clear that the known forms of hydrogen storage are complex in relation to the containers used, which are much too heavy and unwieldy for everyday use on a small scale.

The aim of the present invention was therefore to bring hydrogen onto the market in inexpensive, easy-to-handle, recyclable single-use containers which are readily available in normal trade and are easily interchangeable at any time.

According to the invention, this goal is achieved in that a recyclable disposable hydrogen cartridge from a container in the manner of a spray can, gas cartouche, soda water cartridge or a lighter gas refill container, which contains a hydrogen-binding material containing hydrogen. The pressure resistance of such containers is legally stipulated in the steam boiler law. In this regard, reference is made in particular to Decree 141 (BgBl 132/81).

The cartridge preferably contains hydride-forming metal alloys, in particular titanium alloys, but also zeolites and ceramic materials, activated carbon or hydrogen-binding plastics as the hydrogen-binding material. Materials that correspond to a lower energy content of approx. 1 kWh / liter of storage substance represent the lower limit of applicability. Substances with too high equilibrium pressures are ruled out for use in aerosol-like containers.

The preferred way of producing the hydrogen cartridges according to the invention is that the hydrogen-binding material is loaded with hydrogen in an openable pressure container and is filled into the cartridge container at a suitably low temperature and possibly increased pressure, whereupon these are sealed. The temperature for the decanting process will advantageously be chosen so that the equilibrium pressure is as low as possible. These processes take place at the manufacturer of the cartridges, so that the consumer is provided with a finished, easy-to-handle container, which is returned to the manufacturer by a collection system after the hydrogen has been consumed. There, the material freed from hydrogen is removed from the containers and recycled to the new hydrogen-laden material.

On the other hand, it should be noted that in the rechargeable hydride stores currently in use, the final consumer mostly buys the hydrogen in pressure bottles and then transfers it to the hydride store. This is extremely expensive because the cylinder gas costs around 100 times the factory price at the producer. It therefore seems advantageous to carry out the loading process of the metal hydride on an industrial scale, directly in the factory, in order to minimize the gas price.

In this way, the large pressure hysteresis between loading and unloading of the hydrogen-binding material is avoided. A memory that is only designed for one-time unloading can be made thin-walled and cheap, since it only has to be dimensioned for low pressure and a short service life.

The storage tanks according to the invention naturally do not have any additional heat exchangers. Although this reduces the rate of unloading, it also increases the energy density, i.e. the energy content per part by weight or volume, because the dead weight is minimized.

The main advantages of the invention thus lie in a cheap hydrogen supply on a small scale through the use of inexpensive, thin-walled disposable containers, factory loading of the hydrogen-absorbing materials with hydrogen and low dead weight by avoiding heat exchangers and other additional devices.

Inexpensive, known and commercially available cartouches are suitable as containers for the hydrogen cartridges according to the invention, e.g. in the form of spray cans, camping gas cartouches, soda water cartridges or lighter gas refill containers.

The finished cartridges are supplied to the end consumer via conventional distribution channels, who uses them as a gas source. The unloaded cartridges are taken back by the dealer and returned to the manufacturer. There the material is recovered from the cartridges, loaded with hydrogen again and filled into new cartridges. The production cycle is now closed.

All process steps for the manufacture of the cartridges according to the invention, such as loading the hydrogen-absorbing material, e.g. In the form of powder, granules or pellets, in suitable pressure vessels under high hydrogen pressure and dissipation of the heat thereby generated, and the filling of the cartridges at low temperature under slightly elevated pressure can be carried out without problems for the person skilled in the art.

The cartridges according to the invention can be used, for example, in the laboratory and in portable devices as a source of high-purity hydrogen, it being possible to provide small cartridges for ultra-pure hydrogen which can be used directly in measuring or analysis devices. It can be used as a gas source for the smallest autogenous welding devices or catalytic soldering irons. A special application is the generation of electrical current in connection with small fuel cells. In general, the use of hydride cartridges makes sense wherever the volume and weight of the memory are to be minimized and rapid reloading (replacement of the cartridges) is desired.

Design example:

1 kilogram of hybrid-forming titanium alloy No. 5777 from HWT, with a specific weight of 3.2-3.8 g / ccm, was slowly charged with hydrogen in a closable pressure vessel. The final pressure was 30 bar, the heat was removed by a water bath. After loading, the pressure vessel and its contents were cooled to -20 ° C. in a freezer. For the alloy mentioned, the equilibrium pressure at 0 ° C in the loaded state is approximately 100 mbar. This alloy can therefore be transferred without pressure and under pressure when deep-frozen. A slight overpressure should only keep other gases away.

The equilibrium pressures of alloy 5777 when loaded, i.e. at about 1.5% by weight H- in the alloy are the following:

20 40 70 100

bar 1 11 70

Even at 70 bar and a "bursting" storage there is no explosion because the hydrogen diffuses out of the hydride only slowly.

In order to keep the wall thickness of the container low in any case, a simple pressure and / or temperature-dependent safety valve can be provided.

The parts of a commercially available 200 ml spray can on deep-drawn steel were obtained from an Austrian producer. The vessel was lined with 3 layers of commercially available chemical-resistant plastic varnish. ₀

The cold pressure container, the parts of the spray can and the necessary tools were placed in a small glove box and the box was filled with hydrogen gas under slight pressure.

The pressure vessel was then opened and the hydride material was filled into the spray can up to approx. 5 mm below the upper edge. An approx. 7 mm thick layer of glass wool was pressed into the free space. The edge of the spray can lid was coated with a thin layer of two-component adhesive and pressed into the can. Finally the edge was carefully squeezed. After the adhesive had hardened, the spray can hydride cartridge was removed from the glovebox and checked for leaks by immersing it in a water bath. The cartridge made was tight.

The weight loss of the cartridge was then observed over 10 days; the weight remained constant within the range of the measurement accuracy.

Finally, the cartridge was discharged through the built-in valve and the amount of hydrogen released was checked volumetrically. The hydrogen content of the cartridge corresponded to a hydrogen concentration of 1.4% in the metal, which was to be expected on the basis of the equilibrium curves for the material.

Claims

PATENT CLAIMS

1. Recyclable disposable hydrogen cartridge, characterized in that it consists of a container in the manner of a spray can, gas cartouche, soda water cartridge or a lighter gas refill container which contains a hydrogen-binding material loaded with hydrogen.

2. Hydrogen cartridge according to claim 1, characterized gekenn¬ characterized in that it contains hydride-forming metal alloys, in particular a titanium alloy, or zeolites, ceramic materials ien, activated carbon or a hydrogen-binding plastic as a hydrogen-binding material.

3. A process for producing a hydrogen cartridge according to claim 1 or 2, characterized in that the hydrogen-binding material is loaded with hydrogen in an openable pressure vessel and is filled into the cartridge container at a suitably low temperature and elevated pressure, whereupon these are sealed.

4. A process for the reprocessing of the cartridges mentioned in claim 1 or 2 after the hydrogen has been released, characterized in that the material substantially freed from hydrogen is removed from the containers and used again in a process according to claim 3 becomes.

5. Use of the hydrogen cartridge according to claim 1 or 2 in combination with fuel cells or as a hydrogen source for small autogenous welding devices, catalytically working soldering irons or measuring or analysis devices.