Tank for storing and accumulating hydrogen

FIELD: hydrogen power engineering.

SUBSTANCE: tank comprises pressure-tight housing, branch pipes, heater, and filler-accumulator of hydrogen mounted inside the housing. The tank is separated with the baffle made of proton-conducting material into anode space filled with water and provided with porous anode and cathode space that receives the solid cathode and heater and is filled with the filler-accumulator of hydrogen made of microporous high-strength material. The microporous material is made of hollow microspheres.

EFFECT: enhanced safety and capacity.

6 cl, 3 dwg

 

The invention relates to the field of hydrogen energy - accumulation and storage of hydrogen, which is currently used in the chemical, transportation and other industries.

The known device for the accumulation and storage of hydrogen, based on the coupling of hydrogen in the solid material (for example, metal hydrides or sorption on the surface of dispersed nanomaterials), (RF patents №2037737, 2038525, IPC F 17 5/04), these devices for the accumulation and storage of hydrogen are the most explosion-existing, since hydrogen has no pressure, but such systems are slow and require a certain time (about several minutes) to get started, the uptake and release of hydrogen occurs with significant thermal effects, in addition, the mass content of hydrogen - weight - hydrogen contained in the battery to the weight of the battery of 4.5% is very low. Mass content depends on the number of hydrogen accumulating material, and the specific weight of the storage material.

Known capacity for hydrogen storage (patent No. 2222749, IPC F 17 C 5/04), representing a sealed casing with an inner vessel for storing liquefied hydrogen, the system gattapone shaped so that it provides in order to reduce the loss of hydrogen, to reduce the time of reservoir filling. This reservoir is used for hydrogen car (Schwartz A. the Car of the future. J. Bulletin, No. 10 (347), p.1-5, 12.05.2004), it is made of durable composite relatively light materials. Last modification has a volume of 90 liters, weight 40 kg, a hydrogen pressure of 400 ATM. Estimates show that in this case the containers can be stored 3.2 kg of hydrogen, therefore, the mass content of hydrogen is a 3.2/40×100%=8%. The disadvantages of capacity is the explosiveness and low hydrogen content per unit volume, up to 400 liters of hydrogen per 1 liter, loss of gas from the container.

It is known that it is possible to store hydrogen in hollow microspheres made of glass with a diameter of 5-200 μm with a wall thickness of 0.5-5 μm (S. p. Malyshenko, Nazarova O. Accumulation of hydrogen. In the collection of articles. "Atomic-hydrogen energy and technology", VIP, page 155-205, 1988). At a temperature of 200-400°under the pressure of the hydrogen actively diffundere through the walls, filling the microspheres and after cooling remains in them under pressure. So when the hydrogen pressure of 500 atmospheres and heating of the microspheres up to these temperatures were obtained bulk hydrogen content in the microspheres 5.5 to 6.0%. At lower pressures the mass of the hydrogen content in the microspheres will be reduced. When heated to 200°receive about 55% and stored in the mikros erah hydrogen and about 75% when heated up to 250° C. When storing hydrogen in a glass microspheres loss by diffusion through the walls comprise about 0.5% per day. In the case of the coating of the microspheres metal films diffusive loss of hydrogen at room temperature is reduced by 10-100 times. A significant drawback is that the charging of the battery with the microspheres is carried out at relatively low hydrogen pressures, since the tensile strength of glass under tension has a low value and is within up to 20 kg/mm2. This doesn't allow the mass of the hydrogen content in the microspheres substantially in excess of 6 wt.%.

Known capacity for storage and hydrogen storage, consisting of a sealed enclosure, process pipes, the internal heat transfer surfaces and filler-hydrogen battery, a powder of intermetallic (RF patent No. 2037737, IPC F 17 5/04 - prototype). The disadvantage of the invention is that the absorption and release of hydrogen occurs with significant thermal effects, in addition, the mass content of hydrogen is the ratio of the weight of the hydrogen contained in the vessel, the weight capacity of 4.5% is very low.

The technical result, which aims invention is the creation of capacity for safe storage and hydrogen storage, ensuring the processes to increase the mass of hydrogen content above 6%.

To do this, the offered capacity for storage and hydrogen storage, consisting of a sealed enclosure, process pipes, heater and filler-hydrogen battery, accommodated in the housing, and the capacity is divided by a partition from prostonaprosto material on the anode cavity filled with water, placed in it a porous anode and cathode cavity located therein a solid cathode and heater and filled with filler-hydrogen battery, made from a material with a tensile strength higher than 30 kg/mm2and having a microporous structure.

When this partition is made in the form of proton membrane.

This microporous structure is made of hollow microspheres.

In addition, the microporous structure is made of polymers group of aramids. Also the microporous structure may be made of nanostructural catalyst, such as Nickel foam, penutian.

In addition, the microporous structure is made from a material with proton properties.

The content of hydrogen in microporous structure is primarily determined by the strength characteristics of the material of this structure. For microporous structures for storage and hydrogen storage suitable high-strength materials with tensile strength σBPabove 30 is g/mm 2. From the strength characteristics depends, what is the maximum pressure of hydrogen can be created with a fixed pore size, as the same hydrogen pressure creates a large voltage in the pores of large size and a lesser voltage in small pores. Increasing pore volume (and hence their size), we get a larger hydrogen content per unit volume of the microporous structure, but increase the size of the pores is limited by limiting the voltage that is generated by the pressure of the hydrogen in these pores. As a result, for each material maximum pore size is determined by the strength characteristics of the material of the microporous structure. In addition, the material of the microporous structure must have significantly different characteristics on the permeability of hydrogen under various conditions, such as temperature change, when exposed to ultrasound, high frequency currents when applying DC or AC voltage, etc. the nature of the effect and its magnitude is determined by the requirements of the rate of hydrogen absorption microporous structure and/or speed of the hydrogen release from it.

The most simple and really created a microporous structure is a structure created from hollow microspheres, especially metals or their alloys, as well as micropores the th structure of the Nickel foam, penutian, other foam materials and polymeric materials.

The microporous structure of the hollow microspheres, for example of steel, is formed into a single rigid structure. This can be done by diffusion welding. With all the free space inside the microspheres and between them will be filled with hydrogen.

Of special interest for the production of porous microstructure are of materials having high strength properties and low specific weight, is primarily a composite of carbon and polymer materials. Thus, the polymers made on the basis of poly-p-phenyleneterephthalamide and other similar polymers of aromatic series (aramides), density of 5.5 times less than steel and strength characteristics of 2.5-3.5 times higher. For high-strength steels tensile strength σBP=160-220 kg/mm2for aramids the tensile strength of 550 kg/mm2(table 1).

Table 1
Material brand (country)Density, kg/m3The tensile strength, kg/mm2
Armos (Russia)1450500-550
RAS (Russia)1430380-420
Terlon (Russia)1450 310
Kevlar-29 (USA)1440292
Kevlar-129 (USA)1440320
Twaron (Netherlands)1440280
Technora (Japan)1390300-340

Figure 1 shows the schematic diagram of the storage and hydrogen storage, where 1 - building capacity, 2 - porous electrode - anode made of a conductor 1-St kind, 3 - pipe supply water to the anode cavity, 4 - pipe exhaust oxygen from the anode cavity, 5 - partition of proton material (membrane), 6 - microporous structure - hydrogen battery, 7 - solid electrode is a cathode made of a conductor 1-St kind, 8 - tube removal of hydrogen from the tank to the engine (to the consumer), 9 - heater.

Figure 2 presents the microporous structure of the microspheres, with 10 being the microsphere.

Figure 3 presents the microporous structure of the polymer material - armoise, where 11 - fibers 12 - pores.

The device operates as follows.

Sealed body 1 of the container is divided by a partition 5 into two cavities. The anode cavity is filled with water through the pipe 3. The water enters the porous anode 2. On the border of the porous anode, made for example of porous titanium and proton membrane 5 which may be made of ceramic, polymer or other material that flows through the oxidation reaction of water:

2H2O+2E-=O2+4H+.

Oxygen through the pores of the anode is allocated in the volume of water through the pipe outlet oxygen 4 is removed. Hydrogen ions (protons) on proton membrane 5 move to the cathode 7, which is reduced to hydrogen. Hydrogen does not pass through solid metal cathode 7 and saturates microporous structure 6. The cathode and the proton membrane form a cathode cavity filled with a porous microstructure 6. This closed volume hydrogen when heated by the heater 9 through the pipe 8 is sent to the consumer, for example, the delivery system of hydrogen in the internal combustion engine or fuel cells. To accelerate the hydrogen saturation microporous structure may have a proton properties. The amount of hydrogen in the porous structure is determined by the magnitude of charging current and charging time.

Compare the characteristics of the storage and hydrogen storage with microporous structure of hollow microspheres of 10 (see figure 2) made of steel and Armos (see figure 3), where 11 - fiber material. In the formation of pores 12 form them can be very diverse from the capillaries to the fields. Consider a spherical pore.

Table 2 presents a comparison of the characteristics of microporous when ructur, made of steel microspheres and a microporous structure with the same pore size, made of Armos. In the table - σϕ - tangential stress on the outer shell of the microsphere, kg/mm2that σRradial tension on the shell of the microspheres, kg/mm2. The specific weight of steel is 8 kg/L. Armos Specific weight - 1.45 kg/l

Table 2
The pressure of hydrogen saturation, ATIThe weight of H2the weight of the microstructure, wt.%The hydrogen content in the microstructure, l/l (g N2/l)σϕ-σRkg/mm2
1245
Microstructure with microspheres with a diameter of 200 μm, the shell thickness of 1 μm. The weight of the shell per volume of the microstructure: steel - 124,3 g/l, from armoise - 22,53 g/l pore Volume of 0.98 l/l
20014,178,1196,8 (17,6)100,5
300of 21.2117,2295,3 (26,4)150,75
40028,3156,2393,8 (35,2)201,0
100070,7390,1984,4 (87,9)502,5

Microstructure of microspheres with a diameter of 100 mm, a shell thickness of 1 μm. The weight of the shell per volume of the microstructure: steel - 246,2 g/l, from armoise - 44,6 g/l pore Volume to 0.97 l/l
40014,077,6387,7 (34,6)101,0
80028,1155, 2mm775,5 (69,2)202,0
100035,1193,9969,2 (86,5)252,5
200070,3388,11938,5 (173,1)505,0
Microstructure of microspheres with a diameter of 10 mm, a shell thickness of 1 μm. The weight of the shell per volume of the microstructure: steel - 1134,9 g/l, from armoise - KZT 205.7 g/l pore Volume is 0.86 l/l
10006,7171,7858,1 (76,6)27,5
1000067,5372,58581,35 (766,2)275,0
20000135,0744,917162,7 (1532,4)550,0
Microstructure of microspheres with a diameter of 3 mm, a shell thickness of 1 μm. The weight of the shell per volume of the microstructure: steel - 3992 g/l, from armoise - 723,6 g/l pore Volume - 0,50 l/l
1000011,261,85010,0 (447,0)100,0

As can be seen from table 2, for the same microporous structures with micropores with a diameter of 200 μm, the weight content of hydrogen in the microstructure is achieved for the best steels 28.3 wt.%, and for armoise 390 wt.%.

Example 1. Capacity for hydrogen storage divided high temperature (up to 300° (C) proton ceramic membrane into two cavities. Cathode cavity volume 0,028 liters filled microporous structure of hollow microspheres of high strength steel with a diameter of microspheres 200 and 80 mm, a shell thickness of 1 μm. Microspheres are connected in a rigid nozzle by diffusion welding. Weight 0,028 l microporous structure is 3.5, the Anode of porous titanium is washed with water. Charging microporous structure was carried out at current density of 1 A/cm2. 20 minutes through the surface of proton membrane was held in the volume of the microporous structure of 7.2 liters of hydrogen. When charging, the temperature of the microporous structure was supported by a special heater at 280°C. the Mass content of hydrogen was 18.4 wt.%.

Example 2. This device was loaded microporous structure on the basis of polymer - armoise representing fiber polymer with a pore size of ˜200 μm. Charging microporous structure is ture hydrogen is continued for 20 minutes. Proton polymer membrane - MF-SC. The microporous structure has absorbed a 7.2 liter of hydrogen. The weight of the porous structure comprised of 0.64, the Mass content of hydrogen in the microstructure - 101%.

Such tanks for storage and hydrogen storage have significant advantages over those that are filled with hydrogen at high pressure or by using cryogenic technology. They are not only safe, but have a very high degree of hydrogen saturation while maintaining small size. They can be delivered not only at petrol stations or special items supply of batteries, these tanks will be able to charge consumers (drivers), it is enough to pour into the cavity with the anode of clean water and connect the tank to the network (power source).

1. Capacity for hydrogen storage, consisting of a sealed enclosure, process pipes, heater and filler-hydrogen battery, accommodated in the housing, characterized in that capacity divided by a partition of the proton material on the anode cavity filled with water, placed in it a porous anode and cathode cavity located therein a solid cathode and heater, and filled with filler-hydrogen battery, made from a material with a tensile strength higher than 30 kg/mm2ikeyslim microporous structure.

2. The container according to claim 1, characterized in that the filler-battery is made of hollow microspheres.

3. The container according to claim 1, characterized in that the filler-battery is made of polymer group aramids.

4. The container according to claim 1, characterized in that the filler-battery is made of nanostructural catalyst, such as Nickel foam, penutian.

5. The container according to claim 1, characterized in that the partition is made in the form of proton membrane.

6. The container according to claim 1, characterized in that the filler-a battery is made from a material with proton properties.



 

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