Microtube hydrogen storage device and manufacturing method thereof

Abstract

The invention discloses a microtube hydrogen storage device and a manufacturing method thereof. The microtube hydrogen storage device is characterized by comprising a hydrogen storage glass microtube bundle (1), a metal valve (2) and a metal connector (3). Wherein the tail end (4) of the hydrogen storage glass microtube bundle is in a sealed state; and the head end (5) of the hydrogen storage glass micro tube bundle is in an open state. The manufacturing method of the device comprises the steps of drawing of the single microtubes, columnar assembly of the single microtubes, drawing of the microtube bundle, sealing of the tail end of the microtube bundle and packaging of the head end of the microtube bundle. Compared with the prior art, higher hydrogen storage pressure and higher mass hydrogen storage density can be realized; and the hydrogen storage container which is smaller in size and can be customized is realized.

Description

Technical Field

[0001] The patent of this invention relates to a microtube hydrogen storage device and a method for manufacturing the same. The microtube hydrogen storage device prepared by the invention can realize a customized hydrogen storage device, which can achieve higher hydrogen storage pressure and higher quality hydrogen storage density, while achieving smaller volume, safer, and hydrogen embrittlement-free hydrogen storage. Background Art

[0002] Under the background of the national strategic goal of carbon peak and carbon neutrality, hydrogen energy is considered to be the new energy with the most development potential in the 21st century because of its advantages such as easy production, abundant sources, safe use, high combustion efficiency, environmental friendliness and sustainability. The safe and efficient storage and transportation of hydrogen is an important link in the widespread application of hydrogen energy. At present, the widely used hydrogen storage equipment is high-pressure metal gas cylinders, but they face the risk of hydrogen embrittlement. At the same time, the low mass hydrogen storage density and volume hydrogen storage density also limit their use in the large-scale production of hydrogen. In order to meet the needs of large-scale hydrogen storage and transportation, glass capillaries are applied to hydrogen storage containers.

[0003] The microtube hydrogen storage device proposed in the Chinese patent "A method for manufacturing a microtube hydrogen storage device" with application publication number CN113357526A has a complicated preparation process and contains a large number of quartz rods inside, which increases the weight of the microtube bundle and thus reduces the mass hydrogen storage density of the microtube bundle.

[0004] In summary, there is a need to propose a microtube hydrogen storage device that has a higher hydrogen storage pressure and a higher mass hydrogen storage density than the existing microtube hydrogen storage device, and the device has the advantages of smaller size, greater safety, and no hydrogen embrittlement. Summary of the invention

[0005] The invention discloses a micro-tube hydrogen storage device and a manufacturing method thereof, wherein the device comprises a hydrogen storage glass micro-tube bundle, a metal valve and a metal connector, wherein the tail end of the hydrogen storage glass micro-tube bundle is in a sealed state, and the head end of the hydrogen storage glass micro-tube bundle is in an open state.

[0006] The purpose of the present invention is to provide a technology for drawing a high-consistency thin-walled microtube single tube from a quartz tube, then arranging the microtube single tube regularly, and drawing it again to obtain a high-consistency microtube bundle, thereby preparing a microtube hydrogen storage device, achieving higher hydrogen storage pressure, higher mass hydrogen storage density, and achieving safer storage of hydrogen without hydrogen embrittlement.

[0007] The technical solution adopted by the present invention is: 1. Design the size of the microtube used in the rod assembly. Use a quartz tube with an outer diameter of 25 mm and a wall thickness of 0.9 mm to draw a single capillary tube with a diameter of 0.5~2 mm at a temperature of 1900~2100 °C; 2. Design the internal structure of the microtube bundle. In order to improve the mass hydrogen storage density of the microtube bundle, a honeycomb microporous structure with a high duty cycle is selected. 60-1750 single-tube capillaries with a diameter of 0.5~2 mm are assembled into a column, placed in an outer sleeve with an outer diameter of 25 mm and a wall thickness of 0.9 mm, and the microtube bundle is drawn under the drawing conditions of a temperature of 1850~2000 °C and a negative pressure of -0.3~-5 Kpa to obtain a uniform glass microtube bundle with a honeycomb microporous structure and a micropore diameter of 0.018~1.2 mm; 3. Seal the tail end of the glass microtube bundle. The tail end of the microtube bundle is sealed by oxyhydrogen flame sintering; 4. Design the head end of the glass micro-tube bundle. The head end of the hydrogen storage glass micro-tube bundle is open and connected to the metal connector by sealing glue. It is the inlet of hydrogen. Hydrogen passes through the metal valve and metal connector and is stored in the glass micro-tube bundle.

[0008] Compared with the prior art, the present invention has the following beneficial effects: 1. Only one specification of glass capillary needs to be drawn during the preparation process, which greatly simplifies the complexity of device preparation and the assembly process is simple; 2. The glass microtube bundles are made of thin-walled glass capillaries and thin-walled quartz outer sleeves, which reduces the weight of the glass microtube bundles and thus improves the mass hydrogen storage density of the hydrogen storage device; 3. The device is flexible in setting and can release hydrogen at any time by adjusting the metal valve; 4. The device has a simple structure and a low damage rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 This is a schematic diagram of a hydrogen storage micro-tube bundle device; Figure 2 Schematic diagram of the high-consistency thin-walled microtube single tube drawing technology; Figure 3 Schematic diagram of high-consistency microtube bundle drawing technology; Figure 4 Schematic diagram of oxyhydrogen flame sintering technology at the tail end of micro-tube bundle; Figure 5 This is a schematic diagram of the microtube bundle head-end packaging technology; in: 1-glass microtube bundle, 2-metal valve, 3-metal connector, 4-tail end of microtube bundle, 5-head end of microtube bundle, 6-quartz tube with large diameter and thick wall, 7-glass capillary with small diameter and thin wall, 8-cylindrical glass microtube bundle after assembly, 9-quartz outer sleeve with large diameter and thin wall, 10-drawn glass microtube bundle, 11-glass tube bundle inside the drawn microtube bundle, 12-hydrogen-oxygen flame, 13-epoxy resin glue. Implementation

[0010] The present invention is further described below in conjunction with the accompanying drawings.

[0011] First, a quartz tube (6) with an outer diameter of 25 mm and a wall thickness of 0.9 mm is placed in a hydrofluoric acid solution with a concentration of 10% to 30% and pickled for 10 to 20 minutes to reduce defects and impurities on the glass surface.

[0012] like Figure 2 As shown in the figure, a highly consistent thin-walled microtube single tube drawing technology is used. A quartz tube (6) with an outer diameter of 25 mm and a wall thickness of 0.9 mm after pickling is placed in a drawing tower or other drawing equipment, and a thin-walled microtube single tube (7) with a diameter of 0.5 to 2 mm is drawn at a drawing temperature of 1900 to 2100 °C. Then, 60 to 1750 thin-walled microtube single tubes (7) are assembled into a regular and orderly cylindrical microtube bundle (8).

[0013] like Figure 3 The figure shows a high consistency microtube bundle drawing technology. The cylindrical microtube bundle (8) is placed in a quartz tube (9) with an outer diameter of 25 mm and a wall thickness of 0.9 mm and is drawn again. At a drawing temperature of 1850~2000 °C and a negative pressure of -0.3~-5 KPa, a glass microtube bundle (10) with a diameter of 1~10 mm is drawn. There are 60-1750 micropores in the microtube bundle, and the micropore diameter is 0.018~1.2 mm.

[0014] Then, the tail end of the prepared glass microtube bundle is permanently encapsulated, e.g. Figure 4 As shown, the present invention achieves permanent sealing of the microtube bundle by oxyhydrogen flame sintering. The oxyhydrogen flame sintering means: by adjusting the ratio of hydrogen and oxygen in the oxyhydrogen flame (12), the flame temperature is increased, the glass viscosity is reduced, the glass microtubes are melted, the opening of the tail end (4) of the microtube bundle is shrunk at high temperature, and the glass viscosity is rapidly increased after the temperature is immediately lowered, thereby achieving the purpose of sealing the tail end.

[0015] Then, the prepared glass microtube bundle head end (5) is effectively encapsulated, such as Figure 5 The figure shows the sealing process of the head end of the microtube bundle. In the present invention, epoxy resin glue (13) is used to glue to achieve effective packaging of the head end (5) of the microtube bundle. The metal connector (3) has a groove with a depth of not less than 5 cm. After the glass microtube bundle (1) is deeply inserted into the groove of the metal component (3), epoxy resin glue is poured into it to achieve effective packaging of the head end (5) of the microtube bundle.

[0016] like Figure 1 The microtube hydrogen storage device shown is prepared, and hydrogen is stored in the glass microtube bundle through the metal valve (2), the metal connector (3), and the microtube bundle head end (5).

[0017] Implementation Case 1: A quartz tube (6) with an outer diameter of 25 mm and a wall thickness of 0.9 mm was placed in a 10% hydrofluoric acid solution for pickling for 10 min, and then a thin-walled microtube single tube (7) with a diameter of 1 mm was drawn at a drawing temperature of 1950 °C. Then 350 thin-walled microtube single tubes (7) were assembled into a regular and orderly cylindrical microtube bundle (8). The cylindrical microtube bundle (8) was placed in a quartz tube (9) with an outer diameter of 25 mm and a wall thickness of 0.9 mm and drawn again. At a drawing temperature of 1970 °C and a negative pressure of -0.3 Kpa, a glass microtube bundle (10) with a diameter of 8 mm was drawn, and there were 350 micropores in the microtube bundle, and the micropore diameter was 0.298 mm. Then, the tail end of the microtube bundle was sealed by oxyhydrogen flame sintering, and the head end of the microtube bundle was encapsulated by gluing with epoxy resin. The microtube bundles prepared under this condition can achieve a maximum pressure resistance of 70 MPa and a mass hydrogen storage density of 5%.

[0018] Implementation Case 2: A quartz tube (6) with an outer diameter of 25 mm and a wall thickness of 0.9 mm was placed in a 10% hydrofluoric acid solution for pickling for 10 min, and then drawn at a drawing temperature of 1970 °C to obtain a thin-walled microtube single tube (7) with a diameter of 2 mm. Then, 93 thin-walled microtube single tubes (7) were assembled into a regular and orderly cylindrical microtube bundle (8). The cylindrical microtube bundle (8) was placed in a quartz tube (9) with an outer diameter of 25 mm and a wall thickness of 0.9 mm and drawn again. At a drawing temperature of 1960 °C and a negative pressure of -0.5 Kpa, a glass microtube bundle (10) with a diameter of 1.5 mm was drawn, and there were 93 micropores in the microtube bundle, and the micropore diameter was 0.113 mm. Then, the tail end of the microtube bundle was sealed by oxyhydrogen flame sintering, and the head end of the microtube bundle was encapsulated by gluing with epoxy resin. The microtube bundles prepared under these conditions can achieve a maximum pressure resistance of 70 MPa and a mass hydrogen storage density of 6.3%.

Claims

1. A micro-tube hydrogen storage device, Features: The components include a hydrogen storage glass micro-tube bundle, a metal valve, and a metal connector. The tail end of the hydrogen storage glass micro-tube bundle is in a sealed state, and the head end of the hydrogen storage glass micro-tube bundle is in an open state.

2. A micro-tube hydrogen storage device according to claim 1, Features The interior of the glass microtube bundle is a glass capillary column bundle made of pure quartz glass.

3. A micro-tube hydrogen storage device according to claim 1, Features The glass microtube bundle is cylindrical on the outside and has closely arranged micropores in a honeycomb shape on the inside, with a pore size of 0.018~1.2 mm.

4. A micro-tube hydrogen storage device according to claim 1, Features The number of micropores inside the glass microtube bundle is 60~1750.

5. A micro-tube hydrogen storage device according to claim 1, Features The length of the glass microtube bundle is 10~25 cm.

6. A micro-tube hydrogen storage device according to claim 1, Features The diameter of the glass microtube bundle is 1~10mm.

7. A micro-tube hydrogen storage device according to claim 1, Features The hydrogen storage device can achieve a mass hydrogen storage density of 1% to 8.1%.

8. A micro-tube hydrogen storage device according to claim 1, Features The hydrogen storage device can achieve a maximum pressure resistance of 35~70 MPa and can maintain pressure for more than 12 hours.

9. A method for manufacturing a microtube hydrogen storage device, Features The glass capillaries inside the glass microtube bundle are drawn from a quartz tube with an outer diameter of 25 mm and a wall thickness of 0.9 mm at a drawing temperature of 1900~2100 °C.

10. A method for manufacturing a micro-tube hydrogen storage device according to claim 9, Features Before drawing, the quartz tube needs to be pickled in a 10% to 30% hydrofluoric acid solution for 10 to 20 minutes.

11. A method for manufacturing a micro-tube hydrogen storage device according to claim 9, Features The drawn glass capillaries are assembled in columnar shape in an orderly manner and then placed in an outer sleeve with an outer diameter of 25 mm and a wall thickness of 0.9 mm for drawing the glass microtube bundle at a drawing temperature of 1850~2000 °C.

12. The method for manufacturing a micro-tube hydrogen storage device according to claim 9, Features Negative pressure needs to be applied during the microtube bundle drawing process, and the negative pressure is -0.3~-5 Kpa.

13. The method for manufacturing a micro-tube hydrogen storage device according to claim 9, Features The glass microtube bundle is connected to the metal connector by means of sealant, and serves as the hydrogen inlet. The hydrogen passes through the metal valve and the metal connector and is stored in the glass microtube bundle.

14. The method for manufacturing a micro-tube hydrogen storage device according to claim 9, Features The tail end of the glass microtube bundle is sealed by oxyhydrogen flame sintering.

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