RU194758U1 - CAPSULE FOR HYDROGEN GENERATOR BASED ON WATER OXIDATION OF A SOLID REAGENT - Google Patents

Abstract

The utility model relates to power equipment, namely to the design of capsules (cartridges) used in hydrogen generators for autonomous power sources on fuel cells, and can be used to create small power plants for stationary distributed energy. The capsule for a hydrogen generator includes a housing with an internal cavity containing a solid reagent for producing hydrogen, and provided with end caps made with the possibility of tight connection with the housing. The capsule is made with the possibility of supplying a liquid reagent inside the capsule and is equipped with a filter element that allows the passage of hydrogen and the retention of solid reaction products and water inside the capsule. In this case, the capsule body on the outside is made in the form of a truncated cone of a gas impermeable heat-conducting material. On the outside, the end cap of a larger case has an element for moving the capsule, and the end cap of a smaller diameter has openings for supplying liquid reagent and hydrogen, sealed on the outside with an airtight protective membrane made with the possibility of its partial destruction by the elements of the hydrogen generator reactor when placing the capsule inside a hydrogen generator reactor. The filter element is mounted on the end cap of a smaller diameter from its inner side. The capsule provides long-term storage of hydrogen in latent form, and when it is placed in the reactor, continuous continuous operation of the hydrogen generator in both manual and automatic mode for a predetermined time determined by the stock of capsules (reagent). 7 cp f-ly, 4 ill.

Description

The utility model relates to power equipment, namely, to the design of capsules (cartridges) used in hydrogen generators for self-contained power sources on fuel cells, and can be used to create small power plants for stationary distributed energy. In addition, the utility model can be used in the storage and transportation of hydrogen in latent form by various modes of transport at any distance. It is possible to use a utility model for the production of hydrogen "on site, on demand" (replacement of electrolyzers), the use of small-sized underwater vehicles and surface ships in power plants, as well as electric locomotives in mines and mines as part of traction power plants.

Today, one of the promising directions for the production of hydrogen is the hydrolysis of light metals, including aluminum, which is one of the most energy-intensive chemical elements. A method of using aluminum energy includes the step of recovering hydrogen from water using aluminum and the step of oxidizing the produced hydrogen in hydrogen-air fuel cells to produce electrical energy.

The prior art various structural solutions for cartridges for a hydrogen generator based on the chemical reaction between water and an aluminum composite.

In particular, a replaceable cartridge for a hydrogen gas generator reactor is known, which includes plates of activated aluminum mounted inside the cartridge and mounted between two disks (patent RU 2407701).

A known cartridge consisting of a container with water and a container filled with activated aluminum particles placed in a sealed enclosure (E. Shkolnikov. Aluminum-hydrogen current sources for portable electronic devices. Modern Electronics, No. 6, 2014; 2Wpower source based on air-hydrogen polymer electrolyte membrane fuel cells and water-aluminum hydrogen micro-generator. Journal of Power Sources, 185, (2008) 967-972; patents RU 72360, RU 87573). The case is sealed with a film that is removed before using the cartridge. In this case, both parts are separated by a membrane element having a predetermined porous structure. Water-retaining separators are located on the hydrogen exit path to retain condensate carried out from the cartridge along with hydrogen.

However, known cartridges having a limited supply of reagent are used in portable devices with manual recharging and do not solve the problem of intense heat generation during the course of the reaction. In this regard, these devices allow only rare use, for example, for recharging batteries.

Closest to the proposed solution is the design of the cartridge described in international application WO 2017135900. The cartridge includes a cylindrical body with a solid reagent, a first cover located at one end of the body, and a second cover located at the opposite end of the body, a liquid distributor in the form of a tube with a plurality of holes located inside the housing along its central axis and a barbed fitting located in the first cover, while the liquid distributor is configured to connect connection with the fitting with the formation of a channel for fluid flow when the cartridge is located inside the reactor vessel. The cartridge housing is made of a hydrophobic semi-permeable material that allows gas to pass through the material and at the same time prevents the passage of liquid or solid substances through it.

This cartridge operates as follows. Hydrogen formed after water is injected into the cartridge exits through a low-heat-conducting cylindrical permeable surface, including filter material, into the reactor cavity. The hydrogen pressure in the cartridge and in the reactor after the production of the reagent is equalized, and almost all the heat of reaction generated remains in the cartridge. This implies the operation of the reactor with a rare periodicity and completely eliminates its continuous long-term operation with automatic reloading of the cartridge, since hydrogen is not removed from the reactor before the end of the reaction, as well as effective cooling of a strongly heated cartridge due to the thermal effect of the reaction. In addition, since the cylindrical surface of the cartridge is permeable to wet gas, the solid reagent cartridge must be stored in a dry box or sealed in a moisture-proof bag or container before use, which also implies only manual operation with a rare frequency. Placing in each cartridge its own liquid distributor in the form of a tube with many holes increases the inefficient mass and increases the cost of each cartridge.

The technical problem that the utility model addresses is the development of a capsule design for a hydrogen generator filled with a solid reagent based on aluminum or other inorganic energy carriers similar in principle to the operation, providing the maximum possible specific mass characteristics of the latent hydrogen content while ensuring the possibility of its long-term storage without special environmental protection measures. The capsule design should provide the possibility of its manual or automatic recharging into the reactor with simultaneous opening to ensure the removal of hydrogen and water supply and effective heat removal from the capsule during the course of the reaction.

The technical result is the development of a capsule for a solid reagent based on aluminum or other inorganic energy carriers that are close in principle, capable of providing long-term storage of hydrogen in latent form, and when placed in a reactor, continuous continuous operation of a hydrogen generator in both manual and automatic mode for a given time, determined by the stock of capsules (reagent).

The technical result is achieved by developing the design of the capsule, comprising a housing with an internal cavity containing a solid reagent for producing hydrogen, and equipped with end caps made with the possibility of tight connection with the housing, while the capsule is configured to supply a liquid reagent to the internal cavity and is equipped with a filter an element providing the transmission of hydrogen and the retention of solid reaction products and water inside the capsule. According to the proposed technical solution, the capsule body on the outside is made in the form of a truncated cone of gas impermeable heat-conducting material, while on the outside, the end cap of the larger case has an element for moving the capsule, and the end cap of a smaller diameter has openings for supplying liquid reagent to the capsule and hydrogen release, externally sealed with a protective membrane impermeable to ambient air, made with the possibility of its partial destruction by ntami reactor the hydrogen generator of the capsule when placed in the reactor of the hydrogen generator, wherein the filter element is fixed to the end cover of smaller diameter on its inner side.

The housing can be made of aluminum alloy with a side wall thickness of 0.1-0.9 mm.

The internal cavity of the capsule may be cylindrical and located coaxially with the conical surface of the housing.

The protective membrane can be made of aluminum foil with a thickness of 0.05-0.1 mm

The capsule contains sealing elements for sealing the area of supply of the liquid reagent into the internal cavity of the capsule.

The element for moving the capsule can be made in the form of a protruding flange or groove.

The capsule may have a volume of 15-60 ml.

As a solid reagent, dispersed and / or activated aluminum can be used.

The filter element is mounted on the end cap of the capsule to prevent its breakthrough or bypassing with solid reaction products.

After placing and fixing the capsule with the reagent in the reactor and injecting water into it, hydrogen evolution begins, which must fall into the receiving buffer capacity of the hydrogen generator for a limited time. The proposed design of the capsule provides the removal of the generated heat of the reaction due to thermal conductivity through the walls of the capsule and the reactor and convective entrainment of heat with a cooling agent. At the same time, the temperature of the reacting mixture in the capsule is kept sufficiently high, which ensures the release of all hydrogen in a limited time, and at the same time, overheating of the capsule is not allowed, which can lead to loss of properties of the filter material and sealing elements of the capsule and reactor, and, as a result ejection of solid sediment from the capsule and clogging of the hydrogen communications of the hydrogen generator. After the production of the reagent, the thin-walled capsule is removed with little effort from the reactor, despite the fact that the pressure developed in it would inevitably lead to its plastic deformation.

The proposed capsule design allows continuous use of a hydrogen generator to provide hydrogen-air (oxygen) fuel cells with electric power up to several kilowatts. Capsules divide the fuel into portions, while the continuity of use is achieved by automatically feeding (and removing) the capsules into the reactor, which provides the reaction conditions inside the capsule, as well as continuous effective removal of the reaction heat. Thus, it becomes possible to create relatively compact autonomous energy sources characterized by increased power with a relatively small volume of the capsule.

The utility model is illustrated by drawings and graphs, where in FIG. 1 shows an exemplary embodiment of a capsule, a longitudinal section, in FIG. 2 - an example of the execution of the end cap of the capsule with a filter element, FIG. 3 - a capsule placed in a hydrogen reactor, a longitudinal section, in FIG. 4 - graphs of the dependence of hydrogen pressure in the buffer tank on time at various initial temperatures of the capsule.

The positions in the drawings indicate: 1 - capsule body; 2 - the internal cavity of the capsule; 3 - end cap of a larger diameter; 4 - end cap of a smaller diameter; 5 - holes for the release of hydrogen from the capsule; 6 - hole for supplying a liquid reagent to the capsule; 7 - a protective membrane, 8 - a needle of a reactor of a hydrogen generator; 9 - filter element; 10 - a sealing ring, 11 - sealing tabs; 12 - element for moving the capsule; 13 - hydrogen generator reactor; 14 - reactor cooling system; 15 - union nut; 16 - ejector; 17 - output for hydrogen; 18 - the cover of the reactor vessel.

The capsule is made in the form of a thin-walled sleeve made of a gas-impervious heat-conducting material (for example, an aluminum alloy), which is a housing 1, the outer surface of which is made in the form of a truncated cone. The housing 1 is provided with an internal cavity 2, a coaxial cone filled with a solid reagent and made, for example, in a cylindrical shape. In this case, the thickness of the side wall of the housing can be from 0.1 to 0.9 mm. From opposite ends, the housing is equipped with end caps 3 and 4, of larger and smaller diameters, respectively. The cap of smaller diameter 4 has openings 5 for discharging hydrogen from the capsule into the pressurized zone of the reactor connected to the communications of the hydrogen generator, and an opening 6 for supplying liquid reagent under pressure into the internal cavity of the capsule, for example, by means of a needle of a hydrogen generator reactor. In particular, the hole 6 can be located in the Central part of the cover 4, the hole 5 is symmetrical about the Central axis of the capsule. On the outside of the lid, the openings 5, 6 are sealed with a protective membrane 7 impervious to ambient air, which protects the contact of the energy carrier in the capsule with the external environment. The membrane 7 can be made of aluminum foil with a thickness of 0.05-0.1 mm and hermetically connected to the cover 4, for example, using epoxy glue and / or rolling. When the capsule is fed into the reactor, the membrane 7 is partially destroyed by the elements of the reactor of the hydrogen generator (for example, needle 8, Fig. 4) to ensure the release of hydrogen from the capsule.

A filter element 9 is mounted to the end cap 4 of a smaller diameter on the inside of the capsule, which is configured to transmit hydrogen and delay solid reaction products and water (droplet liquid). The filter material from which the filter element is made must have sufficient strength at elevated temperature (about 100 ° C) during the course of the reaction so that it cannot break through or bypass solid reaction products (protect against the release of solid powders). The filter element 9 can be attached to the end cap 4, for example, by means of adhesive bonding (for example, using epoxy glue) along the outer perimeter and around the perimeter of the central hole 6. For reliable fastening, the perimeters of the filter element 9 can be rolled as an option. In the filter element 9, a central hole can be made, which is located coaxially with the hole 6 and made smaller in diameter, for the passage of the needle 8. As a material for the filter element, felt, for example, 2-3 mm thick, can be used. To prevent the accumulation of water in the filter material, it can be hydrophobized. In FIG. 2 shows an example of an end cap 4 with a filter element 9. The cap 4 is provided with sealing elements (O-ring 10, tabs 11) to seal the needle installation area.

In a preferred embodiment, the parts of the lid 4 are made of the same material as the capsule body. Caps 3 and 4 can be connected to the capsule body, for example, by rolling, with preliminary coating of the compound with epoxy glue or in any other way, ensuring the tightness of the case.

The end cap 3 of a larger diameter is provided with an element 12 for moving the capsule located on the outside of the cap and adapted to engage it by the reactor recharge mechanism (shutter). Element 12 for moving the capsule may be integral with the housing. Element 12 may be a fungus or protruding rim (for example, as in the cartridge 7.62 × 54R) or a groove (as in the cartridge 7.62 × 51). The rim can be an annular protrusion or protrusion and a groove at the cover 3 (the base of the sleeve), and can be performed by rolling.

As a solid reagent filling the internal cavity 2 of the capsule, dispersed or activated aluminum with particle sizes in the range of 0.005-0.5 mm can be used. As a solid reagent can also be used the reagent described in patents RU 87573, RU 72360.

The size of the capsule used for the operation of the hydrogen generator depends on the power of a particular hydrogen generator and can be from 20 to 40 mm in diameter and from 50 to 150 mm in length. The volume of the capsule can be from 15 to 60 ml.

The proposed capsule geometry is optimized for production on automatic lines similar to the production of small-caliber artillery ammunition shells or small arms.

The utility model works as follows.

In the operating cycle of the hydrogen generator in automatic operation, the capsule with the solid reagent is sent by the shutter of the capsule recharging mechanism (for example, by connecting the ejector 16 mounted on the shutter with the element 12 for moving the capsule) into the internal cavity of the reactor vessel 13 of the hydrogen generator until the outer surface of the capsule comes into contact with the inner conical surface of the wall of the reactor vessel. In this case, the hydrogen cavity is sealed with sealing elements of the reactor (for example, a sealing cuff). At the same time, the elements of the reactor, for example, a fixed needle 8 fixed in the reactor, destroy the protective membrane 7 on the end cap 4 of the capsule. In FIG. 3 shows an example of placement of a capsule in a reactor vessel with a needle. The needle 8 passes through the Central hole 6 in the cover and the filter element 9 and penetrates into the reagent located in the capsule. Then, with the capsule fully held by the closure, water enters through the needle 8 into the internal cavity 2 of the capsule. As a result of the chemical reaction of the reagent with water, hydrogen is formed, which passes through the filter element 9, then through the destroyed membrane 7 and leaves the capsule. The heat generated as a result of the reaction is removed to the outside through the capsule body 1, which is in contact with the cooling system of the reactor 14 (for example, radiators mounted on the outer surface of the reactor, or a water jacket covering the reactor body from the outside). After completion of the reaction, the ejector 16, mounted on the shutter, interacts with the capsule displacement element 12 (edge / groove), engages with it, and pulls the capsule out of the reactor, freeing up space for the next capsule.

In this case, the capsule can also be manually inserted into the reactor cavity. When manually installing the capsule, it is fixed in the reactor vessel, for example, by means of a union nut 15 (Fig. 3). When automatically installed on the same thread, another flare nut may have, for example, a flange for attaching the shutter of the capsule recharge mechanism.

Capsules for the hydrogen generator were made of aluminum alloy D16. The total length of the capsule with the element for movement (“fungus”) was 120 mm, the effective length minus both caps was about 100 mm, the inner diameter of the capsule was 23 mm, and the cone angle was 1 ° with a tolerance of plus / minus 5 minutes. The wall thickness of the capsule from the side of the smaller diameter was 0.3 mm, the largest wall thickness was 0.9 mm. The useful volume of the capsule was about 40 cm ³ . As a filter element, an element whose construction is depicted in FIG. 2, the filter material is felt 2.5 mm thick. As a membrane, aluminum foil 0.05 mm thick was used.

A series of experiments were carried out to test the regimes for the process of generating hydrogen in capsules with the indicated parameters, as well as to study the effect of the initial temperature of the capsule on the efficiency of hydrogen generation. The initial temperature of the reaction mixture corresponded to the initial temperature of the reactor. In turn, the reactor was heated (or cooled) to the required temperature using a thermostat. About 3 g of dispersed aluminum with a particle diameter of 0.1-0.5 mm was loaded into the capsule. One batch of aluminum was used, activated with a 5% mixture of tin and bismuth. An end cap 4 of smaller diameter with a filter element 9 was fixed in the capsule body, after which the capsule was manually inserted into the reactor 13 and fixed with a union nut 15, as shown in FIG. 3. Water was supplied through a perforated needle 8. Hydrogen was collected in a special buffer tank, the volume of which together with the communications was about 1.5 liters. The hydrogen yield was controlled by the pressure of hydrogen in the buffer tank.

In FIG. Figure 4 shows an example of the results obtained at three initial temperatures in the form of cumulative curves of the increase in hydrogen pressure over time. The curves are aligned along the time axis to the origin corresponding to the time of the first water injection. As follows from the graphs, despite the fact that the initial temperatures differed significantly, in all three experiments the hydrogen yield was close to 100%. It can be seen that at 60 ° C the pressure rises from the first seconds, i.e. induction time is close to zero. Naturally, the induction time increases with decreasing initial temperature. In this case, the integral average rate turned out to be the highest at room initial temperature, and therefore such an important parameter as the total reaction time was the shortest at room temperature. The total time at 7.2 ° C and 60 ° C turned out to be almost the same, which is a favorable fact for solving the problem of cold start of a hydrogen generator.

In all three cases, the technical result at the level of elementary acts of the process of generating hydrogen in the capsule was achieved. Everything went under normal conditions, and almost all of the hydrogen was released in a limited time. The capsules also fully justified their purpose: the reacted alumina remained in the capsule, the filter material did not visually change its properties, the capsules were easily removed from the reactor and did not undergo any deformation. The prepared capsules were stored in sealed form for 4 months, after which the reagent completely retained its property.

Thus, the proposed solution makes it possible to create one of the main components of an automatic hydrogen generator - a capsule for a solid reagent based on aluminum or other inorganic energy carriers close in principle, capable of providing long-term storage of hydrogen in latent form, as well as being placed in a reactor hydrogen in both manual and automatic mode for a given time, determined by the stock of capsules. In addition, the proposed solution provides quick refueling of the hydrogen generator with reagents by automatically changing the capsules, which are easily refilled and removed from the reactor vessel. The execution of the body and capsules of the aluminum alloy creates an additional advantage in the disposal of capsules for the regeneration of aluminum reagent (facilitates its secondary use), because The spent capsule contains mainly aluminum and its oxides. In addition, the manufacture of capsules made of aluminum alloy allows you to achieve its low weight and high corrosion resistance. Thin capsule walls increase the mass fraction of the active aluminum composition in the gross mass of the stored reagent. The capsule containing the solid reagent is completely sealed during storage and transportation, and can be stored for a long time.

Claims (8)

1. A capsule for a hydrogen generator, comprising a housing with an internal cavity containing a solid reagent for producing hydrogen, and equipped with end caps made with the possibility of tight connection with the housing, while the capsule is configured to supply a liquid reagent to the internal cavity and is equipped with a filter element, ensuring the transmission of hydrogen and the retention of solid reaction products and water inside the capsule, characterized in that the housing on the outside is made in the form of a truncated cone of impermeable gas for the heat-conducting material, while on the outside the end cover of a larger case has an element for moving the capsule, and the end cover of a smaller diameter has openings for supplying liquid reagent to the capsule and the release of hydrogen, sealed on the outside with an airtight protective membrane, made with the possibility of its partial destruction by the elements of the reactor of the hydrogen generator when placing the capsule inside the reactor of the hydrogen generator, while the filter element mounted on the end cap of a smaller diameter on its inner side. 2. The capsule according to claim 1, characterized in that the housing is made of aluminum alloy with a side wall thickness of 0.1-0.9 mm. 3. The capsule according to claim 1, characterized in that its internal cavity is cylindrical and is located coaxially with the conical surface of the housing. 4. The capsule according to claim 1, characterized in that the protective membrane is made of aluminum foil with a thickness of 0.05-0.1 mm 5. The capsule according to claim 1, characterized in that it contains sealing elements for sealing the supply region of the liquid reagent into the internal cavity of the capsule. 6. The capsule according to claim 1, characterized in that the element for moving the capsule is made in the form of a protruding flange or groove. 7. The capsule according to claim 1, characterized in that it is made in a volume of 15-60 ml. 8. The capsule according to claim 1, characterized in that dispersed and / or activated aluminum is used as a solid reagent.

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