RU2735285C1 - Compressed hydrogen producing method and device for implementation thereof - Google Patents

Abstract

FIELD: chemistry; power engineering.

SUBSTANCE: invention relates to hydrogen power engineering, namely to technology and equipment for production of hydrogen and filling of vessels to required pressure for use as autonomous mobile plants for generation of hydrogen under high pressure with its subsequent filling into cylinders, intended for supply of fuel elements, providing operation of unmanned aerial vehicles, telecommunication equipment, computer equipment and other independent objects of power consumption. Method of producing compressed hydrogen involves chemical reaction of a hydrogen-generating material with a liquid reagent in reactor 1 with hydrogen evolution and filling it with filled balloon 12, wherein hydrogen generating material is magnesium, magnesium alloys or magnesium hydride, liquid reagent is aqueous acid solution, selected from the group: citric, acetic, hydrochloric, sulphuric, liquid reagent is preliminarily placed in separate tank 6 connected to reactor 1 by tube 3 with tap 4 separating reservoir 6 from reactor 1, displacing air from free volume of reservoir 6, hydrogen monitoring and purification system associated with reservoir 6 and refuelling balloon 12 or reactor 1, opening valve 4 separating said reservoir 6 with liquid reagent from reactor 1, and obtained hydrogen through gas outlet tube 16 is directed into reservoir 6 with liquid reagent, then into control and cleaning system, after which is collected in one or several successively filled to required pressure cylinders 12. Method is implemented in device including reactor 1, filled balloon 12, separate reservoir 6 for liquid reagent; doser-metering device 2 equipped with tube 14 for supply of liquid reagent directly to hydrogen-generating material and gas-venting tube 16, wherein pipe 3 for connection of reactor 1 and tank 6 with valve 4 for separation thereof is passed through metering nozzle 2. Nozzle 7 for connection of reservoir 6 and gas outlet tube 16 with control system and purification of evolved hydrogen containing pressure sensor 10, safety valve 9, filter elements 11; overpressure relief system comprising tube 18, safety valve 19 and valve 20, wherein the liquid reagent supply pipe 14 is equipped with a filter and is installed so that its outlet hole is located in the hydrogen generating material zone, the gas outlet pipe 16 is equipped with a filter, tap 17 and is located between nozzle-proportioner 2 and nozzle 7 for connection of reservoir 6 and gas discharge tube 16 with purification system of released hydrogen 10, 9, 11.

EFFECT: disclosed method of producing compressed hydrogen, comprising conducting a chemical reaction of a hydrogen-generating material with a liquid reagent in a closed volume, carried out in the disclosed device, having mobility and simple detachable structure and functioning without using additional power sources, makes it possible to obtain hydrogen in field conditions and to fill it with one or several successively filled cylinders to the required pressure.

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Description

HYDROGEN The invention relates to hydrogen energy, namely to methods and devices designed to produce hydrogen and fill it with vessels to the required pressure.

The method and device for producing compressed hydrogen proposed by the application can be used as autonomous mobile units for generating hydrogen under high pressure with its subsequent filling into cylinders designed to power fuel cells that ensure the operation of unmanned aerial vehicles, telecommunications equipment, computer equipment and other autonomous objects power consumption.

Hydrogen can be obtained and compressed using standard equipment: an electrolyzer and a compressor, but such a scheme is unsuitable for devices operating in field conditions and requiring mobile sources of hydrogen production and compression. Therefore, there are many methods and devices for solving the above problem, based on the use of hydrogen-generating materials, which are subject to the following requirements: simplicity and safety of storage, availability.

Known apparatus [US 1752187] for producing hydrogen under pressure by the reaction of silicon or ferrosilicon with an alkali solution at 100 ° C. The essence of the invention lies in the fact that an alkali solution is poured onto the bottom of the sealed gas cylinder, and metal is poured into it through the lower end of the distributor tube by swinging the cylinder. The disadvantage of this technical solution is the presence of free space above the alkali due to the presence of a distributor tube, which does not allow completely filling the connected container with hydrogen, because some of it remains in the cylinder, and the presence of an aggressive environment (hot alkali solution) can lead to corrosion of the cylinder and the impossibility of its further use.

The proposed device [US 7078012] for filling cylinders with gases (including hydrogen) with a pressure of more than 7 atm, consisting of two containers for storing reagents, a pump for pumping them into a third reactor vessel for the reaction and a gas cylinder. To move the hydrogen-generating component, an inert liquid is applied to it, or this component is enclosed in a fragile shell, which is destroyed by a special device located in front of the reactor. The disadvantage of this device is a lot of technical devices, incl. a pump that requires an external power supply.

Known device [WO 2017094603], where a suspension of magnesium hydride (1-20 wt.%) In water is pumped from the reservoir to the reactor, heated to a temperature of 125-365 ° C. Despite the high yield of hydrogen in the hydrolysis reaction (> 99%) and the use of readily available reagents, the need to use high temperatures to start the reaction dramatically reduces the scope of this device and imposes special requirements on the materials from which it is made.

In the patent [US 8636961] a chemical hydrogen generator is proposed without the use of additional energy sources. The main components are a liquid oxidant and a hydrogen-generating reagent, separated by a fragile membrane. To start the reaction, this membrane is destroyed by a rotating rod, hermetically embedded in the generator housing. The disadvantage of this design is the inability to stop the chemical reaction. In the same patent, the authors propose a modernized version of the generator, the rate of hydrogen evolution in which can be adjusted, however, the final product and the need to manufacture many cells with reagents separated by a membrane seem extremely complicated. And the presence of a fragile membrane separating the reagents can be fraught with uncontrolled destruction of all cells, which makes strict requirements for working with such a generator.

Closest to the claimed invention is the method and device described in [US 7037483], according to which hydrogen is produced by a chemical reaction between water and a hydrogen-generating component (with possible catalyst additions) without additional power sources. A hydrogen-generating component is placed in a container intended for the reaction, then water is poured through a tube with a tap. The filled container is combined with the balloon to be filled. After the reaction, the compressed hydrogen balloon is disconnected from the container. This device was chosen as the prototype of the present invention.

According to the technical solution described in the description of the prototype patent, to carry out the reaction, it is necessary to quickly add the entire volume of water to a container with a hydrogen-generating component and then attach a filled balloon. In this case, the reaction between the components at the initial moment of time can proceed quite intensively, therefore, to prevent the release of reagents into the filled cylinder, a buffer volume with a discharged or inert atmosphere is required, which is filled with the released gas in the process, which reduces the amount of hydrogen received by the consumer. Also, for a complete reaction, it is necessary to use active hydrogen-generating reagents, such as alkali metals, their hydrides or borohydrides, submicron activated particles of magnesium (or its hydride), which creates the need for special storage methods for such reagents and methods for their preparation. The described disadvantages make it difficult to use the specified device in the field.

The objective of the invention is to develop a method and a mobile device for producing and filling containers with compressed hydrogen to the required pressure in the field without using additional energy sources.

The problem is solved by the claimed method, in which the production of hydrogen is carried out due to the interaction of a hydrogen-generating material (HMM) with an oxidizing agent - an aqueous acid solution. To implement the method, magnesium or magnesium alloys in the form of powder, foil, granules, or magnesium compounds (hydride, borohydride, etc.) can be used as HMO, and an aqueous solution of acid (citric, acetic, hydrochloric, sulfuric, etc.) can be used as an oxidizing agent. others), in the process of interaction of which with HMM a water-soluble salt is obtained and hydrogen is released.

The problem is also solved by a device designed to implement a method for producing compressed hydrogen. The diagram of the proposed device is shown in Fig. 1.

A tube 3 is connected to the loaded reactor 1 through the dosing nozzle 2 to connect the reactor 1 and the tank 6 with the valve 4 to separate the tank 6 from the reactor 1, to which the tank 6 is connected through the nozzle 5 for connecting the tank 6 with the valve 4, which serves to store the solution acid. Through the fitting 7 for connecting the reservoir 6 and the gas outlet pipe 16 with the hydrogen purification system into the reactor 1, the pipe 3 for connecting the reactor 1 and the reservoir 6 and the reservoir 6, such an amount of water is placed so that the citric acid added then occupies the entire free volume of the reservoir 6. To avoid the ingress of liquid into the pipe 8 for connecting the elements of the hydrogen purification system due to the displacement of liquid from the reactor 1 into the reservoir 6 during the reaction, it is possible to leave some volume in the reservoir 6 free. A safety valve 9 of a hydrogen purification system, a pressure sensor 10 and filter elements 11 are installed in the tube 8 for connecting the elements of the hydrogen purification system. The refillable cylinder 12 is connected to the device through the valve 13 of the refilled cylinder 13.

After all the above operations, the valve 4 must be opened to separate the reservoir 6 from the reactor 1. The acid solution will begin to flow into the reactor 1, first through the pipe 3 to connect the reactor 1 and the reservoir 6, then through the pipe 14 for supplying the liquid reagent, fixed with a seal 15 in the metering nozzle 2, and the evolved hydrogen through the gas outlet pipe 16, equipped with a tap 17 of the gas outlet pipe 16 - into the reservoir 6. If it is necessary to stop the filling of the refilled cylinder 12, it is necessary to close the valve 4 to separate the reservoir 6 from the reactor 1. At the same time, to prevent the destruction of the reactor 1 due to the high pressure of hydrogen formed as a result of the interaction with the VGM liquid supplied to the reactor 1 before closing the valve 4 for separating the reservoir 6 from the reactor 1, the presence of an overpressure relief system is provided, consisting of a tube 18, a safety valve 19 and / or a valve 20 of the overpressure relief system. It is also possible to arrange the gas outlet tube 16 inside the tube 3 for connecting the reactor 1 and the reservoir 6, while the valve 4 for separating the reservoir 6 from the reactor 1, the valve 17 of the gas outlet tube 16 and related operations are excluded.

Composite or any other cylinders, the material of which is inert to reagents and reaction products, can be used as the reactor and reservoir.

Example 1. 78 g of magnesium grade MPF-3 are poured into the reactor. The entire free volume of the reactor and the tube for connecting the reactor and the reservoir is filled with water, then the valve is closed to separate the reservoir from the reactor, after which 100 ml of water is poured into the reservoir with a volume of 1900 ml. Then added 1600 ml of citric acid solution with a concentration of 4 mol / l. Air was removed from the free volume of the tank, the hydrogen purification system and the refillable cylinder with a volume of 1 liter, and the valve was opened to separate the tank from the reactor. Over a period of 300 minutes, 62 NL of hydrogen was evolved, which made it possible to create a hydrogen pressure of 52 bar in the refilled cylinder.

Example 2. In the reactor is placed 40 g of magnesium hydride. The reactor is connected to a 1900 ml tank with a tube to connect the reactor to the tank. Air was removed from the reactor, then the valve to separate the reservoir from the reactor and the valve of the gas outlet tube were closed to prevent air from entering the reactor. The reservoir contains 100 ml of water and 1600 ml of citric acid solution with a concentration of 4 mol / l. Air was removed from the free volume of the reservoir and the hydrogen purification system, the valve for separating the reservoir from the reactor and the valve of the gas outlet tube were opened. During 120 min, 57 nL of hydrogen was evolved.

Thus, the proposed method for producing compressed hydrogen, which consists in carrying out a chemical reaction of HMM with a liquid reagent in a closed volume, carried out in the inventive device, which has a simple collapsible design and operates without the use of additional energy sources, makes it possible to obtain hydrogen and fill it with one or several sequentially charged cylinders to the required pressure.

1. Reactor.

2. The dosing connection.

3. Tubing for connecting the reactor and the reservoir.

4. Tap for separating the reservoir from the reactor.

5. Fitting for connecting the tank to the tap.

6. Reservoir.

7. Nipple for connecting the reservoir and the gas outlet tube with the hydrogen purification system.

8. Tube for connecting elements of the hydrogen purification system.

9. Safety valve for hydrogen purification system.

10. Pressure sensor.

11. Filtering elements.

12. Refillable bottle.

13. The valve of the filled cylinder.

14. Tube for supplying liquid reagent.

15. Sealing of the dosing nozzle.

16. Gas outlet tube.

17. Gas outlet pipe valve.

18. Tube of overpressure relief system.

19. Overpressure relief valve.

20. Overpressure relief valve.

Claims (4)

1. A method of producing compressed hydrogen, including carrying out a chemical reaction of a hydrogen-generating material with a liquid reagent in a reactor with the release of hydrogen and filling it with a refilled cylinder, characterized in that magnesium, magnesium alloys or magnesium hydride are used as the hydrogen-generating material, as liquid reagent - an aqueous solution of an acid selected from the group: citric, acetic, hydrochloric, sulfuric, liquid reagent is preliminarily placed in a separate tank connected to the reactor by a tube with a tap that separates the tank from the reactor, air is displaced from the free volume of the tank, control and cleaning systems hydrogen associated with the reservoir and the refilled cylinder or reactor, open the valve separating the specified reservoir with the liquid reagent from the reactor, and the obtained hydrogen is directed through the gas outlet pipe to the reservoir with the liquid reagent, then to the control and cleaning system, and then collected in one or several consecutive requests cylinders driven to the required pressure. 2. A method according to claim 1, characterized in that a liquid, inert or weakly active to reagents, reaction products and equipment materials, is poured into the reactor and reservoir, which is necessary to displace air, eliminate empty space, and increase heat capacity. 3. A method according to claim 1, characterized in that the hydrogen-generating material is used in the form of a powder, foil or granules. 4. A device for implementing the method according to claim 1, comprising a reactor, fittings and a refillable cylinder, characterized in that it is additionally equipped with a separate reservoir for a liquid reagent; a dosing nozzle equipped with a tube for supplying a liquid reagent directly to the hydrogen-generating material, and a gas outlet pipe, while a pipe is passed through the dosing nozzle to connect the reactor and a reservoir with a valve for their separation; a fitting for connecting a reservoir and a gas outlet tube with a system for monitoring and purifying the evolved hydrogen containing a pressure sensor, a safety valve, filter elements; an overpressure relief system containing a pipe, a safety valve and a tap, while the liquid reagent supply pipe is equipped with a filter and installed in such a way that its outlet is located in the zone of the hydrogen-generating material, the gas outlet pipe is equipped with a filter, a tap and is located between the fitting a dispenser and a fitting for connecting the reservoir and the gas outlet pipe to the system for purifying the evolved hydrogen.

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