CN114427657B - High-pressure hydrogen storage method and gas cylinder - Google Patents

High-pressure hydrogen storage method and gas cylinder Download PDF

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Publication number
CN114427657B
CN114427657B CN202210114509.3A CN202210114509A CN114427657B CN 114427657 B CN114427657 B CN 114427657B CN 202210114509 A CN202210114509 A CN 202210114509A CN 114427657 B CN114427657 B CN 114427657B
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hydrogen storage
capillary
capillary tube
tube
hydrogen
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CN114427657A (en
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洪正鹏
赵东林
商红岩
孟闻捷
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Beijing Dongfang Hongsheng New Energy Application Technology Research Institute Co ltd
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Beijing Dongfang Hongsheng New Energy Application Technology Research Institute Co ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/005—Storage of gas or gaseous mixture at high pressure and at high density condition, e.g. in the single state phase
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/02—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
    • F17C1/04—Protecting sheathings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C13/00—Details of vessels or of the filling or discharging of vessels
    • F17C13/002—Details of vessels or of the filling or discharging of vessels for vessels under pressure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C13/00—Details of vessels or of the filling or discharging of vessels
    • F17C13/04—Arrangement or mounting of valves
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C13/00—Details of vessels or of the filling or discharging of vessels
    • F17C13/06—Closures, e.g. cap, breakable member
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0104—Shape cylindrical
    • F17C2201/0109—Shape cylindrical with exteriorly curved end-piece
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0612—Wall structures
    • F17C2203/0614—Single wall
    • F17C2203/0619—Single wall with two layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/01—Mounting arrangements
    • F17C2205/0123—Mounting arrangements characterised by number of vessels
    • F17C2205/0126—One vessel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
    • F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
    • F17C2205/0323—Valves
    • F17C2205/0332—Safety valves or pressure relief valves
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
    • F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
    • F17C2205/0323—Valves
    • F17C2205/0335—Check-valves or non-return valves
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2209/00—Vessel construction, in particular methods of manufacturing
    • F17C2209/21—Shaping processes
    • F17C2209/219—Working processes for non metal materials, e.g. extruding
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2209/00—Vessel construction, in particular methods of manufacturing
    • F17C2209/23—Manufacturing of particular parts or at special locations
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/012—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0107—Single phase
    • F17C2223/0138—Single phase solid
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
    • F17C2223/036—Very high pressure (>80 bar)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2265/00—Effects achieved by gas storage or gas handling
    • F17C2265/06—Fluid distribution
    • F17C2265/065—Fluid distribution for refuelling vehicle fuel tanks
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0165—Applications for fluid transport or storage on the road
    • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
    • F17C2270/0178—Cars
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0165—Applications for fluid transport or storage on the road
    • F17C2270/0184—Fuel cells

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

The invention discloses a high-pressure hydrogen storage method and a gas cylinder, which comprise a plurality of hydrogen storage capillaries for storing hydrogen, wherein a metal organic framework adsorption material and a covalent organic compound adsorption material are sequentially synthesized in situ in each hydrogen storage capillary, the plurality of hydrogen storage capillaries form a capillary bundle, external compressed hydrogen is accessed from one end of the capillary bundle, and the hydrogen is stored in each hydrogen storage capillary in the capillary bundle. The invention adopts the integrated low-density capillary tube bundle which is internally filled with the metal organic framework adsorption material and the covalent organic compound adsorption material at the same time for hydrogen storage, has high hydrogen storage pressure, strong hydrogen storage capacity and low manufacturing cost, realizes the storage of high-pressure hydrogen in a relatively light container, and has higher commercial application value.

Description

High-pressure hydrogen storage method and gas cylinder
Technical Field
The invention relates to the technical field of hydrogen storage, in particular to a high-pressure hydrogen storage method and a gas cylinder.
Background
Hydrogen storage is a key challenge for the development of hydrogen energy applications. Two main objectives have prompted improvements in cylinders. First, the transportation cost of H 2 must be reduced. For example, the total capital and operating costs of a tube trailer account for a major portion of the price of delivering hydrogen. Second, the functional requirements of the hydrogen energy system, such as weight and bulk density, must be satisfied enough to match a hydrogen fuel cell vehicle with an equivalent gasoline vehicle.
For many years, steel cylinders have been the most widely used technology for storing compressed hydrogen and gas. It provides a relatively low weight and bulk storage density. Alternatives to steel cylinders include liquid H 2 tanks, composite compressed hydrogen tanks, gas tanks, adsorbents, metal hydrides and chemical hydrides.
The composite compressed H 2 air tanks are typically made of aluminum or polymer liners lined with a polymer/carbon fiber coating. They are designated as type III and type IV. They provide weight and bulk storage densities of 5wt% and 26g/L, respectively. Because of the relatively high cost of carbon fiber, composite cylinders made of carbon fiber are much more expensive than steel cylinders. Due to the wide application of carbon fibers in aerospace composites, mass production of carbon fibers is not possible to reduce their high cost.
Chemical hydrides are metal hydrogen compounds that produce hydrogen at the point of use by irreversible reactions. The waste reaction products need to be recovered at a central facility. They can provide very high gravimetric capacities (sodium borohydride > 100%). However, chemical hydrides are relatively expensive. Furthermore, the operability of the H 2 generator and the flow of recycled reaction products are major disadvantages.
The adsorbent operates by physical adsorption and H 2 molecules bind weakly to the microporous surface. A considerable storage capacity can only be obtained at low temperatures approaching 77K. In sorbent-based storage tanks, H 2 is stored both as a sorbent and in the gas phase. The gas phase cannot access the volume occupied by the adsorbent framework. Above a certain pressure, this repulsive effect of the adsorbent skeleton becomes too severe and the efficiency of removing the adsorbent becomes higher.
In recent years, activated carbon is the best adsorbent for low temperature adsorption. However, its performance does not lead to commercialization, and the use of flammable adsorbents (such as activated carbon) at low temperatures presents a potential build-up of contaminating oxygen.
Glass microspheres have been proposed for many years as miniature hydrogen storage containers. Glass microspheres are attractive because failure of one microsphere is not expected to have an impact on safety and the amount of hydrogen released is small. Filling and release is accomplished by heating the microspheres at ambient temperature. When the hydrogen permeability in the microsphere is small, the temperature range is 100-4000 ℃, at which the hydrogen permeability in the microsphere is allowed to fill or release depending on the pressure differential across the microsphere wall. However, to date, glass microsphere systems are considered to be not competitive with alternative hydrogen storage technologies. For example, one project demonstrated weight and volume capacities of only 2.2wt% and 4g/L, respectively, well below type III and type IV cylinders.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the high-pressure hydrogen storage method and the gas cylinder, which are characterized in that the high-pressure hydrogen storage is carried out through the capillary tube bundle with the MOF and COF materials filled in situ in the integrated part, one end of the capillary tube bundle is inflated, the other end of the capillary tube bundle is deflated, the structure is simple, the high-pressure hydrogen storage method and the gas cylinder are efficient in use, the hydrogen can be repeatedly filled, the cost is low, and the high-pressure hydrogen can be stored in a relatively light container.
The invention adopts the following technical scheme:
A high-pressure hydrogen storage method comprises a plurality of hydrogen storage capillaries for storing hydrogen, wherein a metal organic framework adsorption material and a covalent organic compound adsorption material are sequentially synthesized in situ in each hydrogen storage capillary; and (3) introducing external compressed hydrogen from one end of the capillary tube bundle, and storing the hydrogen in each hydrogen storage capillary tube in the capillary tube bundle.
The method for in-situ synthesis of the metal organic framework adsorption material in the hydrogen storage capillary tube comprises the following steps:
S1-1, dissolving zinc nitrate Zn (NO 3)2 6H2 0 and 4,4' -benzene-1, 3, 5-triacyltritcarboxylic acid in N, N-diethyl formamide to form a first solution;
s1-2, making the first solution enter the hydrogen storage capillary tube through vacuumizing, reacting for two days at 80-85 ℃ to generate micro crystals, and pouring out yellow solution after cooling;
s1-3, washing the crystal with N, N-dimethylformamide for 2-4 times, and then soaking in chloroform for 48-96 hours;
s1-4, placing the soaked crystals into a vacuum oven, and drying at 110-120 ℃ for 6-8 hours to obtain the metal-organic framework adsorption material distributed in the capillary tube.
The method for in-situ synthesis of the covalent organic compound adsorbing material in the hydrogen storage capillary tube comprises the following steps:
s2-1, uniformly mixing a mixed solution of mesitylene and dioxane with tetra (4-boric acid phenyl) methane to form a second solution;
S2-2, making the second solution enter the hydrogen storage capillary tube through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain white precipitate I, and pouring out the residual solution;
s2-3, washing the obtained white precipitate I with anhydrous tetrahydrofuran, and then vacuum drying at room temperature to remove the solvent to obtain the covalent organic compound adsorption material distributed in the capillary;
or the method for in-situ synthesis of the covalent organic compound adsorbing material in the hydrogen storage capillary tube comprises the following steps:
S3-1, uniformly mixing a mixed solution of mesitylene and dioxane with tetra (4-boric acid phenyl) silane to form a second solution;
S3-2, making the second solution enter the hydrogen storage capillary tube through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain white precipitate II, and pouring out the residual solution;
S3-3, washing the obtained white precipitate II with anhydrous tetrahydrofuran, and then drying in vacuum at room temperature to remove the solvent to obtain the covalent organic compound adsorbing material distributed in the capillary.
The mass/volume ratio of zinc nitrate Zn (NO 3)2 6H2 0, 4' -benzene-1, 3, 5-triacyltritcarboxylic acid and N, N-diethyl formamide) in the S1-1 is (17-20 mg) (3.5-4.5 mg) 1mL;
The volume/mass ratio of the trimethylbenzene, the dioxane and the tetra (4-boric acid phenyl) methane in the S2-1 is 1 mL/1 mL (40-60 mg);
The volume/mass ratio of trimethylbenzene, dioxane and tetra (4-boric acid phenyl) silane in the S3-1 is 3 mL/1 mL (50-60 mg).
The high-pressure hydrogen storage bottle comprises a capillary tube bundle for storing hydrogen, a tube plate and an end cover, wherein the capillary tube bundle consists of a plurality of hydrogen storage capillaries, a metal organic framework adsorption material and a covalent organic compound adsorption material are sequentially synthesized in situ in each hydrogen storage capillary, each hydrogen storage capillary in the capillary tube bundle vertically passes through the tube plate, two ends of each hydrogen storage capillary are opened, and the ends of each hydrogen storage capillary are respectively flush with the end face of the tube plate; the end covers are two, namely a first end cover provided with an air inlet and a second end cover provided with an air outlet, the opening end of the first end cover is in sealing connection with the end face of the tube plate at one end of the capillary tube bundle, the opening end of the second end cover is in sealing connection with the end face of the tube plate at the other end of the capillary tube bundle, and two ends of each hydrogen storage capillary tube are respectively communicated with the first end cover and the second end cover.
The tube plate is provided with a plurality of through holes vertically penetrating through the tube plate, and each hydrogen storage capillary tube in the capillary tube bundle correspondingly and respectively penetrates through each through hole.
The tube plates comprise a first tube plate and a second tube plate, the upper end face of the first tube plate corresponds to the first end cover, the lower end face of the second tube plate corresponds to the second end cover, and each hydrogen storage capillary on the capillary tube bundle penetrates through the corresponding through holes in the first tube plate and the second tube plate respectively.
The outer edge of the tube plate is provided with an inner liner layer and an outer shell layer in the length direction of the capillary tube bundle, the inner liner layer coats the tube plate, and the outer shell layer is arranged on the outer side of the inner liner layer and extends to the end covers from two ends or covers the end covers.
The air inlet of the first end cover is integrated with a first adapter for storing external compressed hydrogen into the capillary tube bundle, and the air outlet of the second end cover is integrated with a second adapter for discharging the compressed hydrogen in the capillary tube bundle.
The hydrogen storage capillary is one of a magnesium aluminum silicate glass capillary, a borosilicate glass capillary and a quartz glass capillary.
The cross section of the hydrogen storage capillary tube is one of a circle, a hexagon, a trapezoid, a rectangle, a triangle or an ellipse, the diameter or the cross section width of the hydrogen storage capillary tube is 0.1mm-8mm, and the number, the end face shape and the size of the through holes are matched with those of the hydrogen storage capillary tube; the particle size of the metal organic framework adsorbing material or the covalent organic compound adsorbing material is 1nm-5 mu m.
The tube plate is a solid polymer tube plate; the inner liner layer is a solid polymer layer or one of a polyamide layer, a polyimide layer and a polysulfone layer which have chemical compatibility with a solid polymer material; the end cover is made of gas compatible steel or alloy, and the thickness of the end cover is matched with the design pressure of the stored hydrogen in the gas cylinder.
Preferably, the tube sheet is a modified epoxy resin sheet.
The end cover is fixed on the tube plate through a high-strength adhesive, or the tube plate is in sealing connection with the end cover through complementary threads.
The ratio of the thickness of the tube plate to the diameter or the section width of the tube plate is more than or equal to 1:1.
Preferably, the ratio of the thickness of the tube plate to the diameter or the section width of the tube plate is more than or equal to 2:1.
The technical scheme of the invention has the following advantages:
A. The invention adopts the integrated low-density capillary tube bundle which is internally filled with the metal organic framework adsorption material and the covalent organic compound adsorption material at the same time for hydrogen storage, has high hydrogen storage pressure (up to 150 MPa), strong hydrogen storage capacity (the weight hydrogen storage density is up to 20-25%, and the volume hydrogen storage density is up to 70-80 g/L), has low manufacturing cost, realizes the storage of high-pressure hydrogen in a relatively lighter container, and has higher commercial application value.
B. the high-pressure hydrogen storage cylinder adopts the bidirectional opening, the end covers at the two ends are respectively provided with the one-way valve, one end is used for air inlet, the other end is used for air outlet, and compared with the conventional container with one opening at one end, the high-pressure hydrogen storage cylinder has the advantages of simple operation, avoiding frequent disassembly and assembly of the ports when the single-port gas cylinder is inflated and deflated, and being more convenient to use.
C. The high-pressure hydrogen storage bottle has high safety, and compared with a high-pressure hydrogen storage bottle, the capillary hydrogen storage technology is formed by combining innumerable tiny compression-resistant capillaries together to form a super-strong stable structure. Each tiny capillary acts as a single pressure vessel, and the hydrogen leakage cannot form an explosive environment because the hydrogen storage quantity of the single capillary is very small.
D. the capillary hydrogen storage technology is convenient to connect and rapid in hydrogen charging. The capillary hydrogen storage technology is a modular structure, and the shape, size and capacity of the hydrogen storage cylinder can be designed and installed at will to be coupled to any desired consumer system. For example, the fuel cell can be mounted on a hydrogen fuel cell automobile to supply power to the fuel cell.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are required for the embodiments will be briefly described, and it will be apparent that the drawings in the following description are some embodiments of the present invention and that other drawings may be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a perspective view of the overall structure of a high-pressure hydrogen storage cylinder provided by the invention;
FIG. 2 is a schematic view of the bottle body in FIG. 1;
Fig. 3 is a schematic cross-sectional view of the capillary bundle of fig. 1.
The figures are identified as follows:
1-capillary bundle, 11-hydrogen storage capillary; 2-tube plate, 21-first tube plate, 22-second tube plate, 23-through hole; 3-an inner liner layer; 4-an outer shell layer; 5-end cap, 51-first end cap, 511-first adapter, 52-second end cap, 521-second adapter.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; the mechanical connection and the electrical connection can be adopted; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The invention provides a high-pressure hydrogen storage method, which comprises a plurality of hydrogen storage capillaries for storing hydrogen, wherein a metal organic framework adsorption Material (MOF) and a covalent organic compound adsorption material (COF) are sequentially synthesized in each hydrogen storage capillary in situ; forming a plurality of hydrogen storage capillaries into a capillary bundle; and (3) introducing external compressed hydrogen from one end of the capillary tube bundle, and storing the hydrogen in each hydrogen storage capillary tube in the capillary tube bundle. MOFs are coordination polymers formed by self-assembly of organic ligands with transition metal ions, which have the advantage of hydrogen storage in that compounds of the MOF series have a high specific surface area and pore volume. The COF is a novel porous material developed on the basis of MOF materials, and because the framework of the COF material is composed of light elements (H, B, O, C, si and the like), the crystal density of the COF material is lower, the absorption of hydrogen is facilitated, and hydrogen elements are connected through strong covalent bonds (C-C, C-O, B-O, si-C and the like), a one-dimensional or three-dimensional porous structure can be formed, the porous material has a very high specific surface area, and is suitable for hydrogen storage. According to the structural characteristics of the capillary, MOF and COF are synthesized in situ in the capillary, and the particle size of the MOF and the COF is 1nm-5 mu m, so that the hydrogen storage advantages of the MOF and the COF are combined together, and a better hydrogen storage effect can be achieved.
Further, the method for synthesizing the metal organic framework adsorbing material in situ in the capillary tube comprises the following steps:
S1-1, zinc nitrate Zn (NO 3)2 6H2 0 and 4,4' -benzene-1, 3, 5-triacyltritcarboxylic acid are dissolved in N, N-diethyl formamide, the mass/volume ratio of the three is (17-20 mg) (3.5-4.5 mg) to 1mL, and a first solution is formed;
s1-2, making the first solution enter the hydrogen storage capillary tube through vacuumizing, reacting for two days at 80-85 ℃ to generate micro crystals, and pouring out yellow solution after cooling;
s1-3, washing the crystal with N, N-dimethylformamide for 2-4 times, and then soaking in chloroform for 48-96 hours;
s1-4, placing the soaked crystals into a vacuum oven, and drying at 110-120 ℃ for 6-8 hours to obtain the metal-organic framework adsorption material distributed in the capillary tube.
The method for in-situ synthesis of the covalent organic compound adsorbing material in the capillary tube comprises the following steps:
S2-1, uniformly mixing the mixed solution of mesitylene and dioxane with 1mL (40-60 mg) of tetra (4-boric acid phenyl) methane according to the volume/mass ratio of 1mL to form a second solution;
S2-2, making the second solution enter the hydrogen storage capillary tube through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain white precipitate I, and pouring out the residual solution;
S2-3, washing the obtained white precipitate I with anhydrous tetrahydrofuran, and then drying in vacuum at room temperature to remove the solvent to obtain the covalent organic compound adsorbing material distributed in the capillary.
Or the method for synthesizing the covalent organic compound adsorbing material in situ inside the capillary is as follows:
S3-1, uniformly mixing the mixed solution of mesitylene and dioxane with 3mL of tetra (4-boric acid phenyl) silane in a volume/mass ratio of (50-60 mg) to form a second solution;
S3-2, making the second solution enter the hydrogen storage capillary tube through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain white precipitate II, and pouring out the residual solution;
S3-3, washing the obtained white precipitate II with anhydrous tetrahydrofuran, and then drying in vacuum at room temperature to remove the solvent to obtain the covalent organic compound adsorbing material distributed in the capillary.
As shown in fig. 1-3, the invention provides a high-pressure hydrogen storage bottle, which comprises a capillary tube bundle 1 for storing hydrogen, a tube plate 2 and an end cover 5, wherein the capillary tube bundle 1 consists of a plurality of hydrogen storage capillaries 11, a metal organic framework adsorption material and a covalent organic compound adsorption material are sequentially synthesized in situ in each hydrogen storage capillary 11, a plurality of through holes 23 vertically penetrating through the tube plate 2 are formed in the tube plate 2, each hydrogen storage capillary 11 in the capillary tube bundle 1 correspondingly penetrates through each through hole 23, both ends of each hydrogen storage capillary 11 are opened, and the ends of each hydrogen storage capillary are flush with the end face of the tube plate 2. The two end covers 5 are respectively a first end cover 51 provided with an air inlet 511 and a second end cover 52 provided with an air outlet 521, the opening end of the first end cover 51 is in sealing connection with the end face of the tube plate 2 at one end of the capillary tube bundle 1, the opening end of the second end cover 52 is in sealing connection with the end face of the tube plate 2 at the other end of the capillary tube bundle 1, and two ends of each hydrogen storage capillary tube 11 are respectively communicated with the first end cover 51 and the second end cover 52. The invention adopts the integrated low-density capillary tube bundle which is internally filled with the metal organic framework adsorption material and the covalent organic compound adsorption material at the same time for hydrogen storage, has high hydrogen storage pressure (150 MPa can be reached), strong hydrogen storage capacity (the weight hydrogen storage density is up to 16% -18%, and the volume hydrogen storage density is up to 60g/L-63 g/L), has low manufacturing cost and realizes the storage of high-pressure hydrogen in a relatively lighter container. The invention has high safety, and compared with a high-pressure hydrogen storage tank, the capillary hydrogen storage technology is combined by innumerable tiny compression-resistant capillaries to form a super-strong stable structure. Each tiny capillary acts as a single pressure vessel, and the hydrogen leakage cannot form an explosive environment because the hydrogen storage quantity of the single capillary is very small.
Further, the tube plate 2 comprises a first tube plate 21 and a second tube plate 22, the upper end face of the first tube plate 21 corresponds to the first end cover 51, the lower end face of the second tube plate 22 corresponds to the second end cover 52, and each hydrogen storage capillary 11 on the capillary tube bundle 1 passes through corresponding through holes 23 on the first tube plate 21 and the second tube plate 22 respectively. The outside of the tube plate 2 is provided with an inner liner layer 3 and an outer shell layer 4 along the length direction of the capillary tube bundle 1, the inner liner layer 3 coats the tube plate 2, the outer shell layer 4 is arranged outside the inner liner layer 3 and extends to the end covers 5 from two ends or covers the end covers 5. The high-pressure area of the high-pressure hydrogen storage cylinder comprises the inside of the hydrogen storage capillary tube 11, the surface of the tube plate 2 and the inner surface of the end cover 5 which are at the level position of the two ends of the hydrogen storage capillary tube 11, and does not comprise the inner lining 3 and the outer shell layer 4.
A first adapter 511 for storing external compressed hydrogen into the capillary tube bundle 1 is integrated at the air inlet of the first end cap 51, and a second adapter 521 for discharging the compressed hydrogen in the capillary tube bundle 1 is integrated at the air outlet of the second end cap 52. The high-pressure hydrogen storage cylinder adopts the bidirectional opening, the end covers at the two ends are respectively provided with the one-way conduction adapter, one end is used for air inlet, the other end is used for air outlet, and compared with the conventional container with one opening at one end, the high-pressure hydrogen storage cylinder has simple operation, avoids frequent disassembly and assembly of the ports when the single-port gas cylinder is charged and discharged, and is more convenient to use.
The hydrogen storage capillary 11 may be made of any type of high tensile strength glass known in the art, preferably one of magnesium alumino silicate glass, borosilicate glass, and quartz glass. The cross-sectional shape of the hydrogen storage capillary 11 is one of a circle, a hexagon, a trapezoid, a rectangle, a triangle, or an ellipse, and the number, the end face shape, and the size of the through holes 23 are matched with those of the hydrogen storage capillary 11. For a given storage pressure, and taking into account the safety factor, glass with a higher tensile strength will allow the thickness of the tubesheet 2 to be smaller, while glass with a lower tensile strength will make the tubesheet 2 thicker. Typically the capillary tube has an outer diameter defined in the range of 0.1mm to 8mm and an inner diameter in the range of 0.05mm to 7.8 mm. The length of the hydrogen storage capillary 11 is 100-1500 mm. The end cover 5 is made of gas compatible steel or alloy, and the thickness of the end cover is matched with the design pressure of the stored hydrogen in the gas cylinder.
The number of hydrogen storage capillaries 11 can vary from two to thousands, with the specific number being determined by the size and shape of the cylinder and the volume of gas required to be stored in the cylinder. The capillaries are arranged parallel to each other. Although the capillary portions outside the tube sheet 2 are not covered, they are covered with the inner liner 3 of the same material as that used for the tube sheet 2 to provide a degree of shock absorption. In addition, the inner liner 3 may be made of a material different from the tube sheet 2, such as polyamide, polyimide, polysulfone, etc. that is chemically compatible with the tube sheet 2 material. It should be noted that the tube sheet 2 material fills the space between the hydrogen storage capillaries 11 so as to form an airtight seal between the hydrogen storage capillaries 11. The tube sheet 2 may be formed of a solid polymer such as an emulsion or liquid resin, a modified epoxy resin, or the like.
The final cross-sectional shape of the tube sheet 2 is determined by the shape of the cylinder and/or the shape required of the end cap 5. Thus, if the cylinder has a circular cross-sectional shape, or the portion of the end cap 5 that is connected to the tube sheet 2 has a circular cross-sectional shape, the tube sheet 2 will typically have a corresponding circular cross-sectional shape. If the capillary bundle 1 has a cross-sectional shape different from that of the end cap 5, the peripheral portion of the tube sheet 2 surrounding the bundled capillaries may be molded or machined to form the desired cross-sectional shape to complement the cross-sectional shape of the end cap 5 so that the end cap 5 and tube sheet 2 are assembled together by an airtight seal. The thickness of the tube sheet 2 in the axial direction of the hydrogen storage capillaries 11 may also be different, but the minimum thickness is determined by the mechanical properties of the material forming the tube sheet 2 and the mechanical properties of the hydrogen storage capillaries 11, in combination with the mechanical properties of the tube sheet 2 material and the hydrogen storage capillaries 11 material, as well as the size or diameter of the tube sheet 2 and the desired gas storage pressure. The ratio of the thickness of the tube sheet 2 to its diameter or cross-sectional width is generally 1:1 or more, preferably 2:1 or more.
The peripheral portion of the tube sheet 2 surrounding the capillary tube bundle 1 is connected to the open end of the end cap 5 to form an airtight seal between the tube sheet 2 and the end cap 5. This airtight relationship may be achieved by any method known in the art. Typically, a sealant such as epoxy is used to adhere the open end of the end cap 5 to the surface tube sheet 2 of the end cap 5 or the inner surface of the open end of the end cap 5 to the circumferential surface of the tube sheet 2 around the capillary tube bundle 1. Or the hermetic seal may be achieved by providing complementary threads on the circumferential surface of the tube sheet 2 and the inner surface of the end cap 5, and a gasket or gasket located between the circumferential surface of the tube sheet 2 and the inner surface of the end cap 5. In this way, the end cap 5 can be screwed onto the tube sheet 2.
The outer shell layer 4 does not constitute a part of a high-pressure environment that encloses the gas to be stored, and therefore, the outer shell layer 4 does not need to be made of a high-strength material capable of withstanding high pressure. Typically made of metal, plastic or composite materials. The outer shell layer 4 is optionally provided with a relief valve having a set point pressure lower than the design pressure of the cylinder, the enclosed space between the outer surface of the capillary bundle 1 and the inner surface of the outer shell layer 4 will never be over-pressurized.
The invention is applicable to the prior art where it is not described.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present invention.

Claims (12)

1. A high-pressure hydrogen storage method comprises a plurality of hydrogen storage capillaries for storing hydrogen, and is characterized in that a metal organic framework adsorption material and a covalent organic compound adsorption material are sequentially synthesized in situ in each hydrogen storage capillary; forming a plurality of hydrogen storage capillaries into a capillary bundle; accessing external compressed hydrogen from one end of the capillary tube bundle, and storing the hydrogen in each hydrogen storage capillary tube in the capillary tube bundle;
The method for in-situ synthesis of the covalent organic compound adsorbing material in the hydrogen storage capillary tube comprises the following steps:
S2-1, uniformly mixing a mixed solution of mesitylene and dioxane with tetra (4-boric acid phenyl) methane to form a second solution;
S2-2, enabling the second solution to enter the hydrogen storage capillary through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain white precipitate I, and pouring out the residual solution;
s2-3, washing the obtained white precipitate I with anhydrous tetrahydrofuran, and then vacuum drying at room temperature to remove the solvent to obtain the covalent organic compound adsorption material distributed in the capillary;
Or the method for in-situ synthesis of the covalent organic compound adsorbing material inside the hydrogen storage capillary tube comprises the following steps:
s3-1, uniformly mixing a mixed solution of mesitylene and dioxane with tetra (4-boric acid phenyl) silane to form a second solution;
s3-2, enabling the second solution to enter the hydrogen storage capillary through vacuumizing, reacting for 80-110 hours at 80-85 ℃ to obtain white precipitate II, and pouring out the residual solution;
S3-3, washing the obtained white precipitate II with anhydrous tetrahydrofuran, and then drying in vacuum at room temperature to remove the solvent to obtain the covalent organic compound adsorbing material distributed in the capillary.
2. The method of claim 1, wherein the method for in-situ synthesis of metal-organic framework adsorbent material inside the hydrogen storage capillary tube is as follows:
S1-1, dissolving zinc nitrate Zn (NO 3)2 6H2 0 and 4,4' -benzene-1, 3, 5-triacyltritcarboxylic acid in N, N-diethyl formamide to form a first solution;
S1-2, enabling the first solution to enter the hydrogen storage capillary tube through vacuumizing, reacting for two days at 80-85 ℃ to generate micro crystals, and pouring out yellow solution after cooling;
s1-3, washing the crystal with N, N-dimethylformamide for 2-4 times, and then soaking in chloroform for 48-96 hours;
S1-4, placing the soaked crystals into a vacuum oven, and drying at 110-120 ℃ for 6-8 hours to obtain the metal-organic framework adsorption material distributed in the capillary tube.
3. The high-pressure hydrogen storage method according to claim 2, wherein,
The mass/volume ratio of zinc nitrate Zn (NO 3)2 6H2 0, 4' -benzene-1, 3, 5-triacyltritcarboxylic acid and N, N-diethyl formamide) in the S1-1 is (17-20 mg) (3.5-4.5 mg) 1mL;
The volume/mass ratio of trimethylbenzene, dioxane and tetrakis (4-boric acid phenyl) methane in the S2-1 is 1 mL/1 mL (40-60 mg);
The volume/mass ratio of trimethylbenzene, dioxane and tetra (4-boric acid phenyl) silane in the S3-1 is 3 mL/1 mL (50-60 mg).
4. A high-pressure hydrogen storage bottle, characterized in that the high-pressure hydrogen storage method as claimed in any one of claims 1-3 is adopted, and the method comprises a capillary tube bundle (1) for storing hydrogen, a tube plate (2) and an end cover (5), wherein the capillary tube bundle (1) consists of a plurality of hydrogen storage capillaries (11), a metal organic framework adsorption material and a covalent organic compound adsorption material are sequentially synthesized in situ in each hydrogen storage capillary (11), each hydrogen storage capillary (11) in the capillary tube bundle (1) vertically passes through the tube plate (2), two ends of each hydrogen storage capillary (11) are opened, and the ends of each hydrogen storage capillary are respectively flush with the end face of the tube plate (2); the end covers (5) are two, namely a first end cover (51) provided with an air inlet and a second end cover (52) provided with an air outlet, the opening end of the first end cover (51) is in sealing connection with the end face of the tube plate (2) at one end of the capillary tube bundle (1), the opening end of the second end cover (52) is in sealing connection with the end face of the tube plate (2) at the other end of the capillary tube bundle (1), and the two ends of each hydrogen storage capillary tube (11) are respectively communicated with the first end cover (51) and the second end cover (52).
5. The high-pressure hydrogen storage cylinder according to claim 4, wherein a plurality of through holes (23) vertically penetrating through the tube plate (2) are formed in the tube plate (2), and each hydrogen storage capillary tube (11) in the capillary tube bundle (1) correspondingly penetrates through each through hole (23).
6. The high-pressure hydrogen storage cylinder according to claim 5, wherein the tube plate (2) comprises a first tube plate (21) and a second tube plate (22), the upper end surface of the first tube plate (21) corresponds to the first end cover (51), the lower end surface of the second tube plate (22) corresponds to the second end cover (52), and each hydrogen storage capillary tube (11) on the capillary tube bundle (1) respectively passes through the corresponding through hole (23) on the first tube plate (21) and the second tube plate (22).
7. The high-pressure hydrogen storage cylinder according to claim 4, wherein an inner liner layer (3) and an outer shell layer (4) are arranged outside the tube plate (2) along the length direction of the capillary tube bundle (1), the inner liner layer (3) coats the tube plate (2), and the outer shell layer (4) is arranged outside the inner liner layer (3) and extends to the end cover (5) from two ends or covers the end cover (5).
8. The high-pressure hydrogen storage cylinder according to claim 4, characterized in that a first adapter (511) for storing external compressed hydrogen into the capillary tube bundle (1) is integrated at the gas inlet of the first end cap (51), and a second adapter (521) for discharging compressed hydrogen from the capillary tube bundle (1) is integrated at the gas outlet of the second end cap (52).
9. The high-pressure hydrogen storage cylinder according to claim 4, wherein the hydrogen storage capillary (11) is one of a magnesium aluminum silicate glass capillary, a borosilicate glass capillary, and a quartz glass capillary.
10. The high-pressure hydrogen storage cylinder according to claim 5, wherein the cross-sectional shape of the hydrogen storage capillary tube (11) is one of a circle, a hexagon, a trapezoid, a rectangle, a triangle, or an ellipse, the diameter or the cross-sectional width of which is 0.1mm-8mm, and the number, the end face shape, and the size of the through holes (23) are matched with those of the hydrogen storage capillary tube (11); the particle size of the metal organic framework adsorbing material or the covalent organic compound adsorbing material is 1nm-5 mu m.
11. The high pressure hydrogen storage cylinder according to claim 7, characterized in that the tube sheet (2) is a solid polymer tube sheet; the inner liner layer (3) is a solid polymer layer or one of a polyamide layer, a polyimide layer and a polysulfone layer which are chemically compatible with a solid polymer material; the end cover (5) is made of gas compatible steel or alloy, and the thickness of the end cover is matched with the design pressure of the stored hydrogen in the gas cylinder.
12. The high-pressure hydrogen storage cylinder according to claim 4, characterized in that the end cap (5) is fixed to the tube plate (2) by a high-strength adhesive or the tube plate (2) and the end cap (5) are connected in a sealing manner by complementary threads.
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