WO2022216164A1

WO2022216164A1 - A device for production of hydrogen and a method for production of hydrogen using the said device

Info

Publication number: WO2022216164A1
Application number: PCT/PL2022/050008
Authority: WO
Inventors: Wiesław NOWAKOWSKI; Jakub NOWAKOWSKI
Original assignee: Nowakowski Wieslaw; Nowakowski Jakub
Priority date: 2021-04-08
Filing date: 2022-02-23
Publication date: 2022-10-13
Also published as: PL437523A1; EP4320072A1; JP2024513360A

Abstract

The subject of the invention is a device for hydrogen generation containing a body (1) with a gas outlet (2a), where the said body (1) contains at least one upper chamber (3) with a liquid reagent (4) and at least one reaction chamber (5a,5b) containing a solid reagent in form of fragmented aluminium material (7) and a catalyst (8) in form of an alkaline material hydroxide. The said device is characteristic in that in a passive state it has at least one continuous aluminium layer (6) tightly separating the upper chamber (3) from the reaction chamber (5a, 5b), while the device in its active state has a permanent perforation (13) in the aluminium layer (6). The subject of the invention also includes the method for hydrogen generation by such device.

Description

DESCRIPTION

Title of the Invention

A DEVICE FOR PRODUCTION OF HYDROGEN AND A METHOD FOR PRODUCTION OF

HYDROGEN USING THE SAID DEVICE Technical Field

[0001] The present invention relates to a device for production of hydrogen and a method for production of hydrogen using the said device. Apart from hydrogen, the said device also generates heat energy. Following a one-time activation, the device and the method executed with the use of the said device do not require supply of energy from external sources, and in particular, electrical, mechanical or heat power. The said device can be portable, of a type of a so-called hydrogen and heat cartridge, and used e.g., to support combustion of hydrocarbons.

Background Art

[0002] Various designs of devices for production of hydrogen and a method for production of hydrogen using devices of this type are known. In those devices, sodium hydroxide is mixed with water and fragmented aluminium to initiate reactions emitting heat and hydrogen. Those substrates are combined using various devices, e.g., presented in the following patent descriptions US7326263B2, CA2720533A1, CN1162320C,

US2004115125A1. Devices presented in those descriptions require a continuous external control over substrate supply to generate hydrogen. The solutions closest to the device disclosed in this patent description verified in the current state of the art are solutions disclosed in patent descriptions JP4719838B2 and W02004092548A2.

[0003] In the Japanese patent description JP4719838B2, a chamber device consisting of a top chamber containing a water solution of sodium hydroxide and a bottom chamber containing fragmented aluminium. A partition separating those two chambers also has a form of a flat chamber, through which hydrogen is transported outside. In this solution, the chamber with sodium hydroxide and the chamber containing fragmented aluminium are joined through outflow control measures, such as a solenoid valve, controlled to open and close the flow of the liquid reagent. The reaction control requires control of that valve, to supply the required quantity of the reagent. Aluminium can be post-consumer, and can include fragments of polymer films.

[0004] In the patent description W02004092548A2, a generator of heat and gaseous hydrogen contains a first chamber with a liquid reagent (sodium hydroxide solution) and a second chamber containing a reducing substance (metallic aluminium), to which the liquid reagent from the first chamber is dosed to initiate exothermic redox reactions resulting in generation of gaseous hydrogen. The top and the bottom chambers are connected by a pipe supplying the mixture, controlled by a valve controlling the mixture flow. The valve for supplying the liquid reagent is opened to feed the aqueous sodium hydroxide solution from the top to the bottom chamber to initiate the reaction generating heat and hydrogen. The heat and hydrogen generator is equipped with visual indicators, automatic emergency valves, manually controlled valves controlling feeding of the mix and relief valves, for complete external monitoring and control of the redox reaction occurring in the bottom chamber of the device. The device additionally contains automatic safety valves to release pressure from the first and the second chamber.

Summary of Invention

Technical Problem

[0005] Technical solutions presented in patent descriptions JP4719838B2 and W02004092548A2 require technical control measures, including valves controlling dosing of the liquid reagent. In those two devices, the liquid reagent is fed from one outlet, while hydrogen is emitted from another outlet duct. The devices specified in those patent descriptions are not automatic, and require monitoring and control during hydrogen generation. Therefore, a possibility of the conscious monitoring by unspecialised users is very limited. Furthermore, those solutions do not disclose a method for purging hydrogen from steam, intensively generated due to heat emitted during the occurring exothermic reactions. The system for quantitative supply of reaction ingredients through evaporation of water and concentration of solid ingredients of those reactions. [0006] The main aim of this invention was to develop a simple design of a device for hydrogen generation, that can be used by a so-called unknowledgeable user (the mass shares of reagents and a way of their reactions are predetermined in a factory, during the device manufacturing). Solution to Problem

[0007] The subject of the invention is a device for production of hydrogen, containing a body with a gas outlet, and the said body contains at least one upper chamber with a liquid reagent and at least one reaction chamber containing a solid reagent in a form of fragmented aluminium material and a catalyst in form of an alkaline metal hydroxide. The said device is characteristic in that in a passive state it has at least one continuous aluminium layer tightly separating the upper chamber from the reaction chamber, while the device in its active state has a permanent perforation in the aluminium layer.

[0008] Preferably, water is the liquid reagent in the upper chamber, while the reaction chamber contains substrates in form of post-consumer fragmented aluminium material and sodium hydroxide.

[0009] It is also advantageous when at least one reaction chamber or the upper chamber contains at least one porous layer, permeable to liquids and gases, made of material not reacting with sodium hydroxide, preferably of copper or nickel.

[0010] Preferably, the device contains two reaction chambers separated from each other with a continuous aluminium layer.

[0011] Preferably, at least one reaction chamber contains at least one aluminium container containing water.

[0012] Optionally, at least one reaction chamber contains additionally at least one aluminium capsule containing sodium hydroxide and/or metallic sodium. [0013] Preferably, walls of aluminium containers, aluminium capsules and/or continuous aluminium layers have different thickness.

[0014] Optionally, fragmented aluminium material is made of particles of different sizes. [0015] In the preferable option of the device, the gas outlet is connected with the gas duct with the container with water, which contains an outlet of the purified gas and a trap, where the trap is connected through a duct with an inlet additionally included in the device body. [0016] It is advantageous when the water container also includes a filling opening tightly closed with a cover.

[0017] The subject of the invention also concerns a method for hydrogen generation in which: a device according to any of the specified options of the device is provided, and then the continuous aluminium layer separating tightly the upper chamber with liquid reagent from the reaction chamber is perforated. Preferably, the layer is perforated with a sharp spike.

Advantageous Effects of Invention

[0018] Preferable effects of the device and the method according to the invention include advantages such as that the developed device is portable, completely safe in its uninitiated (inactive) state, and its activation is technically simple (perforation of the bottom of the chamber containing the aqueous reagent). Following the activation, the device does not require supply of energy from external sources, and in particular, electrical, mechanical or heat power. The fragmented aluminium material can be post-consumer (so-called recycled material). The variable size of the fragmented aluminium material particles, determining the developed surface being in contact with the aqueous solution of the alkaline metal hydroxide, as well as an option for gradual automatic increase in the reagents share by additional reaction chambers and aluminium containers with waters and capsules with sodium hydroxide and/or metallic sodium allow for planning the quantity of hydrogen and heat emitted in consequence of occurring reactions. Furthermore, the device ensures an effective way for separating gaseous hydrogen from steam, which, in turn, following its condensation ensures a return of required share of the regent (water) in a balance of occurring chemical reactions. It should also be emphasised that the reaction of water, sodium hydroxide and aluminium generates sodium aluminates completely harmless to the environment. For many years, hydrous aluminates have been used at sewage treatment plants as an agent improving treatment processes. Following dehydration, it can also be supplied to aluminium mills, where it is used as a semi-product in a process for production of pure aluminium (the Bayer process). It can also be used in soap production. Furthermore, it has many other applications, so in consequence, no chemical compounds impacting the environment are generated.

Brief Description of Drawings

[0019] Examples of the invention embodiment were illustrated in the drawing in which individual figures present:

Fig. 1 - the device with one reaction chamber, containing sodium hydroxide and aluminium containers with water and capsules with sodium hydroxide and/or metallic sodium;

Fig. 2 - a spike for activation and the device with two reaction chambers, containing sodium hydroxide and aluminium containers with water and capsules with sodium hydroxide and/or metallic sodium; Fig. 3 - shows the top view of a body of the device in figs. 1 and 2;

Fig. 4 - the device containing only the outlet (without an inlet) and with two reaction chambers, where the upper chamber contains only sodium hydroxide, and the bottom contains fragmented aluminium material;

Fig. 5 - a container with water and a trap, to separate hydrogen from steam (so- called bubbler) with ducts;

Fig. 6 - the device with the connected bubbler, shown in fig. 5;

Fig. 7 - a diagram of crimping a connection between a peripherally profiled wall of the body and the aluminium layer (partition).

Description of Embodiments [0020] In various versions of the invention embodiment, the device for hydrogen generation contains a body 1 made of tinned steel. By coating the metal sheet with a thin layer of tin, the device (so-called hydrogen cartridge) is protected against corrosion. A preferable modification of the body 1 is embossing of its bottom la and the upper cover lb in such way that the embossing on the bottom la penetrates inside, and the embossing on the cover (lb) penetrates outside the device. The device body 1 can contain additional embossing, reinforcements or flanges, to increase its resistance to high gas pressure, and to ensure its easy stable fixing during transport, storage, use and recycling of this device. [0021] In one example of embodiment, bedsides the gas inlet 2a the body can contain an additional inlet 2b for water from condensed steam. The upper chamber 3 with the liquid reagent 4 in form of water is separated from the adjoining reaction chamber 5a with an aluminium layer 6 separating tightly those two chambers 3, 5a. In one example of the invention embodiment, the body 1 contains one upper chamber 3 with the liquid reagent 4 (water) and two reaction chambers 5a, 5b containing solid reagents in form of the fragmented aluminium material 7 and the catalyst 8 (sodium hydroxide). Reaction chambers 5a, 5b were tightly separated from each other with a continuous aluminium layer 9. In another option of an example of embodiment, the device contained just one reaction chamber 5a. In preferable examples of the invention embodiment, the use of sodium hydroxide, widely available in the market was assumed, as the catalyst 8 of the reaction, mainly intending to ensure the maximum level of safety for a non-professional user and aiming to achieve the smallest possible weight and volume of the hydrogen cartridge (device).

[0022] In one example of embodiment, the reaction chambers 5a, 5b contain the post- consumer fragmented aluminium material 7 of various degree of fragmentation, sodium hydroxide 8, aluminium containers 10 with water (aluminium cans with water) and aluminium capsules 11 with sodium hydroxide and/or metallic sodium. In this patent description, especially in the claims, 'aluminium' or 'aluminium material' should be understood as any item or material consisting of pure aluminium (Al), alloys of that element, or other material compositions containing that element.

[0023] In other possible example of embodiment, the bottom reaction chamber 5b contains fragmented aluminium 7, while the upper reaction chamber 5a contained solely sodium hydroxide 8, which on reaction with water dissolved the aluminium layer 9 separating reaction chambers 5a, 5b. [0024] Obviously, many possible examples of the device embodiment are possible, depending on a number of chambers and qualitative and quantitative composition of reagents present in those chambers in their free form or in aluminium containers 10 and/or capsules 11.

[0025] The gas outlet 2a in the cover lb can be used for activation of the device by placing the pointed spike 12 in it to perforate IB the aluminium layer 6. The gas outlet 2a can have an inner 2a-l or outer 2a-2 thread for connection of duct 14a to remove hydrogen. Other commonly used connections with ducts 14a, 15b ensuring tightness of the device can also be used. To ensure tightness and prevent outflow of the liquid reagent 4 (water), in the factory design the gas outlet 2a is secured with a cover 16 in form of a plug, a cap or a heat sealed protective layer (a condition before the device is activated).

[0026] When the cover 16 is removed and the device is activated (the perforation 13 is made in the aluminium layer 6), the first reaction occurring is hydration of sodium hydroxide. It is an exothermic reaction increasing the solution temperature:

2Na0H+2H₂0 = 2NaOHaq + heat (1)

[0027] The aqueous sodium hydroxide reacts exothermically with aluminium, causing further increase in the solution temperature and, depending on amount of water in the device, sodium aluminates are formed. Depending on quantities of reaction substrates, with the excess of water (hhO) the reaction occurs in the following known way:

2AI+2NaOH+10H2O = 2Na[AI(OH)e] + 5H₂† + heat (2)

However, when the stoichiometric quantity of sodium hydroxide (NaOH) is used, the reaction occurs in the following known way:

2AI+2Na0H+6H₂0=2Na[AI(0H)4]+3H₂ + heat (3)

In turn, when the excess of sodium hydroxide is used, the following reaction will occur:

2AI+6Na0H+6H₂0 = 2Na3[AI(OH)e] + 3H₂† + heat (4)

[0028] In consequence of the conducted reactions (2, 3, and 4), atomic hydrogen is generated. The life span of atomic hydrogen amounts to ca. 0.3 to 0.5 of a second. During that time, hydrogen forms a molecule undergoing recombination and emitting significant quantities of heat:

H + H = H2 + heat (5) ln general, atomic hydrogen recombination occurs on inner walls of the body 1. To effectively use the heat generated during the reaction, it is preferable to ensure hydrogen recombination in a solution, and not on the upper cover lb of the body 1. Therefore, below the aluminium layer 6 separating the upper chamber 3 from the reaction chamber 5a there is the porous layer 17 on the entire cross-section of the device, of a material not reacting with sodium hydroxide, which has a very developed surface, and at the same time has a good permeability to hydrogen. Atomic hydrogen, being the lightest gas, moves upwards and encountering the porous layer 17 on its way recombines, transforming into a molecular form, emitting the recombination heat into the surrounding solution. In the examples of embodiment, layers 17 of copper, nickel, tungsten, vanadium or titanium are used, which do not react with sodium hydroxide. In other, less preferable option, the layer 17 of polymer foam resistant to agents of the occurring reactions can be used.

[0029] For the majority of hydrogen applications, it is preferable to obtain hydrogen with the smallest possible admixture of water. Therefore, in the preferable example of embodiment, an additional tank (18) was used, made of plastic and containing water. Hydrogen and steam flowing through the duct (14a) of the device flow through water in the tank 18, and in consequence the purified hydrogen is discharged to the target location through the outlet 19, while the cooled and condensed water flows through the trap 20 back to the upper chamber 3. When the water level in the tank 18 increases, its excess is returned gravitationally through the trap 20 to the upper chamber 3, and this is a condition for a complete reaction of all reaction substrates. The tank 18 with the installed trap 20 that can be called a bubbler, can represent additional equipment of the device and can be used many times in other devices of this type. Obviously, the trap 20 can have various shapes, including bent several times, used to achieve the same effect.

[0030] Small particles of aluminium material 7, due to their highly developed surface calculated in relation to their weight, quickly initiate the reaction and dissolve quickly. This results in a rapid increase in the solution temperature, leading to a fast course of chemical reactions at the beginning. However, when the required reaction temperature is reached, it is preferable to maintain it on a relatively stable level To ensure a long-term and stable process for hydrogen and heat generation, it is preferable to use aluminium of a varying degree of fragmentation, to ensure less rapid but longer lasting process of aluminium dissolution, which ensures longer and stable generation of hydrogen and heat. When aluminium containers 10 with water and/or capsules 11 with sodium hydroxide and/or metallic sodium are used, it is also preferable to vary thickness of walls of those containers 10 and/or capsules 11, so following their chemical dissolution successive substrates are supplied at various time intervals; thus limiting excessive heat emission on one hand, and extending the process of hydrogen generation on the other. The differentiation of wall thickness in the aluminium containers 10 with water and/or capsules 11 with sodium hydroxide and/or metallic sodium allows to plan preferably the reaction speed, and thus the quantity of generated heat and hydrogen per unit of time. For better control of the reaction, the appropriate thickness of the aluminium layer 9 can also be selected. Eventually, depending on the quantity of substrates used, the same quantity of hydrogen and the same quantity of heat will be generated, but spread over time in a way preferable for the user. Once initiated, the reactions continue spontaneously until all substrates react in accordance with reactions (2, 3 and 4) specified above.

[0031] In general, the quantity of solid sodium hydroxide must be selected to ensure that following its hydration its concentration in individual chambers is maintained at a level required to react with a successive aluminium layer 9 located below and with aluminium walls of containers 10 and capsules 11. The conducted tests show that the use of the sodium hydroxide solution of a correct concentration destroys the passivation layer (AI2O3) that can form in the aluminium surface layer.

[0032] The disclosed information enables a complete embodiment of the invention specified in the claims. However, the device effectiveness layer will depend on the quantitative and qualitative composition of reagents in individual chambers. That composition is determined at the factory, and after the device activation the user cannot interfere with the factory designed process of the hydrogen and heat emission.

[0033] In the examples of embodiment, the body 1 of the device is made as other known containers, e.g., aluminium cans for drinks or steel cans for food or paints. First, a fragment is cut out of a metal sheet, which is then stamped to form a cylinder with a characteristic embossing on its bottom la. Both the cover lb of the body 1 and the transverse layers 6, 9 are joined by crimping together with the appropriately profiled wall of the initially formed cylindrical section of the body 1. Before individual transverse layers 6, 9 are crimped together with peripherally profiled fragments of the side wall of the body 1, reagents are dosed into individual chambers 5b, 5a, 3 according to developed formulations of the reagents, depending on the size and the intended use of the device. The porous layer 17 is also joined with the appropriately peripherally profiled wall of the body 1 by crimping them together (similarly as in aluminium covers of drink cans). The areas where parts are joined by crimping can be sealed with a layer of aluminium coating, similarly as in aluminium cans for sparkling drinks. Alternately, in other ways of embodiment, it is also possible to heat seal the cover lb and the transverse layers 6, 9, 17 with the cylindrical side wall of the body 1.

Claims

1. The device for hydrogen generation containing a body (1) with a gas outlet (2a), where the said body (1) contains at least one upper chamber (3) with a liquid reagent (4) and at least one reaction chamber (5a, 5b) containing a solid reagent in form of fragmented aluminium material (7) and a catalyst (8) in form of alkaline metal hydroxide, characterised in that the device in a passive state contains at least one continuous aluminium layer (6) separating tightly the upper chamber (3) from the reaction chamber (5a, 5b), while the device in its active state contains permanent perforation (13) in the aluminium layer (6).

2. The device according to claim 1 characterised in that in the upper chamber (3) the liquid reagent (4) is water, while the reaction chamber (5a, 5b) contains substrates in form of post-consumer fragmented aluminium material (7) and sodium hydroxide (8).

3. The device according to any of claims 1 to 2 characterised in that at least one reaction chamber (5a, 5b) or the upper chamber (3) contains at least one porous layer (17) permeable to liquids and gases, made of material not reacting with sodium hydroxide, preferably of copper or nickel.

4. The device according to any of claims 1 to 3 characterised in that it contains two reaction chambers (5a, 5b) separated by a continuous aluminium layer (9).

5. The device according to any of claims 1 to 4 characterised in that at least one reaction chamber (5a, 5b) contains at least one aluminium container (10) containing water.

6. The device according to any of claims 1 to 5 characterised in that at least one reaction chamber (5a, 5b) contains at least one aluminium capsule (11) containing sodium hydroxide and/or metallic sodium.

7. The device according to any of claims 4 to 6 characterised in that walls of aluminium containers (10), aluminium capsules (11) and/or continuous aluminium layers (9) are of different thickness.

8. The device according to any of claims 1 to 7 characterised in that the fragmented aluminium material (7) is made of particles of different sizes.

9. The device according to any of claims 1 to 8 characterised in that the body (1) contains additionally an inlet (2b).

10. The device according to claim 9 characterised in that it is additionally connected with ducts (14a, 14b) with a tank (18) with water that contains an outlet (19) of purified hydrogen and a trap (20), where the trap (20) is connected with ducts (15a, 15b) with the inlet (2b) on the body (1).

11. The device according to claim 10 characterised in that the tank (18) has a filling opening (20a) tightly closed with a cover (20b).

12. The method for hydrogen generation, in which: a device according to any of claims 1 to 11 is provided, and then the perforation (13) is made in the aluminium layer (6).

13. The method for hydrogen generation according to claim 12 characterised in that the perforation (13) is made with a sharp spike (12).